Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SIZING COMPOSITION
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to novel sizing compositions, their preparation and use.
Description of the Related Art
The use of curing components in sizes based on blocked polyisocyanates is
known, for example, from EP-A 0 792 900. Aralkylamine-blocked
polyisocyanates and their particular suitability in sizes, especially glass
fibre sizes,
is not described.
The major compounds used for the blocking of polyisocyanates are E-
caprolactam,
butanone oxime, malonates, secondary amines, and triazole and pyrazole
derivatives, as described, for example, in patents EP-A 0 576 952, EP-A 0 566
953, EP-A 0 159 117, US-A 4 482 721, WO 97/12924 or EP-A 0 744 423.
Secondary amine blocking agents, including aralkyl-substituted amines, are
known from EP-A 0 096 210. The use of such amines in aqueous systems,
particularly in sizes, however, is not known from EP-A 0 096 210.
Although the formula depicted on page 2, lines 20-24 of EP-A 0 096 210
embraces a large number of diamines, page 3 line 8 ff. nevertheless points out
that
all secondary amines are suitable blocking agents. According to page 5 lines
20-
29, only a very small number of such diamines is listed as being suitable. The
DOCSMTL: 3895302\1
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examples on page 9 and 10 as well relate only to diallylamines such as
diisopropylainin.e, substituted secondary cycloaliphatic amines such as
substituted
cyclohexylamines or c.ycloaliphatic N-heterocycles such as 2,2,4,6
tetrarnethyipiperidine. With the exception of diisopropylamine, these
compounds
are reacted with isocyanates at temperatures of at least 120 C, and so the
person
skilled in the art must assume that the elimination of these blocking agents,
necessary for further reaction, takes place only at much higher temperatures.
EP-A 0 178 398 specified solid blocked isophorone diisocyanate as a curing
agent
for powder coating materials. Here again, aralkyl-substituted secondary amines
as
blocking agents and N-tert-butyl-benzylamine were mentioned, albeit without a
specific example. EP-A 0 787 754 claimed such blocking agents for selected
polyisocyanates as curing agents for powder coating materials; N-tert-butyl-
benzylamine or other aralkyl-substituted diamines, however, are mentioned
neither in the disclosure nor in the examples. Liquid solvent-based
formulations or
aqueous or water-dilutable blocked polyisocyanates, and especially their
suitability for sizes, are mentioned in neither document.
In preparing sizes, especially glass fibre sizes, water-dispersible or water-
soluble
isocyan.ates are used, usually blocked with c-caprolactarn and butanone oxime.
Whereas in the case of s-caprolactam-blocked isocyanates it is common to
employ
baking temperatures around 160 C, blocked curing agents for which butanone
oxime was the blocking agent used can be deblocked at temperatures 10-20 C
lower. At these temperatures, however, in many sizes the desired properties
are no
longer achieved. Moreover, high deblocking and/or drying temperatures often
result in an unwanted thermal yellowing of the sizes. Furthermore, these
deblocking temperatures are now perceived as being too high, on cost grounds,
so
giving rise to a demand for sizes comprising crosslinker systems which
crosslink
at lower temperatures than in the case of butanone oxime.
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The principle of the preparation of water-dispersible or water-soluble blocked
polyisocyanates is known and is described, for example, in I)E-A 24 56 469 and
DE-A 28 53 937.
B UEF SUMMARY OF THE INVENTION
The object of the present invention is therefore to provide sizing
compositions
comprising water-dispersible or water-soluble blocked isocyanates having a
significantly lower deblocking temperature as compared with prior art curing
agents.
1.0
It has now been found that sizes comprising hydrophilicized and aralkylamine-
blocked polyisocyanates which are soluble or dispersible in water meet the
above-
mentioned profile of requirements and as well as a much lower crosslinking
temperature exhibit a significantly improved hydrolysis resistance.
The present invention accordingly provides sizing compositions comprising:
1) water-dispersible and/or water-soluble and aralkylarnine-blocked
polyisocyanates,
2) film-forming resins,
3) coupling agents,
4) lubricants,
5) if desired, antistats, and
6) if desired, further additives and auxiliaries.
The water-dispersible and/or water-soluble blocked polyisocyanates 1) are
synthesized from:
A) at least one polyisocyanate containing aliphatically, cycloaliphatically
araliphatically and/or aromatically attached isocyanate groups,
B) at least one ionic and/or potentially ionic and/or nonionic compound,
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C) at least one blocking agent of which at least 20% by weight consists of
aralkylamines,
D) if desired, one or more (cyclo)aliphatic monoamines and/or polyamines
having from 1 to 4 amino groups, from the molecular weight range up to
300,
E) if desired, one or more polyhydric alcohols having from 1 to 4 hydroxyl
groups, from the molecular weight range up to 250
and
F) if desired, stabilizers and other auxiliaries, and
G) if desired, solvents.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, unless otherwise expressly specified, all of the numerical
ranges,
amounts, values and percentages such as those for amounts of materials, times
and
temperatures of reaction, ratios of amounts, values for molecular weight, and
others in the following portion of the specification may be read as if
prefaced by
the word "about" even though the term "about" may not expressly appear with
the
value, amount or range.
The term "molecular weight range" refers to a molecular weight approximately
equal to that of the monomeric form of the identified substance, or to that of
the
simplest member of a group of substances having an identified functional
group.
The water-dispersible and/or water-soluble, aralkylamine-blocked
polyisocyanates
1) preferably contain from 20 to 80% by weight of component A), from I to 40%
by weight of component B), from 15 to 60% by weight of component C) from 0 to
15% by weight of component D), from 0 to 15% by weight of component E) from
0 to 15% by weight of component F) and from 0 to 20% by weight of component
G), the sum of A to G) adding up to 100% by weight.
