Note: Descriptions are shown in the official language in which they were submitted.
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SPECIFICATION
REPAIR AND REINFORCEMENT METHOD FOR PREEXISTING STRUCTURES
AND AN ANISOTROPIC TEXTILE USED THEREFOR
Technical Field
The present invention relates to a repair and
reinforcement method for preexisting structures such as
bridge columns, piers, bridges, and buildings,
and in particular, relates to a repair and reinforcement
method for concrete structures, and to an anisotropic
textile used in this method.
Background Art
The repair and reinforcement of preexisting
structures comprising concrete such as bridge columns,
piers, bridges, and the like by the use of a
unidirectional sheet material, in which carbon fibers,
glass fibers, or high strength organic fibers are arranged
in one direction, these are impregnated in advance with a
small amount of resin, and are restricted in the weft
direction and the thickness direction, or common textile
materials, wherein these are affixed to the structures
while impregnating with resin, and are then left to cure,
is generally known.
In this case, cold-curing type epoxy resins, which
have a long period of use and are comparatively easily
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0
handled, are most broadly employed as the matrix resin
which is impregnated into the sheet material.
Furthermore, repair and reinforcement methods are
also known in which, in order to shorten the work period
at the site and to obtain stable properties, a so-called
prepreg, which has been impregnated in advance with an
appropriate amount of resin, is affixed, and this is then
cured.
However, when the cold-curing epoxy resin which is
commonly employed as a matrix resin in this field is used,
although this is termed a cold-curing resin, the curing
properties decline markedly below 10°C and in particular
below 5°C, and this leads to defects in curing and leads
to a lengthening of the execution period.
On the other hand, there has been much
consideration given to the use of reinforcing materials
(hereinbelow referred to as sheet materials) which form
fiber-reinforced resin with resin. When a textile
material comprising common reinforcement fibers is
employed, the fibers run in two directions, so that the
strength in one direction is less than half, and this is
extremely disadvantageous when strengthening is
particularly to be carried out in one direction, so that
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the use of a variety of unidirectional sheet materials has
been considered.
(1) Use of reinforcement fiber bundles
A technique in which reinforcement fiber bundles
are wrapped around spots to be repaired and reinforced in
preexisting structures while resin is being applied
thereto is disclosed in Japanese Patent Application, First
Publication No. Sho 62-33973 and Japanese Patent
Application, First Publication No. Sho 62-244979.
(2) Use of a so-called prepreg in which resin is
impregnated in advance into reinforcement fibers
A technique in which a sheet material, in which a
net-shaped material is applied to a prepreg, in which
reinforcement fiber bundles are arranged and impregnated
with resin so that the amount of resin contained is 15
weight percent or less, is applied to portions to be
repaired or reinforced of preexisting structures, and
curable resin is applied and impregnated from the surface
thereof, is disclosed in Japanese Patent Application,
- First Publication No. Hei 7=228714.
(3) Use of reinforcement fiber cloth in which resin
is not impregnated in advance into the reinforcement
fibers
A technique in which a screen shaped sheet material
in which carbon fibers are woven horizontally and
vertically is applied to spots to be repaired and
reinforced of preexisting structures, and a curable resin
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is applied and impregnated from the surface thereof, is
disclosed in Japanese Patent Application, First
Publication No. Sho 63-201269.
(4) Use of a material which can be positioned
between that of (2) and (3)
A technique in which a sheet material, in which
arranged reinforcement fiber bundles are applied to a
supporting sheet via an adhesive layer, is applied to
spots to be repaired and reinforced of preexisting
structures. and a curable resin is applied and impregnated
from the surface thereof, is disclosed in Japanese Patent
Application, First Publication No. Hei 3-224901, Japanese
Patent Application, First Publication No. Hei 4-149366,
and Japanese Patent Application, First Publication No. Hei
5-32804.
However, in technique (1) above, in order to
impregnate the reinforcement fiber bundles with resin and
to wrap these around spots to be repaired and reinforced,
it is necessary to use a dedicated.wrapping machine, and
work is required to bring this machine to the site, and it
is also difficult to use such a machine at sites for
repair and reinforcement having a variety of conditions.
Furthermore, the sheet material which is employed
in the technique described in (2) above is a sheet-shaped
material in which, in order to ensure good handling
properties during the carrying out of repairs, slightly
more resin is applied to the reinforcement fibers than in
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the case of the level of a common sizing agents the gaps
between fibers are restricted, and a further net-shaped
body is laid thereon, so that it is difficult to
impregnate resin thereinto at the site in a short period
of time, and it is not easy to use resin having a short
period of use.
Furthermore, in the technique of (3) above, in the
same way as in the case of a common textile material, a
flat support body which is made unitary through the
application of an amount of resin or an adhesive layer is
not used however, because of the severe restriction of
the space between the reinforcement fibers themselves, the
impregnation of resin is not easy, and resin having a
short period of use cannot be employed.
Furthermore, in the technique described in (4)
above, the arranged reinforcement fiber bundles are
attached to a planar support body comprising a non-woven
cloth or a net-shaped textile via adhesive layers, and
this is made unitary, so that it is difficult to
impregnate the resin in a short time at the site, and
resin having a short period of use cannot be employed.
Furthermore, when sheet materials such as those
described in (2) and (4) above are employed, when a resin
having a low viscosity and great dissolving power such as
an acrylic monomer or unsaturated polyester resins is
impregnated. the resin which is to be impregnated is
impregnated while dissolving the resin which was
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previously deposited in order to restrict the fibers, so
that the fiber orientation becomes chaotic during the
execution of the procedure, and it is impossible to obtain
sufficient strength.
The present invention solves the problems described
in the conventional art above; it has as an object thereof
to provide a repair and reinforcement method for
preexisting structures which is capable of execution even
in poor conditions such as low temperature, and which is
capable of exhibiting superior repair and reinforcement
effects in a short period of time, as well as to provide
an anisotropic textile which has superior handling
properties and resin impregnation properties, and which
also generates superior strength when hardened.
DISCLOSURE OF THE INVENTION
The present invention comprises a repair and
reinforcement method for preexisting structures, wherein,
during the repair and reinforcement of preexisting
structures using a fiber-reinforced resin layer in which
resin is impregnated into a sheet material comprising
reinforced fibers and this resin is cured, the resin which
is employed is a reactive mixture having a gelling time at
20°C of 15 minutes or more and which initiates
polymerization even at 5°C, and is curable
in a period of time of 6
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hours less even at 5°C, and which has as the chief
components thereof (1) a monomer having vinyl groups and
(2) a reactive oligomer and/or a thermoplastic polymer
having vinyl groups; and an anisotropic textile, having as
the warp thereof a high strength and highly elastic fiber
having a tensile strength of 3 GPa or more and a tensile
elastic modulus of 150 GPa or more, and a fiber having a
tensile elastic modulus lower than that of the warp as the
weft thereof, wherein the weft comprises a compound thread
having a weight of 0.1 g or less per one meter of fiber
and comprising two types of fibers, the difference in the
melting point of which is 50°C or more, the gap in. the
weft in the direction of the warp is within a range of 3 -
15 mm, and the warp and weft are caused to adhere to one
another by means of the fiber having a low melting point
comprising the weft.
The anisotropic textile of the present invention
has superior handling properties and resin impregnation
properties, and generates superior strength when cured,
and is thus useful in the repair and reinforcement of
preexisting structures.
Furthermore the repair and reinforcement method for
preexisting structures of the present invention which
employs this anisotropic textile and specified resins even
in a sheet-form material comprising reinforcement fibers
may be carried out in poor conditions such as low
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temperatures, and is capable of exhibiting superior repair
and reinforcement effects in a short period of time.
BEST MODE FOR CARRYING OUT THE INVENTION
First, the repair and reinforcement method for
preexisting structures of the present invention will be
explained.
In the repair and reinforcement method for
preexisting structures in accordance with the present
invention, during the repair and reinforcement of
preexisting structures using a fiber-reinforced resin
layer in which resin is impregnated into a sheet material
comprising reinforcement fibers and cured, the resin which
is employed is a reactive mixture (matrix resin) which has
a gelling time at 20°C of 15 minutes or more and which
initiates polymerization even at 5°C, and is capable of
sufficient curing in a comparatively short period of time
(within 6 hours) even at 5°C, and which, moreover, has as
the chief components thereof (1) a monomer having vinyl
groups and (2) a reactive oligomer and/or a thermoplastic
polymer having vinyl groups, and this is affixed to the
preexisting structure while impregnating the sheet
material comprising reinforcement fibers with this resin,
and this is allowed to stand and cure.
Examples of high strength or highly elastic fibers
which may be employed as the strengthening fibers used in
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the sheet material comprising reinforcement fibers
include, for example, inorganic fibers such as carbon
fibers, glass fibers, and the like, or organic fibers such
as aramid fibers or the like, which are commonly employed
as reinforcement fibers. Furthermore, if these
reinforcement fibers are mixed it presents no problem.
Among these, high strength and highly elastic
fibers having a tensile strength of 3 GPa or more and a
tensile elastic modulus of 150 GPa or more are
particularly preferable for use as the warp of the
anisotropic textile described above, and high strength
carbon fibers having a tensile strength of 4 GPa or more
are preferable. Examples of the sheet material comprising
reinforcement fibers used in the present invention
include, for example, woven cloth, unidirectionally
oriented sheets, non-woven cloth, mats and the like
comprising such reinforcement fibers, combinations of
these, and such sheet materials comprising the
reinforcement fibers into which the acrylic system resin
described hereinbelow has been impregnated; anisotropic
textiles are preferably employed.
In particular, in the present invention, a material
(a) in which fibers are disposed so as to cross a sheet
material in which reinforcement fibers are arranged in one
direction is preferable for use as the sheet material
comprising reinforcement fibers in which the reinforcement
fibers are oriented in one direction and restricted in the
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horizontal direction; a material (b) in which heat-fusible
fibers are disposed, with gaps Within a range of 3 - 15 mm
along the longitudinal direction of the reinforcement
fibers, in a direction perpendicular to that of the
reinforcement fibers in at least one surface of a sheet
material in which reinforcement fibers are arranged in one
direction, and these are heat-fused, is preferable for use
as the sheet material comprising reinforcement fibers; and
a material (c) in which a heat-fusible fiber cloth
comprising thermoplastic resin, or comprising a web-shaped
support body or net-shaped support body covered with
thermoplastic resin, is heat-fused to at least one surface
of a sheet material arranged in one direction, is
preferable for use as the sheet material comprising
reinforcement fibers.
Here, material (a) disclosed above is produced by
disposing reinforcement fibers as the warp, and
reinforcement fibers or other fibers, such as polyamide
fibers, acrylic fibers, or fibers resulting from placing
acrylic system resins or methacrylic system resins in a
fiber shape, as the weft: in other words, from weaving or
twining these.
Furthermore, material tb) is produced by arranging
reinforcement fibers in a single direction as a sheet,
disposing heat-fusible fibers along the width direction of
the reinforcement fibers, and heat-fusing these. What is
meant by the heat-fusible fibers employed here are fibers
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which melt and exhibit adhesive properties at temperatures
above room temperature, or fibers which are coated on the
surfaces thereof with substances which exhibit heat-fusing
properties, or threads resulting from an intertwining of
heat-fusible fibers and non-heat-fusible fibers, or a
combination of any of these fibers. Examples thereof
include fibers of polyethylene, polypropylene, polyamide,
or acrylic or methacrylic system resins, as well as fibers
resulting from a lightly heat-fusible finishing on such
fibers, and fibers in which a substance which is heat-
fusible such as polyamide or the like is deposited on the
surface of fibers such as glass fibers or the like, or
fibers resulting from an intertwining of fibers such as
glass fibers and nylon threads: however, these fibers are
not necessarily limited to these examples. What is meant
by the arrangement of the fibers in this case may be the
simple placement of the fibers in the surface, or the
weaving or intertwining of strengthening fibers as the
warp and heat-fusible fibers as the weft.
