Note: Descriptions are shown in the official language in which they were submitted.
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DESCRIPTION
METHOD FOR CLEANING AND/OR DESOILING A HARD SURFACE
TECHNICAL FIELD
The present invention relates to a method for cleaning and/or desoiling a hard
~ surface.
BACKGROUND ART
Depending on the location of use, various types of soil deposit on the hard
surfaces of
baths, washstands, restrooms, and other damp locations. For example, the soil
in baths
comprises proteins and other nitrogenous compounds, fatty acid metal salts, or
the like; the
soil in washstands comprises fatty acid nletal salts and the like; and the
soil in restrooms
comprises urolith deposits, soil that is based on fecal matter, urine, and
other types of
excrenient, and the like. In addition, these hard surfaces undergo repeated
drying after
coming into constant contact with tap water, so silicate scale or carbonate
scale derived from
tap water are concentrated and deposited locally, producing soil commonly
referred to as
"water spots" or "water stains." In particular, the restroom bowls, washbowls,
and other
ceramic fixtures, as well as mirrors and other -lass surfaces in restroom
areas are hydrophilic,
and therefore tend to be covered with water stains.
If such water stains continue to build up over a long time, the water stains
bond firmly
with the hard surfaces, and not only does removal become more difficult, but
the components
of the water stains tend to become a breeding ground for nlold and gemis
together with other
types of soil, and sanitary probleins are encountered. Initial water stains
can be removed
relatively easily by careful cleaning, but currently the situation is such
that the frequency of
cleaning tends to decrease due to the streamlining of cleaning operations.
h1 view of this, a need exists for detergents that have the ability (anti-
soiling effect) to
reduce deposits of water stains and other types of soil, and detergents that
clean and at the
same tiine endow cleaned surfaces with the anti-soiling effect have come to be
developed in
order to prevent water stains from firmly adhering to hard surfaces.
Detergents endowed with
the ability to form films on the cleaned surfaces and to provide an anti-
soiling effect by the
incorporation of specific organopolysitoxanes into the detergent composition
have been
proposed as products that combine such an anti-soiling effect.
Examples of disclosed detergents that combine an anti-soiling effect and
contain such
organopolysiloxanes include compositions for bathtub cleanint', that contain
amino-modified
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organopolysiloxanes and nonionic surfactants, inhibit redeposition of water-
formed deposits,
and have protective action on bathtub materials (refer, for example, to
Japanese Patent
Application Laid-open No. S51-83608), as well as detergent compositions that
contain
specific organopolysiloxane and provide delustering and surface protection to
bath fixtures
(refer, for example, to Japanese Patent Application Laid-open No. H3-197596).
Also
disclosed is a detergent composition for the desoiling and antibacterial
cleaning of hard
surfaces that contains specific cationic surfactants, cation-based
bactericidal agents, and
hydrophilic organopolysiloxanes and has an anti-soiling effect and
antibacterial action (refer,
for example, to Japanese Patent Application Laid-open No. 2000-198999).
Japanese Patent Application Laid-open Nos. S51-83608 and H3-197596 disclose
detergent compositions that have excellent anti-soiling effects and detergency
with respect to
water-formed deposits and soil, but there is no mention of an anti-soiling
effect on water
stains, nor is there any disclosure made concerning sustained anti-soiling
effects or storage
stability, which are believed to be important in practical terms. Japanese
Patent Application
Laid-open No. 2000-198999 discloses a detergent composition that has an
excellent anti-
soiling effect on water stains.
DISCLOSURE OF THE INVENTION
The prior art does not disclose or recognize the need for storage stability or
details of
detergency, and a detergent that simultaneously satisfies all the requirements
related to
enhanced detergency, excellent anti-soiling effects, and adequate storage
stability has yet to
be developed.
A need therefore exists for developing a detergent that would exhibit
excellent anti-
soiling effects and storage stability in addition to excellent detergency even
in restrooms,
washstands, baths, and other locations in repeated contact with tap water.