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The water-dispersible and/or water-soluble, aralkylamine-blocked.
polyisocyanates
1) contain with particular preference rom25 to 75% by weight of component A),
from 1 to 35% by weight of component B), from 20 to 50% by weight of
component C), from 0 to 10% by weight of component D), from 0 to 10% by
weight of component E), from 0 to 10% by weight of component F) and from 0 to
15% by weight of component G), the sun of A to G) adding up to 100% by
weight.
The water-dispersible and/or water-soluble, aralkylamine-blocked
polyisocyanates
1) contain with very particular preference from 30 to 70% by weight of
component A) from 5 to 30% by weight of component B), from 25 to 45% by
weight of component C), from 0 to 5% by weight of component D), from 0 to 5%
by weight of component E), from 0 to 5% by weight of component F) and from 0
to 10% by weight of component C), the sure of A to C) adding up to 100% by
weight.
The water-dispersible blocked polyisocyanates 1) can be used in the sizes of
the
invention as an aqueous solution or dispersion. The solution or dispersion of
the
polyisocyanates 1) has a solids content of between 10 to 70% by weight,
preferably from 20 to 60% by weight and with particular preference from 25 to
50% by weight and the fraction of G) in the overall composition is preferably
less
than 15% by weight and with particular preference less than 10% by weight and
with very particular preference less than 5% by weight.
The blocked polyisocyanates 1) have an (average) NCO functionality of from 2.0
to 5.0, preferably from 2.3 to 4.5, an isocyanate groups (nonblocked and
blocked)
content of from 5.0 to 27.0% by weight, preferably from 14.0 to 24.0% by
weight
and a monomeric diisocyanate content of less than I% by weight, preferably
less
than 0.5% by weight. At least 50%, preferably at least 60% and with particular
preference at least 70% of the isocyanate groups of the polyisocyanates A) of
the
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water-dispersible and/or water-soluble blocked polyisocyanates 1) are in
blocked
form.
Suitable polyisocyanates A) are polyisocyanates which have a uretdione,
isocyanurate, allophanate, biuret, irninooxadiazinedione and/or
oxadiazinetrione
structure which are prepared by modifying simple aliphatic, cycloaliphatic,
araliphatic and/or aromatic diisocyanates and are synthesized with at least
two
diisocyanates, such polyisocyanates being as described by way of example in,
for
example, J. Prakt. Chem. 336 (1994) page 185-200.
Suitable diisocyanates for preparing the polyisocyanates A) are diisocyanates
from the molecular weight range from 140 to 400 which are obtainable by
phosgenation or by phosgene-free processes, for example by thermal urethane
cleavage, and contain aliphatically, cycloaliphatically, araliphatically
and/or
aromatically attached isocyanate groups, such as, for example,
1,4-diisocyanatobexane, 1,6-diisocyanatohexane (HDI), 2-methyl-
1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and/or
2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyannatodecane, 1,3- and
1,4-diisocyanatohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone
diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexyhnethane, 1-isocyanato-
1-methyl-4(3)isocyanato-methylcyclohexane, bis(isocyanatomethyl)-norbornane,
1,3- and 1,4-bis(2-isocyanatoprop-2-yl)benzene (TMXDI), 2,4- and
2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphen. ylmethane,
1,5-diisocyanatonaphthalene or any desired mixtures of such diisocyanates.
The starting components A) are preferably polyisocyanates or polyisocyanate
mixtures of the type mentioned, containing exclusively aliphatically and/or
cycloaliphatically attached isocyanate groups.
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More preferred starting components A) are polyisocyanates or polyisocyanate
mixtures having an isocyanurate and/or biuret structure, based on HDI, IPDT
and/or 4,4'-di.isocyanatodicyclohexylmetliane.
Suitable compounds for component B) are ionic or potentially ionic and/or
nonionic compounds.
Nonionic compounds are, for example, monohydric polyalkylene oxide polyether
alcohols containing on average from 5 to 70, preferably from 7 to 55, ethylene
oxide units per molecule, such as are obtainable conventionally by
alkoxylating
suitable starter molecules (e.g. in Ullmanns Encyclopadie der technischen
Chemie, 4th Edition, Volume 19, Verlag ("hemie, Weinh.eim pp. 31-38).
Examples of suitable starter molecules are saturated monoalcohols such as
methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-
butanol, the
isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol,
n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric
methylcyclohexanols or hydroxynethylcyclohexane, 3-ethyl-
3-hydroxymethyloxetane, or tetrahydrofurfuryl alcohol; diethylene glycol
monoalkyl ethers such as diethylene glycol monobuty). ether, for example;
unsaturated alcohols such as ally/ alcohol, 1, 1 -dimethylallyl alcohol or
oleyl
alcohol, aromatic alcohols such as phenol, the isomeric cresols or
methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisyl alcohol or
cinnamyl alcohol; secondary monoamines such as dimethylamine, diethylamine,
dipropylamine, diisopropylamine, dibutylamine, bis(2-ethylhexyl)ainine,
N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine and also
heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or
1H-
pyrazole.
Preferred starter molecules are saturated monoalcohols and also diethylene
glycol
monoalkyl ethers. More preference is given to using diethylene glycol
monobutyl
ether as a starter molecule.
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Alkylene oxides suitable for the alkoxylation reaction are, in particular,
ethylene
oxide and propylene oxide, which can be used in any order or else in a mixture
in
the alkoxy,Iation reaction.
The polyalkylene oxide polyether alcohols are either pure polyethylene oxide
polyethers or mixed polyalkylene oxide polyethers, at least 30 mol% preferably
at
least 40 mol% of whose alkylene oxide units consist of ethylene oxide units.
Preferred nonionic compounds are monofunctional mixed polyalkylene oxide
polyethers containing at least 40 mol% ethylene oxide units and not more than
60 mol% propylene oxide units.