After the heat-fusible fibers are arranged, it is
possible to obtain material (b) by heating these, and
causing a fusion with the reinforcement fibers.
Among these, the anisotropic textile described
above employing a sheet material comprising reinforcement
fibers is more preferably employed.
Additionally, material (c) above may be produced by
heat-fusing a heat-fusible fiber cloth comprising a
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thermoplastic resin exhibiting melting and adhesive
properties at temperatures above room temperature, or
comprising a web-shaped support or net-shaped support body
covered with thermoplastic resin, to at least one surface
of a sheet-form material in which reinforcement fibers are
arranged in one direction,.
Examples of the heat-fusible fibers include fibers
comprising polypropylene, polyamide, acrylic resin,
methacrylic resin, or the likes and the net aperture~of
the net-shaped support body is preferably wider from the
point of view of the impregnation of the resin, so that it
is preferable that one polygonal side of the aperture
portion be 1 mm or greater, and the surface area of the
aperture should be 10 mm2 or more. It is more preferable
if one side has a length of 2.5 mm or more, while the
aperture surface area is 15 mm2 or more. On the other
hand, from the point of view of preventing the loosening
of the reinforcement fibers and the handling properties
during cutting, it is preferable that the aperture be
small, so that it is preferable that one side have a
length of 20 mm or less and the aperture surface area be
500 mmz or less .
What is meant by a web-shaped support body is a
sheet material resulting from an intertwining of short
fibers or long fibers.
From the point of view of maintenance of interlayer
shear strength and resin permeability among the mechanical
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properties of the substance obtained, it is preferable
that the net- or web-shaped support body have a weight of
20 g/m' or less.
With respect to the materials employed in the
fibers used for restricting the reinforcement fibers or
the fusible fiber cloth or the like, the use of materials
having good adhesive properties with the resin which is
impregnated is preferable, so that after curing, superior
strength and reinforcement effects can be generated.
When carbon fibers are employed as the
reinforcement fibers, optimal carbon fibers for use in the
sheet material should preferably be within a range of 100
- 800 g/m2, and more preferably within a range of 150 -
600 g/m2.
When the weight is less than 100 g/m2, although the
impregnation of the resin is satisfactory, the handling
properties of the sheet material worsen, and in
particular, the trend is towards the generation of slits
in the carbon fibers bundles, and the number of layers
affixed increases, so that the operation becomes complex.
When this is in excess of 800 g/m2, the impregnation of
the resin worsens, and this is not desirable.
An explanation will now be given of the reason for
the use of a reactive mixture as the resin in the present
invention.
The resin which is employed in the present
invention exhibits sufficient repair and reinforcement
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effects in a comparatively short period of time without
requiring control of the conditions; it is important that
this resin be capable of initiating polymerization even at
5°C, and that curing proceed to a level which exhibits
sufficient strength in a comparatively short period of
time. One benchmark for the time during which curing
proceeds to a level exhibiting sufficient strength is a
period of 24 hours; however, a period of 6 hours or less
is preferable in order to effectively conduct the
procedure, and a period of 3 hours or less is even more
preferable. On the other hand, from the point of view of
feasibility of the process of impregnating resin into the
sheet material from the reinforcement fibers, it is
necessary that the resin employed have a period of use at
room temperature of 10 minutes or more, and preferably 15
minutes or more, and accordingly, a reactive mixture in
which a curing reaction proceeds rapidly after the
initiation of polymerization, and which is cured with a
radical chain reaction, is preferable. The most
preferable reactive mixture is a reactive mixture having
as chief components thereof the components described
hereinbelow, which has a period of use of 30 minutes or
more at room temperature, and in which curing progresses
to a level at which a sufficient strength is exhibited
within a period of 3 hours.
Examples of component (1), a monomer having vinyl
groups, include (meth)acrylate, (meth)acrylic acid,
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styrene, vinyl toluene, vinyl acetate, and the like. From
the point of view of reactivity and the weather resistance
of the resin after curing, the inclusion of (meth)acrylate
as a chief component is preferable. What is indicated
here by '(meth)acrylate' is acrylate and/or methacrylate.
Concrete examples thereof include: (meth)acrylate
monomers having one functional group such as methyl
(meth)acrylate, ethyl (meth)acrylate, propyl
(meth)acrylate, n-butyl (meth)acrylate, t-butyl
(meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl
(meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl
(meth)acrylate, dicyclopentenyl (meth)acrylate, 2-
dicyclopentenoxyethyl (meth)acrylate, isobornyl
(meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl
(meth)acrylate; butoxyethyl (meth)acrylate,
methoxyethoxyethyl (meth)acrylate, ethoxyethoxyethyl
(meth)acrylate, tetrohydrofurfuryl (meth)acrylate, 2-
hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, 4-hydroxybutyl (meth)acrylate,
(meth)acrylic acid, (meth)acryloyl morpholine and the
like; (meth)acrylate monomers with two functional groups
such as ethylene glycol ditmeth)acrylate, 1,2-propylene
glycol di(meth)acrylate, 1,4-heptanediol di(meth)acrylate,
1,6-hexanediol (meth)acrylate, diethylene glycol
di(meth)acrylate, neopentylglycol di(meth)acrylate,
tetraethylene glycol di(meth)acrylate, 2-buten-1,4-
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di(meth)acrylate, cyclohexane-1,4-dimethanol
(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate,
1,5-pentane di(meth)acrylate, trimethylolethane
di(meth)acrylate, tricyclodecane dimethanol
di(meth)acrylate, trimethylolpropane di(meth)acrylate,
dipropylene glycol di(meth)acrylate, 1,3-butylene glycol
di(meth)acrylate, 2,2-bis-(4-
(meth)acryloxypropoxyphenyl)propane, 2,2-bis-(4-
(meth)acryloxy(2-hydroxypropoxy)phenyl)propane, bis-(2-
(meth)acryloyloxyethyl)phthalate, and the like; and
(meth)acrylate monomers having three or more functional
groups such as trimethylolpropane tri(meth)acrylate,
trimethylolpropane ethylene glycol addition product of
tri(meth)acrylate, ditrimethylolpropane
tetra(meth)acrylate, trisacryloylethyl isocyanurate, and
the like.
Among these, particularly preferable concrete
examples are those which have good curing properties and
low viscosity. including methyl (meth)acrylate. ethyl
(meth)acrylate, propyl (meth)acrylate, n-butyl
(meth)acrylate, t-butyl (meth)acrylafie, isobutyl_
(meth)acrylate, 2-ethylhexyl (meth)acrylate, ethylene
glycol di(meth)acrylate, diethylene glycol
di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate,
and tetrahydrofurfuryl (meth)acrylate.
These monomers having vinyl groups may be used
singly, or two or more may be used concomitantly.
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Examples of component (2), the reactive oligomer
having vinyl groups, include, in addition to the so-called
macromonomers which result from the addition of a
(meth)acrylic group to the end of a comparatively low
molecular weight (meth)acrylate copolymer, styrene
copolymer, or styrene - acrylonitrile copolymer; polyester
(meth)acrylate, which is obtained by reacting a polybasic
acid such as phthalic acid, adipic acid or the like with a
polyhydric alcohol such as ethylene glycol, butanediol or
the like, and (meth)acrylic acid: polyester (meth)acrylate
containing allyl ether groups, which is obtained by the
reaction of a polybasic acid such as phthalic acid, adipic
acid or the like with a polyhydric alcohol such as
ethylene glycol, butanediol or the like, and an alcohol
containing allyl ether groups such as pentaerythritol
triallyl ether, trimethylolpropane diallyl ether or the
like, and (meth)acrylic acid: polyester containing allyl
ether groups, which was obtained by reacting a polybasic
acid such as phthalic acid, adipic acid or the like with a
polyhydric alcohol such as ethylene glycol, butanediol or
the like, and an alcohol containing allyl ether groups
such as pentaerythritol triallyl ether, trimethylolpropane
diallyl ether or the like; epoxy (meth)acrylate obtained
by reacting an epoxy resin with (meth)acrylic acid; epoxy
(meth)acrylate containing allyl ether groups, obtained by
reacting a polybasic acid such as phthalic acid, adipic
acid or the like with an epoxy resin and an alcohol
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containing allyl ether groups, such as pentaerythritol
triallyl ether, trimethylolpropane diallyl ether and the
like; urethane (meth)acrylate, which is obtained by
reacting polyol, polyisocyanate and a monomer contain
hydroxyl groups such as 2-hydroxyethyl (meth)acrylate or
the like; urethane (meth)acrylate containing allyl ether
groups, obtained by reacting polyol, polyisocyanate and an
alcohol containing allyl ether groups such as
pentaerythritol triallyl ether, trimethylolpropane diallyl
ether or the like, and a monomer containing hydroxyl
groups such 2-hydroxyethyl (meth)acrylate or the like; and
urethane containing allyl ether groups, obtained by
reacting polyol, polyisocyanate and an alcohol containing
allyl ether groups such as pentaerythritol triallyl ether,
trimethylolpropane diallyl ether or the like.
Preferable among these reactive oligomers are
polyester (meth)acrylate containing allyl ether groups,
obtained by reacting a polybasic acid, a polyhydric
alcohol, an alcohol containing allyl ether groups and
(meth)acrylic acid: epoxy (meth)acrylate, obtained by
reacting an epoxy resin with (meth)acrylic acid, and epoxy
(meth)acrylate containing allyl ether groups, obtained by
reacting a polybasic acid, an epoxy resin, an alcohol
containing allyl ether groups and (meth)acrylic acid; more
preferable is such a reactive oligomer in solution in
component (1). and particularly preferable is a reactive
oligomer obtained using phthalic acid as the polybasic
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acid, bisphenol A and/or bisphenol F type epoxy resin
having an epoxy equivalent of 970 or less as the epoxy
resin, and pentaerythritol triallyl ether as the alcohol
containing allyl ether groups. The epoxy equivalent
weight of the epoxy resin employed is set to this level
because at greater amounts the solubility in component (1)
is reduced, and it thus becomes difficult to prepare a
uniform resin and to apply and impregnate this resin
uniformly into the sheet material comprising reinforcement
fibers.
Further examples of component (2), the
thermoplastic polymer, include, in addition to polymers or
copolymers of (meth)acrylate monomers having one
functional group, such as methyl (meth)acrylate, ethyl
(meth)acrylate, propyl (meth)acrylate, n-butyl
(meth)acrylate, t-butyl (meth)acrylate, isobutyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl
(meth)acrylate. cyclohexyl (meth)acrylate, benzyl
(meth)acrylate, dicyclopentanyl (meth)acrylate,
dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl
(meth)acrylate, isobornyl (meth)acrylate, methoxyethyl
(meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl
(meth)acrylate, methoxyethoxyethyl (meth)acrylate,
ethoxyethoxyethyl (meth)acrylate, tetrohydrofurfuryl
(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-
hydroxypropyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate. (meth)acrylic acid, and (meth)acryloyl
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morpholine and the like, copolymers of (meth)acrylate
monomers and monomers which are copolymerizable with
(meth)acrylate monomers such as styrene, polymers of
monomers which are copolymerizable with (meth)acrylate
monomers, cellulose system macromolecules such as
cellulose acetate butyrate, cellulose acetate propionate,
and the like, diallyl phthalate resin, epoxy resin, vinyl
resins such as vinyl chloride and vinyl acetate resin and
the like,~and various thermoplastic elastomers; these
thermoplastic polymers may be used singly or together.