An object of the present invention is to provide a detergent composition that
combines
an excellent anti-soiling effect on cleaned surfaces, preserves this anti-
soiling effect, and
exhibits excellent storage stability in addition to having excellent
detergency. More
specifically, the object is to provide an anti-soiling detergent composition
that can be used to
advantage for cleaning and anti-soiling of hard surfaces such as those of
plastic, stainless
steel, porcelain, tile, glass, ceramic, granite/terrazzo, and other natural
stone materials in
restrooms, washstands, baths, and other damp locations; particularly, for
cleaning and anti-
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soiling of water stains on hard surfaces such as those of tile, glass, and
ceramic in restroom
and washstands.
The inventors have discovered that an anti-soiling detergent composition that
has an
excellent anti-soiling effect on cleaned surfaces, preserves this anti-
soi.ling effect, and exhibits
excellent storage stability in addition to having excellent detergency can be
obtained by
combining a polyetheramide-nlodified organopolysiloxane andJor amino-modified
organopolysiloxane, a surfactant, a metal chelating agent, and water. The
present invention
was perfected on the basis of this discovery.
Specifically, the present invention provides a method for cleaning and/or
desoiling a
hard surface comprising contacting said hard surface with a composition which
compreses:
(A) 0.05 to 10 mass% of a polyetlieramide-modified organopolysiloxane and/or
anlino-modified organopolysiloxane;
(B) 0.1 to 30 mass% of at least one type of surfactant selected from nonionic
surfactants, aniphoteric surfactants, and cationic surfactants;
(C) 0.1 to 20 mass% of a metal chelating agent; and
(D) water.
The anti-soiling detergent composition of the invention may also contain (E)
0.01 to
5 mass% of a thickener in addition to components (A) to (D).
The anti-soiling detergent composition of the invention may further contain
(F) 0_ 1 to
20 mass% of a water-soluble solvent in addition to the above components.
The anti-soiling detergent composition of the present invention contains
components (A), (B), (C), and (D) as essential ingredients.
The component (A) used in the present invention is a polyetheramide-modified
organopolysiloxane andlor amino-modified organopolysiloxane, and it is added
with the
purpose of endowing the cleaned surface with an anti-soiling effect.
The polyetheramide-modified organopolysiloxane of component (A) used in the
present invention may be a organopolysiloxane having polyoxyethylene groups
and amido
groups expressed by average compositional fonnula (1)
~
R I aR-hQ cQ-dS10(q_a_b_c_d), Z 1
O
tn average compositional formula (1), a and d are zero or positive numbers; b
and c
arc positive numbers such that 1.9 S a + b + c + d< 2.2; and Ri is a hvdrogen
atom, a
hydroxyl group, or a substituted or unsubstitute.d monovalent hydrocarbon
group -with 1 to 6
carbon atoms. Specific examples of such monovalent hydrocarbon groups include
methyl,
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ethyl, propyl, butyl, pentyl, hexyl, and other alkyl groups; phenyl, tolyl,
xylyl, and other aryl
groups; benzyl, phenethyl, and other aralkyl groups; and 3-chloropropyl,
3,3,3-trifluoropropyl, and other halo-substituted alkyl groups.
In formula (1), R2 is a monovalent hydrocarbon group with I to 6 carbon atoms,
specific examples of which include methyl, ethyl, propyl, butyl, pentyl,
hexyl, vinyl, and
phenyl groups.
In formula (1), Ql is a divalent organic group having an amido group expressed
by
general formula (2) or (3)
[Chemical Formula 4]
R 4 0
I 11 (2)
~- R S-ivT': -- C _ X
RA R SO
I I 0 (3)
-- R ~ -~- N -.. R ~ --= N - C - X
In general formulae (2) and (3), R3 and RS are divalent hydrocarbon groups
with 2 to 18
carbon atoms, specific examples of which include ethylene, propylene,
butylene, isobutylene,
pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl
groups. In
the formulae, R4 and R6 are hydrogen atoms or monovalent hydrocarbon groups
with 1 to 6
carbon atoms, specific examples of which include methyl, ethyl, propyl, butyl,
pentyl, hexyl,
and other alkyl groups; phenyl, tolyl, xylyl, and other aryl groups; benzyl,
phenethyl, and
other aralkyl groups; and 3-chloropropyl, 3,3,3-trifluoropropyl, and other
halo-substituted
alkyl groups.
In general formulae (2) and (3), X is a monovalent organic group expressed by
general
formula (4)
-R'eOf-(C2H40)g (R80)h-Y (4),
where e andf are each 0 or 1, and g and h are zeros or positive integers of 1
or greater.