Suitable compounds for component B) are likewise ionic or potentially ionic
compounds which can be used in addition to or instead of the nonionic
compounds, such as, for example, mono- and dihydroxycarboxylic acids, mono-
and diaminocarboxylic acids, mono- and dihydroxysul font c acids, mono- and
diaminosulfonic acids, and also mono- and dihydroxyphosphonic acids and/or
mono- and diaminophosphon.ic acids and their salts such as dimethylolpropionic
acid, hydroxypivalic acid, N-(2-aminoethyl) -13-alanine, 2-(2-aminoethyl-
amino)ethanesulfonic acid, ethylenediamine-propyl- or butylsulfonic acid, 1,2-
or
1,3-propylenediamine-Ii-ethylsulfonic acid, lysine, 3,5-diaminobenzoic acid,
the
hydrophilicizing agent according to Example 1 of EP-.A 0 916 647 .and the
alkali
metal salts and/or ammonium salts thereof; the adduct of sodium bi.sulfite
with
but-2-ene-1,4-diol, polyethersulfonate, the propoxylated adduct of 2-
butenediol
and NaHSO3 (e.g. in DE-A 2 446 440, page 5-9, formula 1-I11), and building
blocks which can be converted into cationic groups, such as
N-methyldiethanolamine, are used as hydrophilic synthesis components.
Preferred
ionic or potential ionic compounds 13) are those which possess carboxyl or
carboxylate and/or sulfonate groups and/or ammonium groups. Particularly
preferred ionic compounds B) are those containing carboxyl and/or sulfonate
groups as ionic or potentially ionic groups, such as the salts of N-
(2==aminoethyl)-
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13-alanine, 2-(2-ami.noethylaminc)ethan.esalfonic acid, of the
hydrophilicizing
agent according to Example 1 of EP-A 0 916 647 and of dimethylolpropionic
acid.
Component B) is preferably a combination of nonionic and ionic
hydrophilicizing
agents. Particular preference is given to combinations of nonionic and anionic
hydrophilicizing agents.
As an example of blocking agents C) according to the invention, mention may be
made of the following: N-methyl-, N-ethyl-, N-(iso)propyl-, N-n-butyl-,
N-iso-butyl-, N-tert-butyl-benzylamine or 1,1-dimethyibenzylamine, N-alkyl-
N-1,1-dimethyimethylphenylamine, adducts of benzylamine with compounds
having activated double bonds such as malonates, N,N-dimethylaminopropyl-
benzylamine and other, optionally substituted benzylamines containing tertiary
amino groups, and/or dibenzylarnine. Naturally it is also possible to use
mixtures
of these amines with one another and/or with other blocking agents. These are,
for
example, alcohols, lactams, oximes, malonic esters, alkyl acetoacetates,
triazoles,
phenols, imidazoles, pyrazoles, and amines, such as butanone oxime,
diisopropylamine, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole, diethyl
malonate, ethyl acetoacetate, acetone oxime, 3,5-dimethylpyrazole, s-
caprolactamn
or any desired mixtures of these blocking agents. Preference is given to using
N-aralkylamines such as N-(iso)propyl-, N-n-butyl-, N-iso-butyl-, N-tert-butyl-
benzylamine as blocking agents C). A more preferred blocking agent C) is N-
tert-
butylbenzylamine.
Suitable components D) include mono-, di-, tri-, and/or tetra-amino-functional
substances from the molecular weight range up to 300, such as ethylenediamine,
1,2- and 1,3-diaminopropane, 1,3-, 1,4- and 1,6-diaminohexane, 1,3-diarni.no-
2,2-dimethylpropane, 1-amino-3,3,5-trimethyl-5-arninoethylcyclohexane (IPDA),
4,4'-diaminodicyclohexylmethane, 2,4- and. 2,6-diamino-l-methylcyclohexane,
4,4'-diamino-3,3'-dimethyldicyclohexyimethane, 1,4-bis(2-arninoprop-2-yl)cyclo-
hexane or mixtures of these compounds.
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Component E) comprises mono-, di-, tri- and/or tetra-hydroxy-functional
substances of molecular weight up to 250, such as ethylene glycol, propylene
glycol, 1,4-butanediol, 1,6-hexanediois, glycerol, trirn-ethylolethane,
trimethylolpropane, the isomeric hexanet-iols, pentaerythritol or mixtures of
these
compounds.
The water-dispersible and/or water-soluble blocked polyisocyanates 1) may
optionally comprise a stabilizer or stabilizer mixture F). Suitable compounds
F)
are, for example, antioxidants such as 2,6-ditert-butyl-4-methylphenol, UV
absorbers of the 2-hydroxyphenylbenzotriazole type or light stabilizers of the
HALS compound type or other commercially customary stabilizers, as described
in, for example, "Lichtschutzmittel far Lacke" (A. Valet, Vincentz Verlag,
Hanover, 1996) and "Stabilization of Polymeric Materials" (H. Zweifel,
Springer
Verlag, Berlin, 1997, Appendix 3, pp. 181-213).
Preference is given to stabilizer mixtures featuring firstly compounds having
a
2,2,6,6-tetramethylpiperidinyl radical (HALS ring). The piperidinyl nitrogen
of
the HALS ring is not substituted and has no hydrazide structures at all. More
preference is given to a compound of the formula (I)
i
r
which is sold, for example, under the name Tinuvin 770 DF by the company
Ciba Spezialitaten (Lampertheim, DE).