These are preferably employed in solution in component
(1), as in the case of the reactive oligomers described
above.
Furthermore, in order to improve various
properties, it is possible to add a variety of additives,
for example, plasticizers, weathering agents, anti-static
agents, lubricants, release agents, paints, pigments,
anti-foaming agents, polymerization inhibitors, and
various types of fillers. In particular, in order to
improve air blast effects, and provide gloss to the cured
surface, and in order to increase dirt resistance, the
addition of paraffins such as paraffin wax,
microcrystalline wax, polyethylene wax, and the like, or
addition of higher fatty acids such as stearic acid, 1,2-
hydroxystearic acid, and the like, is preferable.
No particular restriction is made with respect to
the curing catalyst which is used for the polymerization
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of such reactive mixtures, insofar as this comprises a
curing catalyst system which meets the curing conditions,
such as the period of use, the polymerization initiation
temperature, and the curing period; catalyst systems which
are commonly employed as curing catalysts for radical
polymerization at room temperature may be used.
Concrete examples thereof include combinations of
organic peroxides which are individually stable at room
temperature (the temperature at the place of use) such as
benzoyl peroxide, methylethylketone peroxide, and the
like, and curing promoters which make possible the
decomposition of such organic peroxides at room
temperatures.
In order to avoid the dangers presented by the
handling of benzoyl peroxide, it is preferable that this
be used in the form of a paste or a powder in which the
concentration is diluted to approximately 50$ using an
inert liquid or solid.
Examples of curing promoters include metallic soaps
such as cobalt naphthenate, cobalt octylate~ and the like
as well as aromatic tertiary amines such as dimethyl
toluidine, diethyl toluidine, diisopropyl toluidine,
dihydroxyethyl toluidine, dimethylaniline, diethyl
aniline, diisopropyl aniline, dihydroxyethyl aniline and
the like. The curing promoters may be used singly, or two
or more may be used concomitantly, however the curing
promoters are not limited to these examples.
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It is preferable, from the point of view of the
coating properties of the resin, the impregnation
properties of the resin into a sheet material comprising
reinforcement fibers, and the penetration into the
concrete structure, that the viscosity of the reactive
mixture be within a range of 5 - 104 centipoise at 20°C,
and more preferably within a range of 5 - 800 centipoise.
In the repair and reinforcement method of the
present invention, the execution of foundation treatment
on the surface of the preexisting structure on which
execution is to be conducted, prior to carrying out the
repair and reinforcement, is highly desirable in order to
obtain sufficient repair and reinforcement effects. This
foundation treatment may be conducted by means of a method
in which initially, where coating or the like has been
carried out on the surface of the structure, this is
removed, and the surface is rendered smooth, whereupon
cracked portions are filled in with a material having good
adhesion properties with the reactive mixture which is
-' employed in the present invention, and where necessary,
this is subjected to further abrasion, and the surface is
rendered smooth. E~rthermore, the application of the
reactive mixture employed in the present invention on to
the surface on which repair and reinforcement is to be
carried out, prior to carrying out the repair and
reinforcement method of the present invention, is
preferable in order to improve the adhesion properties.
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Representative embodied configurations of the
repair and reinforcement method of the present invention
are given below.
(Embodied Configuration 1)
A reactive mixture in which an organic peroxide and
a curing promoter are uniformly mixed is first applied to
those portions on which repair and reinforcement is to be
carried out, and after a sheet material comprising
reinforcement fibers, and preferably an anisotropic
textile, has been applied to the surfaces to which the
reactive mixture was applied; the same reactive mixture is
impregnated from the opposite side, and allowed to cure.
(Embodied Configuration 2)
A repair and reinforcement method for preexisting
structures, in which a reactive mixture (liquid A)
containing an organic peroxide but not containing a curing
promoter is mixed with a reactive mixture (liquid B)
containing a curing promoter but not containing an organic
peroxide, using a two-liquid mixing-type coater provided
with a cleaning pump, the mixed resin liquid is applied to
those portions of the preexisting structure which are to
be repaired and reinforced, a sheet material comprising
strengthening fibers, and preferably an anisotropic
textile, is applied to the surfaces to which the resin
liquid was applied, liquid A and liquid B are again mixed
using the two-liquid mixing-type coater, and the mixed
resin liquid is applied to the outer surface of the sheet
CA 02399416 2002-09-05
24
material comprising reinforcement fibers which was affixed
and this resin is then allowed to cure.
(Embodied Configuration 3)
A reactive mixture (liquid A) containing an organic
peroxide but not containing a curing promoter is first
applied to those portions of the preexisting structure
which are to be repaired and reinforced, and then a sheet
material comprising reinforcement fibers, and preferably
an anisotropic textile, is affixed thereto, whereupon a
reactive mixture (liquid B) containing a curing promoter
but not containing an organic peroxide is impregnated, and
by means of the contact and mixture of liquid A and liquid
B, curing is carried out.
Alternatively, liquid B may first be applied to
those portions of the preexisting structure which are to
be repaired and reinforced, a sheet material comprising
reinforcement fibers, and preferably an anisotropic
v textile, is then affixed, whereupon liquid A is
impregnated, and as a result of the contact and mixture of
liquid A and liquid B, curing is carried out. The
adoption of such a method is particularly desirable when a
sufficient reactive mixture period of use is to be
guaranteed. Liquid A and liquid B may of course be used
in reverse order.
(Embodied Configuration 4)
A compound comprising the curing promoter of the
reactive mixture may be deposited in advance on the sheet
CA 02399416 2002-09-05
material comprising reinforcement fibers, and preferably
on an anisotropic textile, and during execution, a
reactive mixture which contains an organic peroxide but
does not contain a curing promoter may be impregnated,
initiating polymerization, and this may then be allowed to
cure.
Alternatively, an organic peroxide may be applied
in advance to the sheet material comprising reinforcement
fibers, preferably an anisotropic textile, and during
execution, this may be impregnated with a reactive mixture
which contains a curing promoter but does not contain an
organic peroxide, initiating polymerization, and thus
carrying out curing.
(Embodied Configuration 5)
A reactive mixture (liquid A) which contains an
organic peroxide but does not contain a curing promoter is
first applied to those portions of the preexisting
structure which are to be repaired and reinforced, and
then a sheet material comprising reinforcement fibers,
preferably an anisotropic textile, is affixed, and
thereafter a reactive mixture (liquid B) which contains a
curing promoter but does not contain an organic peroxide
is impregnated, and on this, liquid A is again
impregnated, and as a result of the contact and mixture of
liquid A and liquid B, curing is carried out.
Alternatively, liquid B may first be applied to
those portions of the preexisting structure which are to
CA 02399416 2002-09-05
2b
repaired and reinforced, a sheet material comprising
reinforcement fibers, preferably an anisotropic textile,
is affixed, and thereafter liquid A is impregnated,
whereupon liquid B is impregnated, and as a result of the
contact and mixture between liquid A and liquid B, curing
is carried out. The adoption of this method is
particularly desirable in cases in which a sufficient
period of use is to be guaranteed for the reactive
mixture, and in which a cured state which is more complete
than a state in which there are few curing deficiency
spots is desired.
In the repair and reinforcement method in
accordance with the present invention, no particular
restriction is made with respect to the method by which
reactive mixtures are applied to the portions of the
preexisting structures which are to be repaired and
reinforced, or to the sheet material comprising
reinforcement fibers: however, it is preferable that this
be carried out in a short period of time by using a common
spray gun, a two-liquid internal-mixing-type spray gun
containing a static mixer, or a two-liquid external-
mixing-type spray gun.
Next, the anisotropic textile will be explained:
this is preferably employed as the sheet material
comprising reinforcement fibers of the method for repair
and reinforcement of preexisting structures described
CA 02399416 2002-09-05
27
above, and is also preferably employed in conventional
repair and reinforcement methods.
in order to effectively conduct the repair and
reinforcement of preexisting structures, the use of a
sheet material in which the high strength and highly
elastic fibers employed are arranged in a single direction
is important; however, a sheet material resulting solely
from such arrangement cannot be handled, and is incapable
of use as the material for repair and reinforcement. The
so-called prepreg method, in which resin is impregnated in
advance, is the most common method used to guarantee
sufficient handling properties for use as a repair and
reinforcement materials however, because the resin which
cures at ordinary temperatures which is employed in such
repair and reinforcement methods cures if it is not used
immediately after impregnation, such resin is
inappropriate for use as the matrix resin used in
prepregs, and the common matrix resin for use in prepregs
must be heated to a high temperature of over 100°C in
order to be cured, so that such resin is also
inappropriate for use in the repair and reinforcement
method for preexisting structures. For this reason, a
method is commonly employed in which the amount of resin
impregnated in advance is set to the lower limit necessary
to guarantee the handling properties, and moreover, a
curing agent is not contained so as to guarantee the
period of use, and during execution, curing is conducted
CA 02399416 2002-09-05
28
using a room-temperature-curing agent contained within a
relatively large amount of resin which is additionally
impregnated; however, the resin which is impregnated
during execution is restricted to the same type of resin
as that which was applied in advance, and it is necessary
to apply a slightly greater amount than the standard
amount of sizing agent in order to guarantee the handling
properties during execution, so that the impregnation
properties of the resin which is impregnated during
execution decline dramatically. Furthermore, in order to
improve the handling properties during execution, it is
common to attach a planar support body such a non-woven
cloth or a net type textile or the like via a resin
applied to the reinforcement fibers, or an adhesive layer
which is specially provided between a planar support body
and the reinforcement fibers; however, although the
handling properties improve, the impregnation properties
of the resin during execution decline even more.
The anisotropic textile of the present invention
does not involve the application of resin to the high
strength and highly elastic fibers which are arranged in a
single direction, so that there are no restrictions on the
type of resin which may be impregnated during execution,
and the impregnation properties are very good. In
particular, resin which polymerizes and cures rapidly even
at low temperatures may be employed as the matrix resin,
so that there is no limitation of the environmental
CA 02399416 2002-09-05
29
conditions during execution, and it is possible achieve a
great shortening of the execution time. Furthermore,
since this textile employs composite threads for the weft
which have a lower tensile elastic modulus than that of
the warp, and after weaving, the textile is heated to a
temperature above the melting point of the low melting
point fibers forming the composite threads and the weft
and warp are appropriately adhered, the handling
properties during execution are extremely good, and
problems such as a disarrangement of the orientation of
the fibers during execution, and a decrease in the
reinforcement effect, do not occur.
In the present invention, it is possible to employ
fibers which are commonly employed as reinforcement fibers
as the fibers used in the warp, so that inorganic fibers
such as carbon fibers or the like, and organic fibers such
as aramide fibers or the like, may be employed: however,
-: high strength and highly elastic fibers having a tensile
strength of 3 GPa or more and a tensile elastic modulus of
150 GPa or more are preferable. High strength carbon
fibers having a tensile strength of 4 GPa or more are
particularly preferable as they provide superior
reinforcement effects.
In the present invention, a composite thread
comprising two types of fibers having a melting point
difference of SO°C or more is used as the weft. The fiber
with the high melting point in the composite thread is the
CA 02399416 2002-09-05
basic weft; this functions as the weft at least until the
end of execution. Accordingly, a certain amount of
strength and elastic modulus is required; however, the
tensile elastic modulus must be less than that of the
warp. When the tensile elastic modulus is greater than
that of the warp, the warp tends to drift in the
longitudinal direction, and sufficient tensile strength is
not attained. The preferred tensile elastic modulus range
of the weft is 50 - 100 GPa. Furthermore, in order to
prevent a disordering of the orientation of the fibers
during execution, it is very important that this does not
dissolve in the resin which forms the matrix resin.