R7 is a divalent hydrocarbon group with 2 to 18 carbon atoms, specific
examples of which
include ethylene, propylene, butylene, isobutylene, pentamethylene,
octamethylene,
decamethylene, dodecamethylene, and cyclohexyl groups. R 8 is a divalent
hydrocarbon group
with 3 to 10 carbon atoms, specific examples of which include propylene,
isopropylene,
butylene, and isobutylene groups. Y is a group selected from among hydrogen
atoms, alkyl
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groups, acyl groups, and isocyanic groups, examples of which include methyl,
ethyl, propyl,
acetyl, and propionyl groups.
In formula (1), Q2 is a monovalent organic group having a polyoxyalkylene
group
expressed by general formula (5)
5 -R9;Oi-(C2H40)k-(Ri00)m Z (5)
where i andj are each 0 or 1; k is a positive integer of 1 or greater; m is
zero or a
positive number of 1 or greater; and R9 is a divalent hydrocarbon group with 2
to 18 carbon
atoms, specific examples of which include ethylene, propylene, butylene,
isobutylene,
pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl
groups.
R10 is a divalent hydrocarbon group with 3 to 10 carbon atoms, specific
examples of which
include propylene, isopropylene, butylene, and isobutylene groups. Z is a
group selected from
among hydrogen atoms, alkyl groups, acyl groups, and isocyanic groups,
examples of which
include methyl, ethyl, propyl, acetyl, and propionyl groups.
The molecular structure of the polyetheramide-modified organopolysiloxane
maybe
not only linear but also branched, cyclic, or reticulated.
The polyetheramide-modified organopolysiloxane having such amido groups and
polyoxyethylene groups may, for example, be a compound expressed by the
following general
formula.
[Chemical Formula 5]
i-ia CHa GHa IIs
CHS--SiO(SiO), (SiO) 0 ~i-~CHa
I I 1 20 ~H9 CHs R" (Ils
(In the formula, Rl l is -(CH2)3NHCO(CH2)qO(CH2CH2O)r(CH2)sH, where n is 10 to
1000, p is 1 to 100, q is 1 to 100, r is 2 to 20, and s is 0 to 20.)
[Chemical Formula 6]
C
I Hs lHC s ?Ha I C H8 fH9
CHS--ISiO( IiC))t (~ i4)~n (~ iCy)p CHS
CH3 CHa R'2 R13 CH3
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(In the formula, R'Z is -(CH2)3NH(CH2)2NHCO(CH2),vH, R13
is -(CH2)3O(CH2CH2O),(CH2CHCH3O)Y(CH2)ZH, t is 10 to 1000, u is 1 to 100, v is
1 to 100,
w is 1 to 20, x is 2 to 20, y is 0 to 20, and z is 0 to 20.)
[Chemical Formula 7]
Cf IO CHO CH3 CHS CH'a
E'--SiO(~IO)m.., (SiC))ma (Si.E))'.sSI--.E2
CH3 CH$ R ~1 R " CHS
(In the formula, R ' is
-(CH2)3NHCO(CH2)m4Oms(CH2CH2O)m6(CH2CHCH3O)m7(CH2)m8H; Rc2
is -(CH2)30(CH2CH2O)m9(CH2CHCH30)mto(CH2)mi 1D1; E' and E2, which may be the
same
or different, are R ', Rcz, -OH, or -(CH2)pyH, and preferably -CH3; D' is -H
or -COCH3; ml
is 10 to 1000; m2 is 1 to 100; m3 is 0 to 100; m4 is 1 to 100; m5 is 0 or 1;
m6 is 0 to 20; m7
is0to20;m8is0to20;m9is2to20;ml0is0to20;m11 is0to20;p1 is 0 to 20; and m3
and m6 cannot both be 0 at the same time.)