Ideally, the abovementioned compounds are combined with substances possessing
hydrazide structures, such as acid hydrazides and acid dihydrazides, for
example
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acetic hydrazide adipic hydrazide, or adipic dihydrazide, or else hydrazine
adducts
of hydrazine and cyclic carbonates, as specified in, for example, EP-A 0 654
490
(p. 3, line 48 to p. 4 line 3). Preference is given to using adipic
dihydrazide and an
adduct of 2 mol of propylene carbonate and 1 mol of hydrazine, of the general
formula (II)
-C -'H-NH- (II)
More preference is given to the adduct of 2 mol of propylene carbonate and 1
mol
of hydrazine, of the general formula (ILI):
C33 N.-, N 0/ ~., ,OH (III)
Y
Suitable organic solvents U) are the conventional paint solvents, such as
ethyl
acetate, butyl acetate, I-methoxy-2-propyl acetate, 3-methoxy-n-butyl acetate,
acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene,
chlorobenzene or white spirit. Mixtures comprising in particular aromatics
with
relatively high degrees or substitution, such as are commercially available,
for
example, under the names Solvent Naphtha, Solvesso (Exxon Chemicals,
Houston, USA), Cypar (Shell Chemicals, Eschborn, DE), Cyclo Sol (Shell
Chemicals, Eschbom, DE), Tolu Solo (Shell Chemicals, Eschborn, DE),
Shellsol & (Shell Chemicals, Eschborn, DE), are likewise suitable. Further
solvents are, for example, carbonates, such as dimethyl carbonate, diethyl
carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones, such
as
f3-propiolactone, y-butyrolactone, s-caprolactone, c-methylcaprolactone,
propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene
glycol.
dimethyl ether, diethylene glycol ethyl and butyl ether acetate, N-methyl-
pyrrolidone and N-methylcaprolactam, or any desired mixtures of such solvents.
Preferred solvents are acetone, 2-butanone, I-methoxy-2-propyl acetate,
xylene,
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toluene, mixtures comprising in particular aromatics with relatively high
degrees
or substitution, such as are commercially available, for example, under the
names
Solvent Naphtha, Solvesso (Exxon Chemicals, Houston, USA), Cypar (Shell
Chemicals, Eschborn, DE), Cyclo Sol @ (Shell Chemicals, Eschborn, DE), Tolu
Sol (Shell Chemicals, Eschborn, DE), Shellsol(D (Shell Chemicals, Eschborn,
DE), and N-methylpyrrolidone. More preference is given to acetone, 2-butanone
and NN?-methylpyrroiidone.
The preparation of the water-dispersible blocked polyisocyanates 1) can take
place
in accordance with known methods of the prior art (e.g. in DE-A 2 456 469,
column 7-8, Example 1-5 and DE-A 2 853 937 pp. 21-26, Example 1-9).
The water-dispersible and/or water-soluble blocked polyisocyanates 1) are
obtained by reacting components A), B), C) and, if desired, D), E), F) in any
order
with the assistance where appropriate of an organic solvent C).
Preferably, first of all, A) is reacted with, where appropriate, a part,
preferably the
nonionic part, of component B) and also, where appropriate, D) and E). Then
blocking with component C) takes place, followed by reaction with the part of
component B) that contains ionic groups. Where appropriate, organic solvents
G)
can be added to the reaction mixture. In a further step, where appropriate,
component F) is added.
The preparation of the aqueous solution or dispersion takes place
subsequently, by
converting the water-dispersible, aralkylarnine-blocked polyisocyanates into
an
aqueous dispersion or solution by adding water. The organic solvent: G), where
used, can be removed by distillation following dispersion. It is preferred not
to use
solvent G)
For the preparation of the aqueous solution or dispersion comprising the water-
dispersible blocked polyisocyanates 1) the amounts of water used are generally
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such that the resulting dispersions or solutions have a solids content of from
10 to
70% by weight, preferably from 20 to 60% by weight and with more preference
from 25 to 50% by weight.
Suitable film-forming resins 2) are polymers which are soluble, emulsifiable
or
dispersible in water. Examples are polyester polymers or epoxy-functional
polyester polymers, polyurethanes, acrylic polymers, vinyl polymers such as
polyvinyl acetate, polyurethane dispersions, polyacrylate dispersions,
polyurethane-polyacrylate hybrid dispersions, polyvinyl ether and/or polyvinyl
ester dispersions, polystyrene and/or polyacrylonitrile dispersions, which can
be
used both in mixtures and in combination with further blocked polyisocyanates
and amino crosslinker resins such as melamine resins, for example. The solids
content of the film-forming resins is preferably from 10 to 100% by weight
with
more preference from 30 to 100% by weight.
Coupling agents 3) used are, for example, the known silane coupling agents,
examples being 3-aminopropyltrimethoxy- or triethoxysilane, N-(2-arninoethyl)-
3-aminopropyltrimethoxysilane, 3-glycidyipropyitrimethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane or 3-methacryloyloxypropyl-
triethoxysilane. The concentration of the silane coupling agents in the sizing
agents of the invention is preferably from 0.05 to 2% by weight with
particular
preference from 0.15 to 0.85% by weight based on the overall size.
The sizes of the invention comprise one or more nonionic and/or ionic
lubricants
4) contained, which may be composed, for example, of the following substance
groups: polyalkylene glycol ethers of fatty alcohols or fatty amines,
polyalkylene
glycol ethers and glycerol esters of fatty acids having 12 to 18 carbon atoms,
polyalkylene glycols, higher fatty acid amides having 12 to 18 carbon atoms of
polyalkylene glycols and/or alkyleneamines, quaternary nitrogen. compounds,
for
example ethoxylated imidazolinium salts, mineral oils and waxes. The
lubricants
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or lubricants are preferably employed in the overall concentration of between
0.05
and 1.5% by weight based on the overall size.
The sizing agents of the invention may comprise one or more antistats 5), such
as
lithium chloride, ammonium chloride, Cr(I I) salts, organotitanium compounds,
arylalkyl sulfates or sulfonates, aryl polyglycol ether sulfonates or
quaternary
nitrogen compounds. The antistats are preferably employed in concentrations of
from 0.01 to 0.8% by weight.