Examples of such high melting point fibers include glass
fibers; however, these fibers are not necessarily limited
to this example.
The low melting point fibers are fibers which are
necessary in order to cause the warp and weft to become
unitary after weaving and in order to provide superior
handling properties. Without these low melting point
fibers, a disordering of the fibers during handling is
likely to occur, and sufficient reinforcement effects
cannot be obtained. Examples of these low melting point
fibers include low melting point polyamide fibers, -
polyester fibers, and polyolefin fibers; however, these
fibers are not necessarily restricted to these examples.
The two types of fibers described above are
necessary components of the composite threads which are
CA 02399416 2002-09-05
31
employed in the weft; however, in order to improve the
handling properties during execution by unifying these two
types of fibers and strengthening the adhesion between the
warp and weft prior to the impregnation of resin, it is
preferable to use composite threads to which have been
applied 0.5 - 10 weight percent of a high molecular
compound which melts or softens at a temperature of 100°C
or less. The high molecular compound which is deposited
is not particularly restricted insofar as it is a compound
which melts or softens at a temperature of 150°C or less;
however, compounds which are water-soluble or are capable
of forming an aqueous emulsion are preferable, since they
facilitate the process of deposition onto the composite
threads. Examples of such high molecular compounds
include polyvinyl acetate, ethylene- vinyl acetate
copolymer, vinyl acetate- acrylic copolymer, polyacrylic
ester, polyester, polyethylene, and polybutadiene system
copolymers; however, these compounds are not necessarily
limited to the examples given.
The low melting point fibers used in the weft of
the present invention and the high molecular compound
which melts or softens at temperatures of 150°C or less
contribute to the superior handling properties of the
anisotropic textiles; however, from the point of view of
the mechanical properties after curing, particularly the
generation of tensile strength, it is desirable that the
restriction of the warp by the weft be weak. Accordingly,
CA 02399416 2002-09-05
32
it is desirable to choose low melting point fibers and a
high molecular compound which gradually change to a non-
adhesive state as a result of the reactive mixture
impregnated during execution, and to control the amount of
high molecular compound deposited. In particular, it is
preferable that the high molecular compound be somewhat
soluble in the reactive mixture which is impregnated
during execution, and it is desirable that this compound
be selected in concert with the reactive mixture which is
impregnated.
E~rthermore, from the point of view of providing
strength after curing, it is desirable that the weft be as
thin as possible, so that the weight per meter of the
fiber is preferably 0.1 g or less, and more preferably
within a range of 0.01 - 0.05 g.
. The preferable ratio of the high melting point
fibers and the low melting point fibers in the composite
threads is such that, in volumetric ratio, with respect to
one unit of high melting point fibers, the low melting
point fibers should be within a range of 0.25 - 2.0, and a
range of 0.5 - 1_5 is more preferable from the point
of view of the adhesive properties and the mechanical
properties.
The weft spacing in theAanisotropic textile of the '
present invention is within a range of 3 - 15 mm. When
the spacing is less than 3 mm, the drift of the warp in
the longitudinal direction cannot be ignored, and
CA 02399416 2002-09-05
33
sufficient tensile strength will not be attained after
curing of impregnation resin, while when the spacing is
greater than 15 mm, the handling properties of the sheet
material worsen, and this is not desirable. A more
preferable weft spacing range is 4 - 10 mm.
Any resin may be employed as the resin which is
used in combination with the anisotropic textile insofar
as it obtains sufficient repair and reinforcement effects,
is easily impregnated into the anisotropic textile at room
temperatures, and exhibits sufficient strength after
curing; however, in order to produce sufficient repair and
reinforcement effects in a comparatively short period of
time without controlling the environmental conditions, it
is necessary to employ a resin which initiates
polymerization even at 5°C, and in which curing proceeds
to a level which exhibits sufficient strength in a
comparatively short period of time. It is possible to use
24 hours as a period during which curing proceeds to a
level which is exhibits sufficient strength; however, a
period of 6 hours or less is preferable in order to
efficiently conduct operations, and a period of 3 hours or
less is even more preferable. On the other hand, from the
point of view of facilitating the operation in which the
resin is impregnated into the anisotropic textile, it is '
necessary that the resin which is employed have a period
of use which is 10 minutes or greater, and preferably 15
minutes or greater, at room temperatures, and accordingly,
CA 02399416 2002-09-05
34
the reactive mixtures described above, in which the curing
reaction proceeds rapidly after the initiation of
polymerization, and curing is conducted with a radical
chain reaction are preferable. The most preferable
reactive mixture is one which has a period of use of 30
minutes or more at room temperature and in which curing
proceeds to a level which exhibits sufficient strength
within a period of 3 hours.
Embodiments
Hereinbelow, the present invention will be
discussed in greater detail using embodiments. In these
embodiments, 'parts' refers to 'parts per weight'.
(Embodiment 1)
Glass fibers (having a tensile elastic modulus of
72.5 GPa, a melting point of 840°C, and a specific gravity
of 2.54 g/cmj) having a TEX number of 22.5 (0.0225 g/m)
were twisted together with low melting point polyamide
multifilaments (having a melting point of 125°C and a
specific gravity of 1.08 g/cm;) having a total denier of
70 deniers, and an ethylene vinyl acetate copolymer
(having a melting point of 80°C) was deposited thereon in
an amount of 1.5g per 1000m of the twisted thread: and a
composite thread, which served as the weft, was'obtained.
The weight per meter of this composite thread was
approximately 0.03 g, and the ratio of the high melting
CA 02399416 2002-09-05
JS
point fibers and the low melting point fibers was 1:0.8 in
volumetric ratio.
Pyrofil TR30G carbon fibers (having a tensile
strength of 4.5 GPa, a tensile elastic modulus of 235 GPa,
and a filament count of 12000) produced by Mitsubishi
Rayon Co. Ltd. were arranged so as to reach 300 g/m2, and
this was used as the warp, while the composite thread
described above was used as the weft, weaving was
accomplished so that the weft spacing was 5 mm, and an
anisotropic textile was obtained. Furthermore, by passing
this textile through a pair of rollers heated to 180°C,
the anisotropic textile of the present invention, in which
the warp and weft partially adhered to one another, was
obtained. The anisotropic textile which was obtained was
flexible and extremely easy to handle, since somewhat
rough handling thereof did not cause disordering of the
fibers or breakdown of the weave.
70 parts of methyl methacrylate, two parts of 1,3-
butylene glycol dimethacrylate, 25 parts of butyl acrylate
macromonomer having a number-average molecular weight of
6;000 and having a methacrylic group on the terminus
thereof, one part of n-paraffin, and 1 part of y-
methacryloxypropyl trimethoxysilane were sufficiently
mixed so as to be uniform, and then finally one part of
N,N-dimethyl-p-toluidine was added and mixed, and this
produced the reactive mixture containing no organic
peroxide.
CA 02399416 2002-09-05
36
The viscosity at 20°C thereof was measured and
found to be 75 centipoise.
.:
A reactive mixture resulting from the addition of
two parts of benzoyl peroxide diluted to 50% with a
plasticizer to 100 parts of the reactive mixture described
above was impregnated into two plies of the above
anisotropic textiles so that the resin weight reached
approximately 1000 g/m2, and this was allowed to stand for
one hour at a standard temperature (20°C), and cured. A
tension test piece was produced from the composite
obtained, and was evaluated. When converted to a fiber
content ratio of 100% (dividing by the theoretical
thickness of the anisotropic textile), the tensile
strength was 390 kgf/mm2(3.82Gpa), and it was thus
confirmed that sufficient strength was present.
Furthermore, the impregnation properties of the resin were
extremely good.
(Embodiment 2)
Two parts of benzoyl peroxide diluted to 50% in a
plasticizer were added to 100 parts of the reactive
mixture of embodiment 1, and this was applied in an amount
of 250 g/m2 to the surface of a concrete bending test piece
in conformity with Japanese Industrial Standard A 1132
established by the Japanese Industrial Standards Committee
and published by the Japanese Standards Association in
1976 (hereinafter "JIS A1132") to which the anisotropic
CA 02399416 2002-09-05
36a
textile was to be affixed (the side subject to tensile
deformation), and an anisotropic textile identical to that
of embodiment 1 was affixed thereto so that the
CA 02399416 2002-09-05
37
orientation direction of the reinforcement fibers was
aligned with the longitudinal direction of the concrete
test piece, and thereafter, the reactive mixture was
applied thereon to amount of 250 g/m2, this was impregnated
into the anisotropic textile, and was allowed to stand.
The gelling time at the standard temperature (20°C) of the
reactive mixture was approximately 25 minutes; however,
since the anisotropic textile was easy to handle and the
impregnation of the reactive mixture was also extremely
good, the operation proceeded smoothly, and it was a
simple matter to conduct the operation of affixing the
textile to six test spots in the space of a few minutes.
The curing was completed in a period of approximately 1
hour from the admixture of an organic peroxide (the
benzoyl peroxide diluted to 50°s in a plasticizer), and the
bonding to the concrete after a period of one hour and a
half was evaluated using a building type tension test in
,- conformity with Japanese Industrial Standard A 6909
established by the Japanese Industrial Standards Committee
and published by the Japanese Standards Association in
1984 (hereinafter "JIS A6909"). Breakage occurred at the
concrete portions, so that it was determined that
sufficient adhesive strength was obtained. Next, a
bending test in accordance with Japanese Industrial
Standard A 1106 established by the Japanese Industrial
Standards Committee and published by the Japanese
CA 02399416 2002-09-05
37a
Standards Association in 1976 (hereinafter "JIS A1106")
was executed, and the reinforcement effects were
confirmed. The results of a bending test without
reinforcement were 90 kgf/cm2(8.8 MPa), while the results
when reinforcement was conducted were 160 kgf/cm2 (15.7
MPa ) .
a
h~.:
CA 02399416 2002-09-05
38
(Embodiment 3)
Test pieces were produced and evaluated in the same
manner as in embodiment 2, with the exception that the
operation in which the textile was affixed to the concrete
test piece was conducted at 5°C. Even at 5°C, curing was
sufficient after 2 hours, and in the bonding test,
breakage occurred at the concrete portion. Furthermore,
the bending strength increased, at 155 kgf/cm2 (15.2 MPa),
and sufficient reinforcement effects were thus confirmed
even as a result of execution at low temperatures.
(Embodiments 4 - 16, Comparative Examples 1 - 6)
Conposite test pieces were produced and evaluated
using anisotropic textiles identical to those of
embodiment 1, with the exception that the composition of
the composite thread used as the weft, and the spacing of
the weft in the anisotropic textile, differed. The
composition of the anisotropic textiles and the results of
the evaluations are shown in tables 1,2,3 and 4. The
abbreviations and references in the tables are as given
below.
CF: Pyrofil TR30G carbon fibers produced by
Mitsubishi Rayon Co. Ltd.
The numbers in the tables refer to the CF areal
weight of the anisotropic textile.
CA 02399416 2002-09-05
39
GF: glass fibers (having a tensile elastic modulus
of 72.5 GPa, a melting point of 840°C and a specific
gravity of 2.54 g/cm3)
PA: low melting point polyamide multifilaments
(having a melting point of 125°C and a specific gravity of
1.08 g/cm.°)
PE: low melting point polyester multifilaments
(having a melting point of 130°C and a specific gravity of
g/cm~) _.