[Chemical Formula 8]
CH3 CH'3 i H3 C143 C~ S
~+3--1 yt~ kSiV)mi2 tw ~~J)m19 (a~ ~.7,~m1~4,i._.E=''~
I HS CH3 R~$ R== I
C ,GH3
(In the formula, Ro3
is -(CH2)3NH(CHz)ZNHCO(CH2)m1sOm16(CH2CHzO)m17(CH2CHCH3O)m]g(CH2)m19H; Ra4
is -(CH2)3O(CH2CH3O),,,20(CH2CHCH3O)iii21(CH2)m22D2; E3 and Ea, which may be
the same
or different, are Ro3, Rc4, -OH, or -(CH2)p2H, and preferably -CH3; D2 is -H
or -COCH3;
m12 is lO to 1000; m13 is 1 to 100; m14 is O to 100; m15 is 1 to 100; m16 is 0
or 1; m17 is 0
to20;m18is0to20;m19is0to20;m20is2to20;m21 is 0 to 20; m22 is 0 to 20; p2 is 0
to
20; and m14 and m17 cannot both be 0 at the same time.)
Compounds having chemical structures such as those shown below can be cited as
specific examples.
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[Chemical Formula 9]
~H3 ~ HO CHa ~ Ha
CHa-i iU(~ft7)~, ( ~fCl)2e ~ i-CHs
CUR Ch;s G' CHa
(In the formula, G' is (CH2)3NHCOCH2O(CH2CH2O)4C12H25.)
[Chemical Formula 10]
CHg i Hg # 9 8
CHS-~ i~,( ~Io)~,D (~'O) ~b ~ i-cn3
CHg CHe 02 CH$
(In the formula, G2 is (CH2)3NH(CH2)2NHCO(CH2)30(CH2CH2O)1OC12H25.)
[Chemical Formula 11 ]
1 H,~ I H,~ ~H9 IHg ~`IHg
Ga- itt)(~ C)eauo (~~
~ )jo (~ i'~)so ?i_G3
k.iRg ~I-13 G" G4 CHS
(In the formula, G3 is (CH2)30(CH2CH2O)lo(CH2CHCH3O)10H, and G4 is
(CH2)3NHCO(CH2)30(CH2CH2O)6C1aH21.)
[Chemical Formula 12]
C
I HS ' CH3 4C Hs 1H'3 fHS
W~-~ io(s~o)m (~ io),O (-` io-),d ~t-o~Ã
CI1& CHa G5 CHS
(In the formula, G5 is (CH2)30(CH2CH2O)IOCOCH3, and G6 is
(CH2)3NH(CH2)2NHCOC 16H33 =)
The polyetheramide-modified organopolysiloxane of component (A) used in the
present invention may also be a organopolysiloxane having an amino group,
polyoxyethylene
group, and amido group expressed by average compositional formula (6)
K 1 aR2bQ 1 cQ2dQ3e 1 S10(4-a-b-c-d-el )/2 (6)
In formula (6), a and d are zeros or positive numbers; b, c, and el are
positive
numbers such that 1.9 <_ a+ b + c + d+ el <_ 2.2; and R' is a hydrogen atom, a
hydroxyl
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group, or a substituted or unsubstituted monovalent hydrocarbon group with 1
to 6 carbon
atoms. Specific examples of such monovalent hydrocarbon groups include methyl,
ethyl,
propyl, butyl, pentyl, hexyl, and other alkyl groups; phenyl, tolyl, xylyl,
and other aryl groups;
benzyl, phenethyl, and other aralkyl groups; and 3-chloropropyl, 3,3,3-
trifluoropropyl, and
other halo-substituted alkyl groups.
In formula (6), R2 is a monovalent hydrocarbon group with 1 to 6 carbon atoms,
specific examples of which include methyl, ethyl, propyl, butyl, pentyl,
hexyl, vinyl, and
phenyl groups.
In formula (6), Ql is a divalent organic group having an amido group expressed
by
general formula (2) or (3)
[Chemical Formula 13]
12"t7
1 11 (2)
--~a -N - G - X
R 4 RgO
i I 11. (3)
R 3 _N _R s_N _C -X
In general formulae (2) and (3), R3 and R5 are divalent hydrocarbon groups
with 2 to
18 carbon atoms, specific examples of which include ethylene, propylene,
butylene,
isobutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene,
and
cyclohexyl groups. In the formulae, R4 and R6 are hydrogen atoms or monovalent
hydrocarbon groups with 1 to 6 carbon atoms, specific examples of which
include methyl,
ethyl, propyl, butyl, pentyl, hexyl, and other alkyl groups; phenyl, tolyl,
xylyl, and other aryl
groups; benzyl, phenethyl, and other aralkyl groups; and 3-chloropropyl,
3,3,3-trifluoropropyl, and other halo-substituted alkyl groups.