Furthermore, the sizes of the invention additionally comprise, where
appropriate,
other auxiliaries and additives 6) known from the prior art, such as are
described
in, for example, K.L. Loewenstein "The Manufacturing Technology of Continous
Glass Fibres", Elsevier Scientific Publishing Corp., Amsterdam, London, New
York, 1983.
The sizes can be prepared by the methods known per se. Preferably, about half
of
the total amount of water needed is charged to a suitable mixing vessel and,
with
stirring, the binder 2), the curing agent 1), and then the lubricant 4) and,
where
appropriate, other, customary auxiliaries 6) are added. Thereafter the pH is
adjusted to 5-7 and then hydrolysate of a conpling agent, for example of a
trialkoxysilane, prepared according to the specifications of the manufacturer
(e.g.
UCC, New York) is added. After a further stirring time of 15 minutes, the size
is
ready to use; where appropriate, the pH is readjusted to 5-7.
The sizes can be applied to a suitable substrate by any desired methods, for
example with the aid of suitable equipment, such as spray applicators or roll
applicators, for example. Suitable substrates are selected for example from
the
group consisting of metal, wood, glass, glass fibres, carbon fibres, stone,
ceramic
minerals, concrete, hard and flexible plastics of a wide variety of kinds,
woven
and non-woven textiles, leather, paper, hard fibres, straw and bitumen which
may
also have been provided, where appropriate, with customary primers prior to
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sizing. Preferred substrates are glass fibres, carbon fibres, metals, textiles
and
leather. A particularly preferred substrate is the glass fibre.
Glass types suitable for the sized glass fibres include not only the known
glass
types used for fibre glass manufacture, such as E, A, C, and S glass, but also
the
other conventional products of the glass fibre producers. Among the types of
glass
mentioned, for the production of continuous glass fibres, the E glass fibres
possess
the greatest importance for the reinf3rcement of plastics, owing to their
freedom
from alkali, high tensile strength and high modulus of elasticity.
The method of production, the method of sizing and the subsequent processing
of
the glass fibres is known and is described in, for example, K.L. Loewenstein
"The
Manufacturing Technology of Continous Glass Fibres", Elsevier Scientific
Publishing Corp., Amsterdam, London, New York, 1983.
The sizes are normally applied to the glass filaments, drawn at high speed
from
spinnerets, immediately following the solidification of the said filaments,
i.e. even
before they are wound up. An alternative option, however, is to size the
fibres in a
dip bath, following the spinning operation. The sized glass fibres can be
processed
either wet or dry to give, for example, chopped glass. The end product or
intermediate is dried at temperatures between 50 to 200 C, preferably 90 to
150 C. Drying in this context means not solely the removal of other volatile
constituents but also, for example, the solidification of the size
constituents. Only
after drying is at an end has the size become the finished coating material.
The
fraction of the size, based on the sized glass fibres, is preferably from 0.1
to 5.0%
by weight with particular preference from 0.1 to 3.0% by weight and with very
particular preference from 0.3 to 1.5% by weight.
As matrix polymers it is possible to use a multiplicity of thermoplastics and
polymers which can be cured to thermosets. Examples of suitable thermoplastic
polymers include the following: polyolefins such as polyethylene or
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polypropylene, polyvinyl chloride, addition polymers such as
styrene/acrylonitrile
copolymers, ABS, polymethacrylate or polyoxymethylene, aromatic and/or
aliphatic polyamides such as polyamide-6 or polyamide-6,6, polycondensates
such
as polycarbonate, polyethylene terephthalate, liquid-crystalline polyaryl
esters,
polyarylene oxide, polysulfone, polyarylene sulfide, polyaryl sulfone,
polyether
sulfone, polyaryl ether or polyether ketone or polyadducts such as
polyurethanes.
Examples that may be mentioned are polymers which can be cured to thermosets
include the following: epoxy resins, unsaturated polyester resins, phenolic
resins,
amine resins, polyurethane resins, polyisocyanurates, epoxy/isocyanurate
combination resins, furan resins, cyanurate resins and bismaleimide resins.
The present invention likewise provides for the use of the sizing composition
of
the invention for producing sized glass fibres.
The present invention additionally provides glass fibres sized with the sizes
of the
invention.
EXAMPLES
The mechanical properties of the sizes of the invention are determined on free
films. Preparation of the free films requires not the complete sizing
compositions
but only the film-forming constituents such as the water-dispersible block
polyisocyanate 1) and a film-forming resin 2), which are mixed with one
another,
since only these are determinants of the mechanical properties and also the
hydrolysis resistance of the size. The mixtures stated are prepared from 60%
by
weight of Baybond* PU 401 (anionic-nonionic PU dispersion having a solids
content of 40% and an average particle size of 100-300 nm, Bayer AG, DE (film-
forming resin 2)) and 40% by weight of a corresponding water-dispersible or
water-soluble blocked polyisocyanate 1). The free films are produced from
these
mixtures as follows: in a film applicator composed of two polished rolls,
which
can be set an exact distance apart, a release paper is inserted in front of
the back
roll. The distance between paper and front roll is adjusted using a feeler
gauge.
*trade-mark
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This distance corresponds to the (wet) film thickness of the resulting
coating, and
can be adjusted to the desired application rate of each coating. It is also
possible to
carrying out coating consecutively in two or more coats. To apply the
individual
coats, the products (aqueous formulations are adjusted to a viscosity of 4500
mPa=s beforehand by adding ammonia/polyacrylic acid) are poured onto the nip
between paper and front roll, the release paper is pulled away vertically
downwards, and the corresponding film is formed on the paper. Where two or
more coats are applied, each individual coat is dried and the paper is
reinserted.
The 100% modulus is determined in accordance with DIN 53504 on films >
100 pm in thickness.