PO: low melting point polyolefin multifilaments
(having a melting point of 100°C and a specific gravity of
g/cm~')
The number shown under headings GF - PO in the
tables indicate the weights per unit length of each fiber
used in the weft of the anisotropic textile.
EV: ethylene vinyl acetate copolymer (having a
melting point of 80°C)
AC: acrylic system copolymer thawing a melting
point of 75°C)
The numerals in the table refer to the weight
percent of high molecular compound in the composite
thread.
Handling properties, impregnation properties of the
resin: Double circle... extremely good, Circle... good,
Triangle... somewhat poor, and X... poor
Tensile strength: shown in units of kgf/mm2
CA 02399416 2002-09-05
40
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CA 02399416 2002-09-05
' 44
(Embodiment 17)
70 parts of methyl methacrylate, two parts of 1,3-
butylene glycol dimethacrylate, 25 parts n-butyl acrylate
macromonomer having a number average molecular weight of
6,000 and having a methacrylic group on the terminal
thereof, one part of n-paraffin, and one part of y-
methacryloxypropyl trimethoxysilane were sufficiently
mixed so as to be uniform, and then two parts of N,N-
dimethyl-p-toluidine were added, and the reactive mixture
A containing no organic peroxides was obtained.
The viscosity at 20°C was measured and found to be
75 centipoise.
Furthermore, a reactive mixture B containing
organic peroxides and containing no curing promoter was
obtained by adding four parts of benzoyl peroxide diluted
to 50$ with a plasticizer in place of the two parts of
N,N-dimethyl-p-toluidine described above.
The viscosity thereof was measured at 20°C and
found to be 75 centipoise.
The reactive mixture A described above was applied
to the surface of a concrete bending test piece to which
the anisotropic textile was to be affixed so as to reach a
level of 250 g/m2, and after an anisotropic textile
identical to that of embodiment 1 was affixed thereto,
reactive mixture B was applied thereon in an amount of 250
g/m-, and this impregnated into the anisotropic textile
and was allowed to stand. Reactive mixture A and reactive
CA 02399416 2002-09-05
' 45
mixture B were both stable at standard temperatures in
isolation; however, after mixing, a reaction rapidly
proceeded, and gelling occurred after approximately 30
minutes. Since both reactive mixtures A and B impregnated
into the anisotropic textile extremely well, the operation
preceded smoothly, and it was possible to complete the
affixing of the textile to six test pieces in a few
minutes. The curing was completed in approximately one
hour after the impregnation of reactive mixture B, and
when a Building Research Institute type test of the
bonding to the concrete was conducted after a period of
one and a half hours, the breakage occurred at the
concrete portions, so that it was confirmed that
sufficient bonding strength was obtained. Next, a bending
test was conducted, and the reinforcement effects were
confirmed. The bending strength when reinforcement was
not carried out was 90 kgf/cm2 (8.8 MPa), whereas the
bending strength when reinforcement was carried out was
150 kgf/cm2 (14.7 MPa).
(Embodiment 18)
parts of N,N-dimethyl-p-toluidine and 20 parts
of n-butyl acrylate macromonomer having a number average
molecular weight of 6,000 were dissolved in 70 parts
methylethylketone, and this was uniformly mixed. By means
of treating an anisotropic textile identical to that of
embodiment 1 with this mixture, an anisotropic textile was
CA 02399416 2002-09-05
46
prepared on which was deposited, per square meter, S g of
N,N-dimethyl-p-toluidi.ne and 10 g of n-butyl acrylate
macromonomer having a number average molecular weight of
6, 000.
70 parts per weight of methyl methacrylate, 2 parts
per weight of 1,3-butylene glycol dimethacrylate, 23 parts
of n-butyl acrylate macromonomer having a number average
molecular weight of 6,000 and having a methacrylate group
on the terminal thereof, one part of n-paraffin, and one
part of Y-methacryloxypropyl trimethoxysilane were mixed
sufficiently so as to become uniform, and then two parts
of benzoyl peroxide diluted to 50$ in a plasticizer were
added, and thus a reactive mixture containing an organic
peroxide but not containing a curing promoter was
prepared.
The viscosity thereof was measured at 20°C and was
found to be 70 centipoise.
The reactive mixture not containing a curing
promoter described above was applied to the surface of a
concrete bending test piece to which the anisotropic
textile was to be affixed, in an amount of 250 g/m2, and
then the anisotropic textile described above, on which
N,N-dimethyl-p-toluidine was deposited, was affixed, and
then the reactive mixture described above was again
applied thereon in an amount of 250 g/m-, and this was
allowed to impregnate into the anisotropic textile and was
allowed to stand.
g/m-, and this impregnated
CA 02399416 2002-09-05
47
The anisotropic textile described above was
extremely easy to handle and the impregnation of the
reactive mixture was also extremely good, so that the
operation proceeded smoothly, and it was possible to affix
the textile to 6 test pieces in the space of a few
minutes. The curing was conducted in approximately 1 hour
from the impregnation of the reactive mixture described
above, and when the Building Research Institute type test
of the bonding to the concrete (described in K.Watanabe k
E.Ono,Eds., Nuriyuka Handbook, Nuriyuka Industry
Association (Kohbunsha Publishing Co., Ltd, 1995)) was
conducted after a period of one and half hours, the
breakage occurred at the concrete portions, so that it was
determined that sufficient bonding strength was obtained.
Next, a bending test was carried out, and the
reinforcement effects were confirmed. As a result of the
reinforcement, the bending strength increased to 165
kgf/cm2 (16 .2 MPa) .
(Embodiment 19)
Concrete bending test pieces_were produced and
evaluated which were reinforced with anisotropic textiles
identical to those of embodiment 2, with the exception
that, in place of the n-butyl acrylate macromonomer, a
polyester methacrylate containing allyl ether groups,
which was produced by reacting phthalic acid, ethylene
glycol, pentaerythritol triallylether, and methacrylic
CA 02399416 2002-09-05
47a
acid, was employed, and one part cobalt naphthenate was
used as a curing promoter. The viscosity of this reactive
mixture at 20°C was found to be 250 centipoise. The
CA 02399416 2002-09-05
48
' gelling time at the standard temperature (20°C) was
approximately 30 minutes, and no problems were presented
by the affixing operation of the anisotropic textile.
Furthermore, the bending strength of the test pieces
reinforced with this anisotropic textile was 160
kgf/cm2(15.7 MPa), and it was thus confirmed that
sufficient reinforcement effects were obtained.
(Embodiment 20)
Concrete bending test pieces were produced and
evaluated which were reinforced with anisotropic textiles
identical to those of embodiment 19, with the exception
that, in place of the polyester methacrylate containing
allyl ether groups, an epoxy methacrylate, which was
obtained by reacting an epoxy resin containing 190 g/eq.
of epoxy with methacrylic acid, was employed.
The viscosity of this reactive mixture at 20°C was
_ found to be 350 centipoise, and the gelling time at the
standard temperature (20°C) was approximately 30 minutes,
so that the affixing operation of the anisotropic textile
presented no difficulties. Furthermore, the bending
strength of the test pieces reinforced with this
anisotropic textile was 155 kgf/cm2(15.2 MPa), and it was
thus confirmed that sufficient reinforcement effects were
obtained.
(Embodiment 21 )
CA 02399416 2002-09-05
49
' Concrete bending test pieces were produced and
evaluated which were reinforced with anisotropic textiles
identical to those of embodiment 19, with the exception
that, in place of the polyester methacrylate containing
allyl ether groups, an epoxy acrylate containing allyl
ether groups, which was obtained by reacting phthalic
acid, a bisphenol A type epoxy resin containing 875 epoxy
equivalents (Epikote 1004, produced by Yuka Shell Epoxy
Corporation), pentaerythritol triallyl ether, and acrylic
acid, was employed.
The viscosity of this reactive mixture at 20°C was
found to be 350 centipoise, and the gelling time thereof
at the standard temperature (20°C) was approximately l5
minutes, and no problems were presented by the affixing
operation of the anisotropic textile. Furthermore, the
bending strength of the test pieces reinforced with this
anisotropic textile was 162 kgf/cm2 (15.9 MPa), and.it was
thus confirmed that sufficient reinforcement effects were
obtained.
Embodiment 22)
Pyrofill TR-30G carbon fibers (with a filament count
of 12,000) produced by Mitsubishi Rayon Co. Ltd. were
arranged in a single direction using a batten and a comb,
with a width of 300 mm and at a spacing of 2.5 mm, and
threads, in which glass fibers having TEX number 22.5 (the
standard of glass fibers ECG225 1/0, as defined in IS02078
CA 02399416 2002-09-05
49a
in the Japanese Industrial Standard R 3413 (1982)) and
low melting point nylon fibers
CA 02399416 2002-09-05
(having a melting point of 125°C) of 70 deniers were
intertwined, were arranged so as to be perpendicular to
the carbon fibers in both surfaces with a spacing in each
surface of 25 mm, arranged in an alternating manner in
both surfaces so that the sheet as a whole had a spacing
of 12.5 mm, and this was then heat melted using a heat
press at a temperature of 180°C, and thereby, a sheet
material 1 comprising reinforcement fibers was obtained.
The preparation of the resin was as follows: first,
as component (1), 60 parts methyl methacrylate/10 parts 2-
ethylhexyl acrylate/2 parts 1,3-butylene glycol
dimethacrylate, 1 part of n-paraffin (having a melting
point within a range of 54 - 56°C) as a paraffin wax, and
one part of Y-methacryioxypropyl trimethoxysilane as a
silane coupling agent, were mixed and heated to a
temperature of 50°C, and then 25 parts of an acrylic
copolymer having an average molecular weight of 42000 and
comprising methyl methacrylate and n-butyl methacrylate in
a 60/40 ratio (by weight) was added as component (2), and
thereafter, while cooling, one part of N,N-dimethyl-p-
toluidine was added, and a resin liquid was obtained. The
viscosity at 20°C was measured at 80 centipoise.
Two parts of benzoyl peroxide diluted to 50$ using
a plasticizes was added to 100 parts of the above resin
liquid, this was mixed, and the reactive mixture was
obtained (this is termed resin liquid 1).
CA 02399416 2002-09-05
51
A base layer of resin liquid 1 was applied to a high
strength quick curing concrete wall, and the sheet
material l comprising reinforcement fibers was affixed on
top of this, and resin liquid 1 was again applied on top
of this, and this was impregnated using a pile roller.
Resin liquid 1 impregnated well into sheet material
1. Furthermore, resin liquid 1 was completely cured after
a period of 30 minutes at standard temperatures (20°C),
and was completely cured after a period of 1 hour even at
a low temperature (5°C) and exhibited sufficient
elasticity and strength. The bonding to the concrete was
good, and when a building type tension test was conducted
after a period of 1 hour of resin curing at the standard
temperature, the strength was found to be 50 kg/cm2(4.9
MPa), and even under low temperature curing conditions,
the strength after 1 hour of curing was found to be 48
kg/cm2(4.7 MPa), and breakage occurred within the concrete.
Bending tests and compression tests were conducted
using concrete sample pieces to which sheet material 1 was
affixed at the standard temperature, and the reinforcement
effects were confirmed. The bending strength was 87 kg/cm2
(8.5 MPa) when reinforcement was not conducted, while when
reinforcement was conducted, this strength rose to 166
kg/cm2(16.3 MPa). The compression strength was tested in
accordance with Japanese Industrial Standard A 1108
established by the Japanese Industrial Standards Committee
CA 02399416 2002-09-05
51a
and published by the Japanese Standards Association in
1976, using a concrete test piece having a diameter of 10
cm and a height of 20 cm, on
CA 02399416 2002-09-05
52
which one layer of sheet material 1 was affixed so at the
standard temperature so that the direction of orientation
of the reinforcement fibers was the axial direction, and
on top of this, another layer was affixed so that the
direction thereof was the circumferencial direction, and
the overlap length was 10 cm. The strength when
reinforcement was not conducted was 274 kg/cm2(26.9 MPa),
whereas when reinforcement was conducted, the strength
rose to 552 kg/cm2(54.1 MPa). The proportion of resin
contained in the repair and reinforcement layer was 62
weight percent.