In general formulae (2) and (3), X is a monovalent organic group expressed by
general
formula (4)
-RIeOf--(C2H4O)g-(RgO)h Y (4),
where e andf are each 0 or 1, and g and h are zeros or positive integers of 1
or greater.
R7 is a divalent hydrocarbon group with 2 to 18 carbon atoms, specific
examples of which
include ethylene, propylene, butylene, isobutylene, pentamethylene,
octamethylene,
decamethylene, dodecamethylene, and cyclohexyl groups. R8 is a divalent
hydrocarbon group
with 3 to 10 carbon atoms, specific examples of which include propylene,
isopropylene,
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butylene, and isobutylene groups. Y is a group selected from among hydrogen
atoms, alkyl
groups, acyl groups, and isocyanic groups, examples of which include methyl,
ethyl, propyl
acetyl, and propionyl groups.
In formula (6), Q2 is a monovalent organic group having a polyoxyalkylene
group
expressed by general formula (5)
-R9;Oi-(C2H4O)k-(Ri0O)m Z (5),
where i and j are each 0 or 1; k is a positive integer of 1 or greater; m is
zero or a
positive integer of 1 or greater; R9 is a divalent hydrocarbon group with 2 to
18 carbon atoms,
specific examples of which include ethylene, propylene, butylene, isobutylene,
pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl
groups;
R10 is a divalent hydrocarbon group with 3 to 10 carbon atoms, specific
examples of which
include propylene, isopropylene, butylene, and isobutylene groups; and Z is a
group selected
from among hydrogen atoms, alkyl groups, acyl groups, and isocyanic groups,
examples of
which include methyl, ethyl, propyl, acetyl, and propioriyl groups.
In formula (6), Q3 is a divalent organic group having an amino group expressed
by
general formula (7) or (8)
[Chemical Formula 141
R 4
- ~ . ~ .,,.. H (7)
R
R 4 R 6
I 1 (8)
R a _ N , R s - N . _. H
In general formulae (7) and (8), R3 to R6 are the same as above.
Because of considerations related to the sustainability of the anti-soiling
effect, the
total amount of the primary and secondary amino groups of general formula (7)
or (8)
contained in the polyetheramide-modified organopolysiloxane molecules is
preferably within
a range of 0.15 to 0.45 mass%. When the total content of the primary and
secondary amino
groups is less than 0.15 mass%, the anti-soiling effect has inferior
sustainability because of
the poor adsorption of the polyetheramide-modified organopolysiloxane on the
cleaned
surfaces, whereas the composition has inferior storage stability when the
content exceeds
0.45 mass%.
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The molecular structure of the polyetheramide-modified organopolysiloxane may
be
not only linear but also branched, cyclic, or reticulated.
The polyetheramide-modified organopolysiloxane having such amido groups,
polyoxyethylene groups, and amino groups may, for example, be a compound
expressed by
5 the following general formula.
[Chemical Formula 15]
~ H~g ~H.g (~',~"~$ 0.~+~3 ~.~.HB ~ H~
rI7-~ io(s~ c~).} t ~ 'O?,2 ( ~i~i)p3(S~O)~S~-~E~
(-;fi'g C,H9 , . R - R ~s ~ le: CHs
(In the formula, R14 is -(CH2)3O(CH2CH2O)õ5(CH2CHCH3O)õ6(CH2)õ7D3; R's
is -(CH2)3NH2; R16 is -
(CH2)3NHCO(CH2)n8Or9(CH2CH2O)nto(CH2CHCH30)n1t(CH2)ni2H;
10 E5 and E6, which may be the same or different, are R14, Rls, R16, -OH, or -
{CH2)p3H, and
preferably -CH3; D3 is -H or -COCH3; nl is 10 to 1000; n2 is 0 to 100; n3 is 1
to 100; n4 is 1
to100;n5is2or20;n6isOto20;n7isOto20;n8is1to100;n9is0orl;nlOisOto20;
nl 1 is 0 to 20; n12 is 0 to 20; p3 is 0 to 20; and n2 and nlO cannot both be
0 at the same
time.)