Film storage under hydrolysis conditions takes place in accordance with DIN EN
12280-3. The mechanical properties of these film samples are determined after
24
hours of storage under standard climate conditions (20 C and 65% air humidity)
in accordance with DIN 53504.
The average particle sizes (the parameter stated is the numerical average) of
the
PU dispersions were determined by means of laser correlation spectroscopy
(instrument: Malvern Zetasizer* 1000, Malver Inst. Limited).
The mixtures set out below, comprising water-dispersible and/or water-soluble
and aralkylamine-blocked polyisocyanates, can be converted into sizes of the
invention by formulating them with the conventional lubricants 4), coupling
agents 3) and antistats 5) in a manner which is likewise conventional.
Example 1 (Inventive):
108.4 g of a polyisocyanate based on 1,6-diisocyanatohexane (HDI), containing
biuret groups and having an NCO content of 23.0%, are taken at 40 C. Over the
course of 10 minutes, 91.1 g of Polyether LB 25 (Bayer AG, DE, monofunctional
*trade-mark
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polyether based on ethylene oxide/propylene oxide having an average molar
weight of 2250 (OHN = 25)) and 1.22g- of the abovementioned hydrazine adduct
of
I mol of hydrazine hydrate and 2 mol of propylene carbonate of molecular
weight
236, of the formula III, are metered in with stirring. The reaction mixture is
subsequently heated to 90 C and stirred at this temperature until the
theoretical
NCO value has been reached. After it has cooled to 65 C, 88.3 g of N-te :-
butylbenzylamine are added dropwise with stirring over the course of 30
minutes
at a rate such that the temperature of the mixture does not exceed 70 C. Then
1.5 g of Tinuvin 770 DF (Ciba Spezialitaten GmbH, Lampertheim, DE) are
added, stirring is continued for 10 minutes and the reaction mixture is cooled
to
60 C. Dispersing is carried out by adding 713.0 g of water (20 C) at 60 C over
the course of 30 minutes. The subsequent stirring time at 40 C is 1 hour.
A storage-stable aqueous dispersion of the blocked polyisocyanate is obtained,
with a solids content of 27.3%.
Example 2 (Comparative example):
147.4 g of a polyisocyanate based on 1,6-diisoeyanatohexane (HDI), containing
biuret groups and having an NCO content of 23.0%, are taken at 40 C. Over the
course of 10 minutes, 121.0 g of Polyether LB 25 (Bayer AG, DE,
monofunctional polyether based on ethylene oxide/propylene oxide having an
average molar weight of 2250 (OHN = 25)) are metered in with stirring. The
reaction mixture is subsequently heated to 90 C and stirred at this
temperature
until the theoretical NCO value has been reached. After it has cooled to 65 C,
62.8 g of butanone oxime are added dropwise with stirring over the course of
30
minutes at a rate such that the temperature of the mixture does not exceed 80
C.
Dispersing is carried out by adding 726.0 g of water (T = 20 C) at 60 C over
the
course of 30 minutes. The subsequent stirring time at 40 C is 1 hour.
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A storage-stable aqueous dispersion of the blocked polyisocyanate is obtained,
with a solids content of 30.0%.
The results shown in T able 1 demonstrate that, with the use of the water-
dispersible, Iti-tert-butylbenzylamine-blocked crosslinker from Example I a
substantially higher hydrolysis resistance is achieved than with prior art
crosslinkers (Example 2). Furthermore, the tensile strength and elongation at
break indicate that, with mixture 1 after a drying time of 10 minutes at 125
C,
significantly higher mechanical, properties are achieved, owing to the lower
deblocking temperature of the blocking agent from crosslinker of Example 1
(N-tert-butylbenzylamine) as compared with mixture 2, which contains a
crosslinker having a prior art blocking agent (butanone oxime) (Example 2).
Table 1: Results of the mechanical properties of free films produced from
Examples 1 and 2 in combination with a binder
~li ~:uE ~l uxture 2
iHl~?yY] i'cy CIfi~;7ar _ti`v~ ,d C33~ e~
Film-forming resin 2): Baybond P1J 401 Baybond PU 401
Proportion 60% by weight 60% by weight
i Curing agent 1): Dispersion from Example I Dispersion from Example 2
(inventive) (comparative example)
Proportion 40% by weight 40% by weight
Blocking agent N-tert-butylbenzylamine Butanone oxime
Average particle size 143 nm 224 nm
Drying conditions 10 min, 125 C 10 min, 125 C
Preparation of the mixture Addition of 1) to 2); Addition of 1) to 2);
5 min stirring at room 5 min stirring at room
temperature temperature
Tensile test: P value
100% modulus [MPa] 2.7 T0.4
Tensile strength [MPa] 20.2 4.2
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Mixture lTl rxtuure
(inventive) J ra ve u1 pie)
Elongation at break [%] 860
Tensile test after 7d hvdrol-.Isis
Tensile strength [MPa] 19.8 Run
Elongation at break [%] 500 Run
Tensile test after 14d hydrolysis
Tensile strength [MPa] 18.3 Run
Elongation at break [%] 240 Run
Tensile test.after-4 weeks hydrolysis
Tensile strength [MPa] 12.2 Run
Elongation at break [%] 190 Run
Tensile test after 6 weeks hydrolysis {
Tensile strength [MPa] 7.2 Run
Elongation at break [%] 130 Run
Tensile test after 8 weeks hydrolysis
Tensile strength [MPa] Run Run
Elongation at break [%] Run Run
Example 3 (Inventive):
13.5 g of Polyether LB 25 (Bayer AG, DE, monofunctional polyether based on
ethylene oxide/propylene oxide having an average molar weight of 2250 (OHN =
25)) and 122.6 g of N-tert-butylbenzylamine are initially taken and are heated
to
90 C with stirring. Then 193.0 of a polyisocyanate based on 1,6-diisoeyanato-
hexane (HDI), containing isocyanurate groups and having an NCO content of
21.8%, are added over the course of 30 minates at a rate such that the
temperature
of the reaction mixture does not exceed 70 C. Following the addition of 11.1 g
of
the abovementioned hydrazine adduct of 1 rnol of hydrazine hydrate and 2 mot
of
propylene carbonate, of molecular weight 236, stirring is continued at 70 C
until
the theoretical NCO value has been reached. Then 3.5 g of Tinuvin 770 DF
(Ciba Spezialitaten GmbH, Lampertheim, DE) are added over 5 minutes at 70 C
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and the reaction mixture is stirred for a further 5 minutes. 24.6 g of the
hydrophilicizing agent KV 1386* (BASF AG, Ludwigshafen, DE) in solution in
73.7 g of water are metered in over the course of 2 minutes and the reaction
mixture is stirred for 15 minutes more. Dispersing by adding 736.4 g of water
(T =
60 C) in 10 min. The subsequent stirring time is 2 hours. A storage-stable
dispersion is obtained having a solids of 27.6%.