(Embodiment 23)
Pyrofill TR-30G carbon fibers (with a filament count
of 12000) produced by Mitsubishi Rayon Co. Ltd. were
used for the warp at 10 per inch, while glass fibers of
the type defined by IS02078 standard of glass fibers ECG
450-1/0; in the Japanese Industrial Standard R 3413 (1982)
(hereinafter "ECG 450 1/0 standard") were used for the
weft at 6 per inch, and these were woven together to
produce a screen shaped carbon fiber woven cloth 2.
The execution properties and reinforcement effects
were assessed in the same manner as in embodiment 22, with
the exception that this woven cloth 2 was used in place of
the sheet material 1.
The resin liquid 1 impregnated well into the woven
cloth 2. Furthermore, the resin liquid 1 cured completely
CA 02399416 2002-09-05
52a
in a period of 30 minutes at standard temperature (20°C),
and even at low temperature (5°C), was completely
CA 02399416 2002-09-05
S3
cured after a period of 1 hour and exhibited sufficient
elasticity and strength.
The bonding to the concrete was good, and when a
bonding test by the Building Research Institute method
was carried out after one hour of resin curing at the
standard temperature, the strength was found to be 48
kg/cm' (4.7 MPa), and the breakage was within the concrete.
The results of a bending test and a compression
test were that the bending strength was 160 kg/cm2 (15.7
MPa), while the compressive strength was 550 kg/cm2 (53.9
MPa). The proportion of resin contained in the repair and
reinforcement layer was 65 weight percent.
(Embodiment 24)
Pyrofil TR-30G carbon fibers (with a filament count
of 12000) produced by Mitsubishi Rayon Co. htd. were used
for the warp at 10 per inch, and threads in which glass
fibers (the ECG 450-1/0 standard) and low melting point
nylon (polyamide) fibers (having a melting point of 125°C)
were intertwined, were used as the weft at 6 per inch, and
these were woven, and subsequently a temperature of 180°C
was applied thereto, to produce a screen shaped carbon
fiber woven cloth 3 (anisotropic textile).
The execution properties and reinforcement effects
were assessed in the same manner as in embodiment 22, with
the exception that this woven cloth 3 was used in place of
the sheet material i.
CA 02399416 2002-09-05
54
The resin liquid 1 impregnated easily into the
woven cloth 3. Furthermore, the resin liquid 1 cured
completely in a period of 30 minutes, and even at low
temperature (5°C), the resin cured completely after a
period of 1 hour, and exhibited sufficient elasticity and
strength.
The bonding to the concrete was good, and when a
bonding test by Building Research Institute method was
carried out after a period of one hour of resin curing at
the standard temperature, the strength was found to be 48
kg/cm2 (4.7 MPa), and even under low temperature curing
conditions, a strength of 48 kg/cm2 (4.7 MPa) was obtained
after a curing period of one hour, and the breakage was
within the concrete.
The results of a bending test and a compression
test were that the bending strength was 160 kg/cm2 (15.7
MPa), while the compressive strength was 552 kg/cm' (54.1
MPa). The proportion of resin contained in the repair and
reinforcement layer was 60 weight percent.
( Embodiment 2 5 )
Pyrofil TR-30G carbon fibers (with a filament count
of 12000) produced by Mitsubishi Rayon Co. Ltd. were
arranged using a batten and a comb in a single direction
with a width of 300 mm and at a spacing of 2.5 mm, and on
both surfaces of this, Nisseki Konwed Net ON5050 (having a
weight of 7 g/m- and an 8 mm x 8 mm knot) produced by
CA 02399416 2002-09-05
Nisseki Sheet Pallet System Corporation were disposed as
heat-fusible nets, and this was passed through heated
rollers at a temperature of 100°C and at a pressure of 1
kg/cm2 (0.1 MPa) for a period of 90 seconds, and by thus
melting the meltable net surfaces and attaching them to
the carbon fibers, a sheet material 4 comprising
reinforcement fibers was obtained.
The execution properties and reinforcement effects
were assessed in the same manner as in embodiment 22, with
the exception that this sheet material 1 was used in place
of the sheet material 4.
The resin liquid 1 impregnated easily into the
woven cloth 4. Furthermore, the resin liquid l cured
completely after a period of 30 minutes, and even at low
temperature (5°C), the curing was completed after a period
of 1 hour, and sufficient elasticity and strength were
exhibited.
The bonding to the concrete was good, and when a
bonding test by the Building Research Institute method was
conducted after a period of one hour of resin curing at
the standard temperature, the strength was found to be 49
kg/cm2 (4.8 MPa), and the breakage was within the
concrete.
The results of a bending test and a compression
test were that the bending strength was 161 kg/cm2 (15.8
MPa), while the compressive strength was 548 kg/cm-' (53.7
MPa ) .
CA 02399416 2002-09-05
' S6
(Embodiment 26)
Pyrofil TR-30G carbon fibers (with a filament count
of 12000) produced by Mitsubishi Rayon Co. Ltd. were
arranged in a single direction using a batten and a comb
at a width of 300 mm and at a spacing of 2.5 mm, and on
both surfaces thereof, the Daiamid span (having a weight
of 13 g/m') produced by Daicell-Huls Ltd. was disposed as
meltable non-woven fabric, and this was passed through
heated rollers at a temperature of 130°C and at a pressure
of 1 kg/cm2 for a period of 40 seconds, and by means of
thus melting the heat-fusible non-woven fabric and
attaching them to the carbon fibers, a sheet material 5
comprising reinforcement fibers was obtained.
The execution properties and reinforcement effects
were assessed in the same manner as in embodiment 22, with
the exception that this sheet material 5 was used in place
of the sheet material 1.
With respect to the execution properties, resin
liquid 1 impregnated easily into sheet material 5.
Furthermore, resin liquid 1 cured completely after a
period of 30 minutes, and even at low temperature (5°C),
the curing was completed after a period of 1 hour, and
sufficient elasticity and strength were exhibited.
The adhesion with the concrete was good, and when a
bonding test by the Building Research Institute method was
conducted after one hour of resin curing at the standard
CA 02399416 2002-09-05
57
temperature. the strength was found to be 45 kg/cm' (4.4
MPa). and the breakage was within the concrete.
The results of a bending test and a compression
test were that the bending strength was 125 kg/cm2 (12.3
MPa), while the compressive strength was 532 kg/cm' (52.2
MPa ) .
(Embodiment 27)
A resin was prepared in the following manner:
first, one part of n-paraffin (having a melting point
within a range of 54 - 56°C) was added as a paraffin wax
to component (1) comprising 51 parts of methyl
methacrylate, 20 parts of n-butyl methacrylate, and 3
parts of ethylene glycol dimethacrylate, and this mixture
was heated to 50°C and mixed, and during this process, a
component (2) comprising 24 parts of an acrylic copolymer
having an average molecular weight of 95,000 and
comprising methyl methacrylate and methyl acrylate in a
ratio of 97/3 (by weight) was added and dissolved therein,
and thereafter, one part of N,N-dimethyl-p-toluidine was
added while cooling as a curing promoter, and the resin
liquid was obtained. The viscosity thereof at 20°C was
found to be 700 centipoise.
Two parts of benzoyl peroxide diluted to 50$ in a
plasticizer was added per 100 parts of the above resin
liquid, and this was used hereinbelow (this is termed
resin liquid 2).
CA 02399416 2002-09-05
5g
The execution properties and reinforcement effects
were assessed in the same manner as in embodiment 22, with
the exception that this resin liquid 2 was used in place
of the resin liquid 1.
Resin liquid 2 impregnated easily into sheet
material 1. Furthermore, resin liquid 2 was completely
cured after a period of 30 minutes, and even at low
temperatures (5°C), the curing was complete after a period
of one hour, and sufficient elasticity and strength were
exhibited. The bonding strength to the concrete was good,
and when a bonding test by the Building Research Institute
method was conducted after a period of one hour of resin
curing at the standard temperature, the strength was found
to be 47 kg/cm2 (4.6 MPa), and the breakage occurred within
the concrete.
The results of the bending test and the compression
test were that the bending strength was 164 kg/cm2 (16.1
MPa) and the compression strength was 550 kg/cm2 (53.9
MPa). The proportion of resin contained in the repair and
reinforcement layer was 63 weight percent.
(Comparative Example 7)
60 parts of bisphenol A type epoxy resin (Ep 828,
produced by Yuka Shell Epoxy Corporation), 40 parts of
trimethylolpropane triglycidyl ether (Adeka Glycerol ED-
505, produced by Asahi Denka Industries) and 45 parts of
an aliphatic polyamine modified curing agent (Ancamine
CA 02399416 2002-09-05
59
2021, produced by ACI Japan) were mixed, and thereby a
room-temperature-curing-type epoxy system resin liquid 3
(5700 centipoise at 20°C using a B type viscometer) was
obtained.
The execution properties and reinforcement effects
were assessed in the same manner as in embodiment 22, with
the exception that this epoxy system resin liquid 3 was
used in place of the resin liquid 1.
It was difficult to impregnate resin liquid 3 into
sheet material 1. Furthermore, although the stickiness of
the resin liquid 3 disappeared after it was allowed to
stand at the standard temperature for half a day. the
elasticity and strength thereof were poor, and a period of
7 days was required before sufficient elasticity and
strength were obtained. Furthermore, at low temperatures,
S days were required for the stickiness thereof to
disappear, and 20 days were required to exhibit sufficient
elasticity and strength, and the adhesion strength with
the concrete was poor, so that when an adhesion test was
conducted after the passage of half a day at the standard
temperature, the strength was 39 kg/cm2 (3.8 MPa), and
breakage occurred at the interface between the concrete
and the sheet material comprising strengthening fibers.
The results of a bending test and a compression
test conducted on a test piece which was allowed to
completely cure at standard temperatures resulted in a
CA 02399416 2002-09-05
bending strength of 164 kg/cm- (16.1 MPa) and a
compression strength of 540 kg/cm' (53.0 MPa).
(Comparative Example 8)
Pyrofii TR-30G carbon fibers (having a filament
count of 12000) produced by Mitsubishi Rayon Co. Ltd. were
disposed so as to have a spacing of 2.5 mm in an arranged
manner on a resin film, in which a bisphenol A type epoxy
resin (Ep 834, produced by Yuka Shell Epoxy Corporation)
was applied on release paper at a weight of 30 g/m2, and
by applying heat pressing, the resin was impregnated into
the carbon fibers, and a sheet material 6 comprising
reinforcement fibers was obtained.
The execution properties were assessed in the same
manner as in embodiment 22, with the exception that this
sheet material 6 was employed in place of sheet material
1.
With respect to the execution properties, resin
liquid 1 impregnated into sheet material 6; however, this
caused great drift and disorder in the carbon fibers.
Furthermore, the surface of resin liquid 1 was free of
sticking after 30 minutes at standard temperatures, but
the interface between the sheet material and the concrete,
and the interior of the sheet material, were not cured,
and these areas remained uncured even after the passage of
5 days. .