[Chemical Formula 16]
CHg CH3 4:H2 CHg CHS CH3
{Si0)n~6~Si0)~r~S11i-Es
E''-6iiU{StlitCy~,,13 (SYg},14
Ol:ig CH3 R 1'
(In the formula, R17 is -(CH2)3O(CH2CH2O)õi7(CH2CHCH3O)n1s(CH2)n19D4; R18
is -(CH2)3NH(CH2)2NH2; R'9
is -(CH2)3NH(CH2)2NHCO(CH2).2oOn2i(CH2CH2O)i22(CH2CHCH3O)n23(CH2)õ24H; E' and
E$, which may be the same or different, are Rl7, R'g, R'9, -OH, or -(CH2)p4H,
and
preferably -CH3; D4 is -H or -COCH3; n13 is 10 to 1000; n14 is 0 to 100; n15
is 1 to 100;
n16 is 1 to 100; n17 is 2 or 20; n18 is O to 20; n19 is O to 20; n20 is 1 or
100; n2l is 0 or 1;
n22 is 0 to 20; n23 is 0 to 20; n24 is 0 to 20; p4 is 0 to 20; and n14 and n22
cannot both be 0
at the same time.)
Compounds having chemical structures such as those shown below can be cited as
specific examples.
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[Chemical Formula 17]
iHg iHy iHg i.~g ~iHg i~g
CHO-- ~ iQ ( IiC)) ¾00 ( 9fJ) 6 ( ~ iO) 5( ~iU) a j i -+Ci~$
CrI 0 C~a G 14 G 7A '"'a CH:3
(Tn the formula G14 is -(CH2)3O(CH2CH2O)5C12H25, Gts is -(CH2)3NH2, and G16
is -(CH2)3NHCOCH2O(CH2CH2O)5C12H25.)
[Chemical Formula 18]
He CHS CH3 CH3 H3 HO
CHS - ~ it? (~it~~'~~o (~ iC)) ta ( ~iCi) ~(S~ fl) j2S~ -+GH3
CH3 Crfa G" G2s GIO CHa
(In the formula G'7 is -(CH2)30(CH2CH2O)1oC10H21i Gl$ is -(CH2)3NH(CH2)2NH2,
and G'9 is -(CH2)3NH(CH2)2NHCOCH2O(CH2CH2O)4CI0H21.)
The amino-modified organopolysiloxane of component (A) used in the present
invention is commonly known as amino-modified organopolysiloxane, which is
commercially
available. It is possible, for example, to use an amino-modified product of a
organopolysiloxane in which some of the methyl groups in the
polydimethylsiloxane are
substituted by at least one type of group selected from organic groups having
amino groups or
substituted amino groups, such as aminomethyl, aminoethyl, aminopropyl,
aminobutyl, and
other aminoalkyl groups, as well as aminoethyl-substituted aminopropyl and
other
aminoalkyl-substituted aminoalkyl groups (other substituents may also be
contained).
Among these, compounds expressed by the following general formula are
preferably
used because of considerations related to anti-soiling effects.
[Chemical Formula 19]
C
I He I C H3 C I Hs ~H3
CH3--r~ iO(~ i.C3)ai(~ i.t'~)bi ;i--CH3
CH$ CHS R' CH$
I+FH-R --NH 2
(In the formula, R' and R" are divalent hydrocarbon groups with 1 to 10 carbon
atoms,
al is zero or a positive number of 1 or greater, and bl is a positive number
of 1 or greater.)
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In the above general formula, the same groups as those described above can be
cited
as examples of the divalent hydrocarbon groups with 1 to 10 carbon atoms.
Using a
polyetheramide-modified organopolysiloxane for component (A) is more preferred
from the
standpoint of storage stability.
The admixed amount of component (A) is selected from the range of 0.05 to
mass%, based on the total mass of the composition. An inferior anti-soiling
effect will be
produced if this amount is less than 0.05 mass%, and the increase in the anti-
soiling effect
will reach saturation and the economic efficiency will actually be low if more
than 10 mass%
is admixed. The admixed amount of component (A) is preferably within a range
of 0.1 to
10 8 mass% because of considerations related to the anti-soiling effect and
storage stability, and
even more preferably within a range of 0.1 to 5 mass% because of
considerations related to
economic efficiency. Component (A) may be used singly or as a combination of
two or more
ingredients.