Example 4 (Comparative example):
963.0 g of a polyisocyanate based on 1,6-diisocyanatohexane (HDI), containing
biuret groups and having an NCO content of 23.0%, are mixed with 39.2 g of
Polyether LB 25 (Bayer AG, DE, monofunctional polyether based on ethylene
oxide/propylene oxide having an average molar weight of 2250 (OHN = 25)) and
7.8 g of the abovementioned hydrazine adduct of 1 mol of hydrazine hydrate and
2 mol of propylene carbonate of molecular weight 236 at 100 C for 30 minutes.
Then 493.0 g of -caprolactam are added over the course of 20 minutes at a
rate
such that the temperature of the reaction mixture does not exceed 110 C. The
mixture is stirred at 110 C until the theoretical NCO value has been reached
and is
then cooled to 90 C. Following the addition of 7.9 g of Tinuvin 770 DF (Ciba
Spezialitaten GmbH, Lampertheim, DE) and a subsequent stirring time of 5
minutes, a mixture of 152.5 g of the hydrophilicizing agent KV 1386 (BASF AG,
Ludwigshafen, DE) and 235.0 g of water is metered in over the course of 2
minutes and stirring is continued for 7 minutes more at neutral temperature.
This
is followed by dispersing, by adding 3341.4 g of water. After a subsequent
stirring
time of 4 hours, a storage-stable aqueous dispersion was obtained having a
solids
content of 29.9%.
*trade-mark
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Table 2: Results of the mechanical properties of free films produced from
Examples 3 and 4 in combination with a binder-
Mixtur, 3
(inventive
Film-forming resin 2): Baybond PU 401 Baybond PU 401
Proportion 60% by weight 60% by weight
Curing agent 1): 1 Dispersion from Example 3 Dispersion from Example 4
(inventive` (comparative example)
Proportion 40% by weight 40% by weight
Blocking agent N-tert-butylbenzylamine c-caprolactam
Average particle size 95 nm 235 nm
1 -
j Drying conditions 10 min, 125 C 10 min, 125 C
Preparation of the mixture Addition of 1) to 2); Addition of 1) to 2);
rain stirring at room 5 mitt stirring at room
terperats re t=erature
Tensile test: O value
100% modulus [MPa] 1.8 1.2
Tensile strength [MPa] 17.3 8.5
Elongation at break [%] 880 1020
Tensile test after 7d hvr,,jlvsis
Tensile strength [MPa] 17.0 has run
Elongation at break [%] 480 has run
-- ---- ---- Tensile test after 14d hydrolysis
i ensile strength [MPa] 17.5 has run
Elongation at break [%] 300 has run
Tensile test after 4 weeks hydrolysis
Tensile strength [MPa] 12.8 1 has run
Elongation at break [%] 300 has run
Tensile test after 6 weeks hydrolysis
Tensile strength [MPa] 6.5 has run
Elongation at break [%] 160 has run
Tensile test after 8 weeks hydrolvsiu
Tensile strength [MPa] has run has run
Elongation at break [%] has run had run
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The results shown in Table 2 demonstrate that, with the use of the water-
dispersible, N-tort-butylbenzylan-tine-blocked crosslinker from Exan'iple 3 a
substantially higher hydrolysis resistance is achieved than with prior art
crosslinkers (Example 4). Furthermore, the tensile strength and elongation at
break indicate that, with mixture 3 after a drying time of 10 minutes at 1 25
C,
significantly higher mechanical properties are achieved, owing to the lower
deblocking temperature of the blocking agent from the crosslinker of Example 3
(N-tert-butylbenzylamine) as compared with mixture 6, which contains a
crosslinker having a prior art blocking agent (caprolactam) (Example 4).
Example 5 (Inventive)
192.6 g of a polyisocyanate based on 1,6-diisocyanatohexane (HDI), containing
biuret groups and having an NCO content of 23.0%, are mixed with 7.8 g of
Polyether LB 25 (Bayer AG, DE, monofunctional polyether based on ethylene
oxide/propylene oxide having an average molar weight of 2250 (OHN = 25)) at
100 C for 30 minutes. Then, at 70 C , 142.0 g ofN-tert-bu.tylbenzyiamine are
added over the course of 30 minutes at a rate such that the temperature of the
reaction mixture does not exceed 75 C. The mixture is stirred at 75 C until
the
theoretical NCO value has been reached. A mixture of 27.5 g of the
hydrophilicizing agent KIT 1386 (BASF AG, Ludwigshafen, DE) and 46.8 g of
water is metered in over the course of 2 minutes and stirring is continued for
7
minutes more at neutral temperature. This is followed by dispersing, by adding
761.3 g of water. After a subsequent stirring time of 4 hours, a storage-
stable
aqueous dispersion was obtained having a solids content of 28.0%.