CA 02399416 2002-09-05
61
' (Embodiment 28)
As a sheet material comprising reinforcement
fibers, Pyrofill TR-30G carbon fibers (having a filament
count of 12000) produced by Mitsubishi Rayon Co. Ltd were
arranged using a batten in a single direction at a width
of 300 mm and spacing of 2.5 mm, and heat-fusible fibers,
resulting from the twining of long glass fibers of ECG 450
1/2 standard as defined by IS02078 in the Japanese
Industrial Standard R 3413 (1982), (having a TEX number of
22.5) and low melting point nylon (polyamide) filaments
(having a melting point of 125°C) of 50 deniers, were
plain woven with a spacing of 10 mm in a direction
perpendicular to that of the carbon fibers, and
thereafter, this was passed through heating rollers at a
temperature of 180°C and at a pressure of 1 kg/cm2 (0.1
MPa) for a period of 40 seconds, and a sheet material I
(anisotropic textile) comprising reinforcement fibers
having a carbon fiber weight of 300 g/m2 was obtained, and
this was taken up on a paper roller.
The preparation of the resin was as follows: first,
one part of n-paraffin (having a melting point within 54 -
56°C), as a paraffin wax, and 1 part of
Y-methacryloxypropyl trimethoxysilane, as a silane
coupling agent, were added to component (1) comprising 60
parts of methyl methacrylate, 10 parts of 2-ethylhexyl
acrylate, and 2 parts of 1,3-butylene glycol
dimethacrylate, and this was heated to 50°C while mixing,
CA 02399416 2002-09-05
61a
and during this process, a component (2) comprising 25
parts of an acrylic copolymer having an average molecular
CA 02399416 2002-09-05
62
weight of 92000 and comprising methyl methacrylate and n-
butyl methacrylate in a ratio of 60/40 (by weight) was
dissolved therein, and while cooling this, two parts of
N,N-dimethyl-p-toluidine was added as a curing promoter,
and a resin liquid A1 was obtained. The viscosity thereof
at 20°C was found to be 80 centipoise.
Instead of adding two parts of N,N-dimethyl-p-
toluidine while cooling, four parts of benzoyl peroxide
diluted to 50~ in a plasticizes was added as an organic
peroxide to 100 parts of the resin liquid after cooling,
and a resin liquid B1 was thus prepared.
The viscosity thereof at 20°C was found to be 85
centipoise.
Both resin liquids exhibited almost no change in
viscosity even when allowed to stand for one week at the
standard temperature, and thus exhibited sufficient
stability.
Using a doctor coater, resin liquid A1 was coated
on release paper so to reach a resin weight of 200 g/m2,
and the sheet material I comprising reinforcement fibers
which was described above, and a separated piece of paper,
were placed there on, and a prepreg Al was obtained by
subjecting this to pressure using rubber rollers at room
temperature.
Resin liquid B1 was first sufficiently applied
using a brush to the concrete surface, and then the
prepreg A1 described above was laid thereon with the
CA 02399416 2002-09-05
~ 63
release paper removed, and after that, resin liquid B1 was
applied thereon to the entire surface of the prepreg using
a roller, and this was allowed to impregnate and mix well.
The prepreg was cured by being allowed to stand for a
period of 30 minutes at room temperature (23°C). A
portion of the cured prepreg was subjected to a bonding
test by the Building Research Institute method in which
this portion was stripped from the concrete, in accordance
with JIS A6909. A strength of 800 kg/1600 mm' (50 kg/cm2,
4.9 MPa) was obtained, and the prepreg was stripped oft
along with concrete, so that sufficient curing properties
and adhesive properties were obtained. Furthermore,
sufficient reinforcement strength was exhibited. The
proportion of resin present in the repair and
reinforcement layer was 57 weight percent.
(Embodiment 29)
Glass fibers (having a tensile elastic modulus of
72.5 GPa, a melting point of 840°C, and a specific gravity
of 2.54 g/cm3) having a TEX number of 22.5 (0.0225 g/m)
were twined together with low melting point polyamide
multifilaments (having a melting point of 125°C and a
specific gravity of 1.08 g/cm;) having a total denier of
70 deniers, and an ethylene vinyl acetate copolymer
(having a melting point of 80°C) was deposited thereon in
an amount of 1.5 g~per 1000 m of the twined thread, to
produce a composite thread. The weight per meter of this
CA 02399416 2002-09-05
' 64
composite thread was approximately 0.03 g, and the
composite ratio between the high melting point fibers and
the low melting point fibers was 1:0.8 in volumetric
ratio.
Using Pyrofil TR30G carbon fibers (having a tensile
strength of 4.5 GPa, a tensile elastic modulus of 235 GPa,
and a filament count of 12000) produced by Mitsubishi
Rayon Co. Ltd. arranged so that the fiber weight was 300
g/m- as the warp, and using the composite thread described
above as the weft, weaving was conducted so that the weft
spacing was 5 mm, and by passing this textile through a
pair of rollers heated to a temperature of 180°C, the warp
and weft partially adhered to one another, and a sheet
material comprising reinforcement fibers (the anisotropic
textile of the present invention) was obtained.
70 parts of methyl methacrylate, two parts of 1,3-
butylene glycol dimethacrylate, 25 parts of n-butyl
acrylate macromonomer having a number average molecular
weight of 6,000 and possessing a methacrylic group on the
terminus thereof, one part of n-paraffin, and one part of
7-methacryloxypropyl trimethoxysilane, were sufficiently
mixed so as to become uniform, and two parts of N,N-
dimethyl-p-toluidine were added thereto and mixed, and
thus a resin liquid A containing a curing promoter but not
containing a curing agent, was obtained. The viscosity of
the resin at 20°C was 75 centipoise.
CA 02399416 2002-09-05
Furthermore, a resin liquid B containing a curing
agent (an organic peroxide) but not containing a curing
promoter was obtained by adding, in place of the two parts
of N,N-dimethyl-p-toluidine, four parts of benzoyl
peroxide. The viscosity of the resin at 20°C was found to
be 75 centipoise.
Resin liquid A was applied to the surface of a
concrete bending test piece in accordance with JIS A1132
to which the sheet material comprising reinforcement
fibers was to be applied, using a pile roller (the roller
having the brand name 'Uu Roller' produced by Otsuka Brush
Mfg. Corporation) so as to reach a level of 125 g/m2, and
then the sheet material comprising reinforcement fibers
was affixed to the concrete test piece so that the
longitudinal direction of the concrete test piece
coincided with the direction of orientation of the
reinforcement fibers, and then the sheet material
comprising reinforcement fibers was lightly pressed into
the surface to which the resin liquid A had been applied,
so that resin liquid A was lightly impregnated. On top of
this, resin liquid B was applied using a pile roller so as
to reach a level of 250 g/m2, and this was impregnated
into the sheet material comprising reinforcement fibers.
Resin liquid A was then applied using a pile roller to the
surface to which the resin liquid B had been applied so as
to reach a level of 125 g/m-, and finally the impregnation
and mixing of both these liquids was promoted using a
CA 02399416 2002-09-05
66
grooving roller, and this was then allowed to stand.
Resin liquid A and resin liquid B were both independently
stable at the standard temperature; however, after mixing,
the reaction rapidly progressed, and curing took place
after approximately 30 minutes. Both resin liquid A and
resin liquid B impregnated easily into the sheet material
comprising reinforcement fibers, and the operation-
proceeded smoothly, so that a single person was easily
able to complete the operation of affixing the material to
20 concrete test pieces with a single round of resin
preparation. Curing was complete within approximately one
hour from the application of resin liquid B, and
confirmation of this surface by touching revealed no
curing deficiencies. The bonding to the concrete was
evaluated using the Building Research Institute method
after a period of one and half hours, and breakage was
found to occur within the concrete portion, so that it was
confirmed that sufficient bonding strength was obtained.
Next, bending tests were carried out in accordance
with JIS A1106, and the reinforcement strength was
confirmed. The bending strength was 90 kgf/cm2 (8.8 MPa)
when no reinforcement was carried out, while when
reinforcement was carried out, this strength rose to 160
kgf/cm' ( 15. 7 MPa) .
(Embodiment 30)
CA 02399416 2002-09-05
' 67
Test pieces were produced and evaluated in the same
manner as in embodiment 29, with the exception that the
affixing operation to the concrete bending test pieces was
carried out under conditions such that the temperature was
5°C. Even at 5°C, curing was sufficient after a period of
2 hours, and no curing deficiencies could be found by
touch. In~the bonding test, the presence o~f breakage
within the concrete was confirmed. Furthermore, the
bending strength was 158 kgf/cm' (15.5 MPa), so that it was
determined that sufficient reinforcement effects were
exhibited even at low temperatures.
(Embodiment 31)
In the same manner as in embodiment 29, a sheet
material comprising reinforcement fibers (the anisotropic
textile of the present invention), and a resin liquid A
and a resin liquid B, were prepared.
The resin liquid A described above was applied to
the surface of concrete test pieces in accordance with JIS
A1132 to which the sheet material comprising reinforcement
fibers was to be affixed, using a pile roller and so as to
achieve a level of 125 g/m2. and the sheet material
comprising reinforcement fibers was affixed to the
concrete test pieces so that the longitudinal direction of
the test pieces coincided with the direction of
orientation of the reinforcement fibers, and the sheet
material comprising reinforcement fibers was lightly
CA 02399416 2002-09-05
68
impregnated with resin liquid A. Then on top of this,
resin liquid B was applied in an amount of 250 g/m', and
this was allowed to impregnate into the sheet material
comprising reinforcement fibers, and furthermore, resin
liquid A was applied in an amount of 250 g/m' to the
surface to which this resin liquid B had been applied, and
a sheet material comprising reinforcement fibers was
affixed to the concrete test piece so that the
longitudinal direction of the concrete test piece
coincided with the direction of orientation of the
reinforcement fibers, and resin liquid A was lightly
impregnated into the sheet material comprising
reinforcement fibers. Next, on top of this, resin liquid
B was applied in a similar manner in an amount of 250
g/m', and this was allowed to impregnate into the sheet
material comprising reinforcement fibers, and then resin
liquid A was applied in an amount of 125 g/m2 in the same
manner to the surface to which the resin liquid B had been
applied, and the impregnation and mixing thereof was
promoted using a grooving roller, and this was then
allowed to stand. Resin liquid A and resin liquid B were
both independently stable at the standard temperature;
however, after mixing, the reaction therebetween proceeded
rapidly, and curing occurred after approximately 30
minutes.
Resin liquid A and resin liquid B both impregnated
easily into the sheet material comprising reinforcement
CA 02399416 2002-09-05
69
fibers, and the operation proceeded comparatively
smoothly, so that the affixing operation onto 6 concrete
test pieces presented no problems.
The curing was completed in approximately 20
minutes from the application of resin liquid B, and no
spots at which curing was deficient could be confirmed by
touch. The bonding to the concrete was tested by the
Building Research Institute method after 1 1/2 hours, and
breakage was determined to occur in the concrete portion,
so that it was confirmed that sufficient bonding strength
was obtained.
(Embodiment 32)
Pyrofill TR-30G carbon fibers (having a filament
count of 12000) produced by Mitsubishi Rayon Co. Ltd. were
arranged unidirectionally in sheet form using a batten and
a comb and having a width of 300 mm and spacing of 2.5 mm~
and Daiamid spans (having a weight of 13 g/m2) produced by
Daicel-Huls Ltd. were disposed on both surfaces thereof as
heat-fusible non-woven fabrics, and this was passed
through heated rollers at a temperature of 130°C and a
pressure of 1 kg/cm2 for a period of 40 seconds, the heat-
fusible non-woven fabric was melted and caused to adhere
the carbon fibers, and thereby, a sheet material 5
comprising reinforcement fibers was obtained in the same
manner as in embodiment 26.
CA 02399416 2002-09-05
The affixing of the sheet material onto concrete
test pieces was conducted in the same manner as in
embodiment 29, with the exception that this sheet material
comprising reinforcement fibers was employed as the
sheet material comprising reinforcement fibers. The
operation of affixing this sheet material to 20 concrete
test pieces was easily completed. Curing was completed
within approximately 1 hour from the application of resin
liquid B, and no spots at which curing was deficient were
revealed by touch. The bonding to the concrete was
evaluated using the Building Research Institute method
after 1 1/2 hours, and breakage was found to occur within
the concrete, so that it was confirmed that sufficient
bonding strength was obtained.
(Embodiment 33)
In the sheet material comprising reinforcement
fibers of embodiment 28, the spacing of the heat-fusible
fibers was set to 5 mm, and a sheet material II comprising
reinforcement fibers (the anisotropic textile of the
present invention) was obtained.
30 m of this sheet material II comprising
reinforcement fibers was measured, and this was wound
around a paper tube of 15.9 cmc~.
The paper tube having the sheet material II
comprising reinforcement fibers described above wound
therearound was placed in a stainless steel container, and
CA 02399416 2002-09-05
the resin liquid A1 of embodiment 28 was poured over this
from above, so that the resin was placed in the container,
this was sealed, and the resin was allowed to impregnate
into the sheet material II comprising reinforcement
fibers. This was allowed to impregnate sufficiently by
allowing the container to stand for a period of 2 days at
room temperature.
After impregnation, the roller containing the sheet
material II comprising reinforcement fibers, containing
sufficient resin liquid A1, was retrieved from the
stainless steel container, and excess resin was removed by
light squeezing between rubber rollers, and the prepreg A2
was thus obtained.
The resin liquid B1 of embodiment 28 was first
sufficiently applied to the concrete surface using a
brush, and then the prepreg A2 described above was laid on
top of this, wherein after resin liquid B1 was applied
over the entire surface of prepreg A2 using a brush and a
roller, and allowed to soak in. The prepreg was cured by
means of being to stand at room temperature (23°C) for 30
minutes.
A Building Research Institute type bonding test was
conducted in which a portion of the cured prepreg was
stripped from the concrete in accordance with JIS A6909.
A strength of 783 kg/i600 mm- (49 kg/cm-,9.8 MPa) was
obtained, and concrete was stripped off along with the
prepreg, so that sufficient curing properties and bonding
CA 02399416 2002-09-05
" 72
properties were obtained. Furthermore, sufficient
reinforcement strength was exhibited. The proportion of
resin contained in the repair and reinforcement layer was
62 weight percent.
(Comparative Example 9)
A mixed resin containing 50 parts per weight of
Epikote 828 (produced by Yuka Shell Epoxy Corporation) and
50 parts per weight of ED505 (produced by Asahi Denka
Corporation) was used in place of the resin liquid A1 of
embodiment 28, and a prepreg (having a resin content of
40~) was obtained in the same manner as in embodiment 28.
1 part per weight of a mercaptan system curing
agent (Capcure WR-6, produced by Yuka Shell Corporation)
and 0.5 parts per weight of tris(dimethylaminomethyl)
phenol (Epicure 3010, produced by Yuka Shell Corporation)
as a curing promoter were dissolved in 1 part per weight
of acetone, and this curing agent solution was applied to
the surface of concrete which had been treated with a
primer, and then the prepreg described above was placed
thereon, and the curing agent solution was again applied
thereto. This was dried and cured at room temperature
(20°C); however, the prepreg remained uncured even after
the passage of 12 hours. After the passage of 5 days,
there was no longer any surface stickiness, so that a
bonding test by the Building Research Institute method was
conducted. The prepreg peeled away at the inner face with
CA 02399416 2002-09-05
t 7;
the concrete, and the strength thereof was 125 kg/1600 mm-
(8 kg/cm-, 0.8 MPa), so that curing was insufficient.
(Embodiment 34)
The sheet material I comprising reinforcement
fibers of embodiment 28 was covered with N,N-diisopropyl-
p-toluidine powder in an average amount of 10 g/m2 as a
curing promoter, and thereby, a sheet material Ia
comprising reinforcement fibers on which a curing promoter
was deposited was obtained.
The resin liquid B1 of embodiment 28 was first
sufficiently applied to a concrete surface using a brush,
and then, the sheet material 1A comprising reinforcement
fibers on which curing promoter was deposited was placed
thereon, and after this, resin liquid B1 of embodiment 28
was again applied over the entire surface of the sheet
using a roller. The resin was cured by allowing this to
stand for 30 minutes at room temperature (23°C).
A bonding test by the Building Research Institute
method in which a portion of the sheet material comprising
reinforcement fibers which was cured was stripped from the
concrete, in accordance with JIS A6909, was conducted, and
it was determined that the strength was 780 kg/1600 mm2
(49 kg/cm', 4.8 MPa) , and the concrete was stripped away
together with the reinforcement fibers, so that sufficient
curing properties and bonding properties were obtained,
and sufficient reinforcement strength was exhibited. The
CA 02399416 2002-09-05
74
proportion of resin contained in the repair and
reinforcement layer was 58 weight percent.
(Embodiment 35)
41.7 parts of Epikote 1004 (produced by Yuka Shell
Epoxy Corporation) were added to 20 parts of methyl
methacrylate containing a polymerization inhibitor, and
this was heated to a temperature of 80°C and dissolved,
and thereafter, 0.8 parts of triethyl amine was added as a
reaction catalyst, and this was allowed to react for a
period of 8 hours while adding 3.5 parts of methacrylic
acid by dripping, and an epoxy methacrylate resin solution
having an acid number of 5 was obtained. To this. resin
solution was added 32 parts of methyl methacrylate, 1 part
of y-methacryloxypropyl trimethoxysilane, and 1 part of n-
paraffin, and this was allowed to dissolve, and was then
cooled, and 4 parts of benzoyl peroxide (diluted to 50~
with a plasticizer) was added, to produce resin liquid B2.
The viscosity of this resin liquid B2 at 20°C was measured
and found to be 220 centipoise. N,N-diethyl-p-toluidine
liquid was sprayed onto a sheet material I identical to
that used in embodiment 28 in an average amount of 10 g/m2
as a curing promoter, and thereby, a reinforcement fiber
sheet material Ib on which a curing promoter was deposited
was obtained.
First, resin liquid B2 was sufficiently applied to
a concrete surface using a brush, and on this, the sheet
CA 02399416 2002-09-05
material Ib comprising reinforcement-fibers on~which a
curing promoter was deposited was laid, and resin liquid
B2 was again applied to the entire surface of the sheet
using a roller. The resin was cured by being allowed to
stand for 30 minutes at a room temperature of 20°C.
A bonding test by the Building Research Institute
method in which a portion of the cured reinforcement
fibers was stripped from the concrete was conducted in
accordance with JIS A6909, and the strength was found to
be 670 kg/1600 mm2 (42 kg/cm2, 4.1 MPa), and concrete was
stripped along with the reinforcement fibers, so that
sufficient curing properties and bonding properties were
exhibited. The proportion of resin contained in the
reinforcement layer was 52 weight percent.
(Embodiment 36)
2 parts per weight of Permec N (55~
methylethylketone peroxide) produced by Nippon Oil
Company, Ltd. was mixed with 100 parts per weight of
Prominate P-991, an unsaturated polyester resin produced
by Takeda Chemical Industry Ltd., and a resin liquid A was
thus prepared. The viscosity of the resin at 20°C was
found to be 700 centipoise.
1 part per weight of 6~ cobalt naphthenate was
added to 100 parts per weight of Prominate P-991, and a
resin liquid B was thus prepared.. The viscosity of the
resin at 20°C was found to be 700 centipoise.
CA 02399416 2002-09-05
76
The resin liquid A obtained was placed in one tank,
and the resin liquid B was placed in the other tank, of a
two liquid airless coater APW-1200 (produced by Asahi
Sanak Corporation) having a mixing ratio of 1 to 1 and
equipped with a compressor, the air pressure thereof was
set to 3 kg/cm2, and the resin liquid A/B mixed by a
static mixer was applied in an amount of 250 g/m2 to the
surface of concrete bending test pieces in accordance with
JIS A1132 to which a sheet material comprising
reinforcement fibers was to be applied, using an airless
roller handgun, the sheet material comprising
reinforcement fibers (the anisotropic textile of the
present invention) of embodiment 29 was applied thereto,
and after eliminating the air present in the sheet
material using a defoaming roller, the mixed resin liquid
A/B was applied using an airless roller handgun in an
amount of 250 g/m2, and the resin liquid A/B was then
sufficiently impregnated using the defoaming roller again,
and this was allowed to stand. The reaction proceeded
rapidly and curing occurred within approximately 30
minutes.
(Embodiment 37)
70 parts of methyl methacrylate, 2 parts of 1,3-
butylene glycol dimethacrylate, 25 parts of N-
butylacrylate macromonomer having a number average
molecular weight of 6,000 and having a methacrylic group
CA 02399416 2002-09-05
77
on the terminus thereof, 1 part of n-paraffin, and 1 part
of Y-methacryloxypropyl trimethoxysilane was mixed so as
to be uniform, and a resin composition was thus obtained.
2 parts of benzoyl peroxide diluted to 50g~ in a
plasticizer was added to this resin composition, and this
was mixed to produce a resin liquid A.
1 part of N,N-dimethyl-P-toluidine was added to the
same resin composition, and a resin liquid B was obtained.
The resin liquid A obtained was placed in one tank, and
the resin liquid B obtained was placed in the other tank,
of a two liquid airless coater APW-1200 (produced by Asahi
Sanak Corporation) having a mixing ratio of 1 to 1 and
provided with a compressor, the air pressure thereof was
regulated to 3 kg/cm2, and the resin liquid A/B mixed by
the static mixer was applied in an amount of 250 g/m2 to
the surface of concrete bending test pieces in accordance
with JIS A1132 to which a sheet material comprising
reinforcement fibers was to be applied, the sheet material
comprising reinforcement fibers (the anisotropic textile
of the present invention) of embodiment 29 was applied
thereto, and the air present in the sheet material was
removed using a defoaming roller, and thereafter, the
mixed resin liquid A/B was applied thereon using an
airless roller handgun in an amount of 250 g/m2, and the
resin liquid A/B was impregnated samewhat using a
defoaming roller, and this was allowed to stand. The
CA 02399416 2002-09-05
78
reaction proceeded quickly and curing occurred in
approximately 30 minutes.
CA 02399416 2002-09-05
79
Industrial Applicability
As described in detail above, in the repair and
reinforcement method in accordance with the present
invention, when resin is impregnated into a sheet material
comprising reinforcement fibers and this resin is cured to
form a fiber-reinforced resin layer which is used to
repair and reinforce preexisting structures, a reactive
mixture having a gelling time of 15 minutes or more at
20°C and which polymerizes even at 5°C and cures in 6
hours or less, and which, moreover, has as the chief
components thereof a monomer containing vinyl groups and a
reactive oligomer containing vinyl groups and/or a
thermoplastic polymer, is used as the resin, so that
execution is possible even under low temperature
conditions, and superior repair and reinforcement effects
are exhibited in a short period of time. Accordingly,
this may be used as a repair and reinforcement method for
preexisting structures such as bridges, bridge piers,
columns, building, and the like.
Furthermore, the anisotropic textile of the present
invention has superior handling properties and resin
impregnation properties, and generates superior strength
when cured, so that it may be employed in the repair and
reinforcement of preexisting structures.