Example 6 (Comparative example):
963.0 g of a polyisocyanate based on 1,6-diisocyanatohexane (HDI), containing
biuret groups and having an NCO content of 23.0%, are mixed with 39.2 g of
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Polvether LB 25 (Bayer AG, DE, mono function a- polyether based on ethylene
oxide/propylene oxide having an average molar weight of 2250 (OHN = 25)) at
100 C for 30 minutes. Then 493.0 g of c-caprolactam are added over the course
of
20 minutes at a rate such that the temperature of the reaction mixture does
not
exceed 110 C. The mixture is stirred at i 10 C until the theoretical NCO value
has
been reached and is then cooled to 90 C. Following a subsequent stirring time
of 5
minutes, a mixture of 152.5 g of the hydrophilicizing agent KV 1386 (BASF AG,
Ludwigshafen; DE) and 235.0 g of water is metered in over the course of 2
minutes and stirring is continued for 7 minutes more at neutral temperature.
This
is followed by dispersing, by adding 3325.1 g of water. After a subsequent
stirring
time of 4 hours, a storage-stable aqueous dispersion is obtained having a
solids
content of 30.0%.
Table 3: Results of the mechanical properties of free films produced from
Examples 5 and 6 in combination with a binder
Film-forming resin 2): Baybond P U 401 Baybond PU 401
Proportion 60% by weight 60% by weight
Curing agent 1): Dispersion from Example ; Dispersion from Example 6
(inventive) (comparative example)
Proportion 40% by weight 40% by weight
Blocking agent N-tert-butylbenzylamine a-caprolactam
Average particle size 110 nm 153 nrn
Drying conditions 10 min, 125 C 10 min, 125 C
Preparation of the mixture Addition of 1) to 2); Addition of 1) to 2);
5 min stirring at room 5 min stirring at room
terry -lerature temperature
Tensile test: 0 value - --- - - 100% modulus [MPa] 2.0 0.8
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Mixture 5 ixturc
(inventive) coif ~i 6l i41.~'~' i e= F e)
Tensile strength [MPa] 16.9 8.4
Elongation at break [%] 1020 1250
Tensile test after 7d hydrolysis
Tensile strength [MPa] 17.8 has run
Elongation at break [%] 190 has run
Tensile test after 14d `hydrolysis
Tensile strength [MPa] 1-8.0 has run
Elongation at break [%] 240 has run
Tensile test after 4 weeks hydrolysis
Tensile strength [MPa] 20.0 has run
Elongation at break [%] 210 has run
Tensile test after 6 weeks hydrolysis
Tensile strength [MPa] 15.7 has run
Elongation at break [%] 200 has run
The results shown in Table 3 demonstrate that, with the use of the water-
dispersible, N-tert-butylbenzylamine-blocked crosslinker from Example 5, a
substantially higher hydrolysis resistance is achieved than with prior art
crosslinkers (Example 6). Furthenrnore, the tensile strength and elongation at
break indicate that, with mixture 5 after a drying time of 10 minutes at 125
C,
significantly higher mechanical properties are achieved, owing to the lower
deblocking temperature of the blocking agent from crosslinker of Example 5
(N-tert-butylbenzylamine) as compared with mixture 6, which contains a
crosslinker having a prior art blocking agent (caprolactam) (Example 6).
Mixtures 1-6 are processed to sizes for example as follows: About half of the
water required is charged to a suitable mixing vessel and, with stirring, in
succession, one of the abovementioned mixtures of film-forming resin 2) and
115 crosslinker 1), lubricant 4) (e.g. Breox(D 50-A 1.40, BP Chemicals) and,
where
appropriate, other, customary auxiliaries 5, 6) are added. Thereafter the pH
is
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adjusted to 5-7 and then hydrolysate of 3-anhinopropyltriethoxysilane (Al 100)
prepared according to the specifications of the manufacturer (e.g. UCC, New
York) is added. After a further stirring time of 15 minutes, the size is ready
to use;
where appropriate, the pH is readjusted to 5-7. The size,:, thus resulting
from
mixture 1, 3 and 5 are then sizing compositions according to the invention.
Size 1 Size 2 Size 3 Size 4 Size 5 Size 6
Water 42.0 kg 142.0 kg 42.0 kg 42.0 kg 42.0 kg 42.0 kg
Binder 15.0 kg i5.0 kg 15.0 kg 15.0 kg 15.0 kg 15.0 kg
mixture 1 mixture 2 mixture 3 mixture 4 mixture 5 mixture 6
A 1100 0.6 kg 0.6 kg 0.6 kg 0.6 kg 0.6 kg 0.6 kg
Breox 0.4 kg 0.4 kg 0.4 kg 0.4 kg 0.4 kg 0.4 kg
50-A140
Water 42.0 kg 42.0 kg 42.0 kg 42.0 kg 42.01 ':g 42.0 kg
Total 100.0 kg 100.0 kg 100.0 kg 100.0 kg 100.0 kg 100.0 kg
Then, in a conventional manner, glass fibres were produced, sized with the
inventive sizes 1, 3 and 5 and with the sizes of the Comparative Examples 2, 4
and
6, chopped and dried. The glass fibres were compounded into a polyamide for
reinforcement. The results of the free films of the mixtures are comparable to
a
very high degree with the results of the sizes on the glass fibre in respect
of
hydrolysis stability and mechanical properties. The mechanical properties of
the
inventive sizes prepared from mixtures 1, 3 and 5 show significantly improved
mechanical properties and strongly improved hydrolysis resistances on the
glass
fibre in comparison with the sizes from mixtures 2, 4 and 6.
Although the invention has been described in detail in the foregoing for the
purpose of illustration, it is to be understood that such detail is solely for
that purpose
and that variations can be made therein by those skilled in the art without
departing
from the spirit and scope of the invention except as it may be limited by the
claims.