The surfactant of component (B) used in the present invention is admixed with
the
purpose of removing the soil adhered to the cleaned surface and solubilizing
the
polyetheramide-modified organopolysiloxane and/or amino-modified
organopolysiloxane,
which is component (A).
At least one type of surfactant selected from among nonionic surfactants,
amphoteric
surfactants, and cationic surfactants is used as the surfactant of component
(B) because of
considerations related to the anti-soiling effect, which is the effect
possessed by
component (A).
Examples of such nonionic surfactants include polyoxyalkylene alkyl ethers,
polyoxyalkylene alkenyl ethers, polyoxyalkylene alkyl phenyl ethers, alkyl
polyglucosides,
fatty acid polyglycerine esters, fatty acid sugar esters, and fatty acid
alkanolamides. In the
present invention, polyoxyalkylene alkyl ethers, alkyl polyglucosides, and
fatty acid
alkanolamides are preferred among these nonionic surfactants because of
considerations
related to detergency, and polyoxyalkylene alkyl ethers and alkyl
polyglucosides are even
more preferred because of considerations related to economic efficiency.
Examples of amphoteric surfactants include alkyl carboxybetaines, alkyl
sulfobetaines, alkyl hydroxysulfobetaines, alkyl amidobetaines, imidazolinium
betaines, alkyl
diaminoethyl glycines, dialkyl diaminoethyl glycines, alkyl amine oxides,
alkyl ether amine
oxides, and amide/amine oxides. In the present invention, alkyl
carboxybetaines, alkyl
sulfobetaines, alkyl hydroxysulfobetaines, alkyl amidobetaines, alkyl amine
oxides, alkyl
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ether amine oxides, and amide/amine oxides are preferred among these
amphoteric
surfactants because of considerations related to detergency, and alkyl
amidobetaines and alkyl
amine oxides are even more preferred because of considerations related to
economic
efficiency.
Examples of cationic surfactants include alkyl trimethylammonium salts,
dialkyl
dimethylammonium salts, alkyl trimethylammonium salts, alkyl dimethylammonium
adipates, benzalkonium salts, benzethonium salts, pyridinium salts,
imidazolinium salts, and
biguanide compounds. The counterions of these cationic surfactants are halogen
ions and the
like. In the present invention, dialkyl dimethylammonium salts, alkyl
dimethylammonium
adipates, benzalkonium salts, benzethonium salts, and biguanide compounds are
preferred
among these cationic surfactants because of considerations related to
bactericidal properties
and economic efficiency, and benzalkonium chloride and dialkyl
dimethylammonium
chlorides are even more preferred because of considerations related to the
anti-soiling effect.
These surfactants may be used singly or as combination of two or more
components,
and can be appropriately selected and used in accordance with detergency on
the soil,
foaming properties, rinsing properties, mildness on the skin, damage to the
material, ease of
wiping, and other required performance attributes.
The admixed amount of component (B) is selected from the range of 0.1 to 30
mass%
of the composition. The detergency and the anti-soiling effect of component
(A) will be
limited if this amount is less than 0.1 mass%, and the increase in detergency
will reach
saturation and the economic efficiency will actually decline if more than 30
mass% is
admixed. The amount in which the surfactant is admixed is preferably within a
range of 1 to
mass%, based on the total mass of the composition, because of considerations
related to
detergency, and even more preferably within a range of 1 to 15 mass% because
of
25 considerations related to economic efficiency.
Examples of the metal chelating agent of component (C) used in the present
invention
include hydroxycarboxylic acids, aminocarboxylic acids, phosphoric acids,
phosphonic acids,
phosphonocarboxylic acids, water-soluble macromolecular polymers, salts
thereof, and other
compounds that are soluble in water and have a chelating capacity. These may
be used singly
30 or as combinations of two or more compounds. The metal chelating agent is
admixed with
the purpose of obtaining enhanced detergency.
Examples of hydroxycarboxylic acids include acetic acid, adipic acid,
monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid,
carboxymethylsuccinic
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acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic
acid, tartaric acid,
carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts
thereof.
Examples of aminocarboxylic acids include nitrilotriacetic acid, iminodiacetic
acid,
ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, N-
hydroxyethyl
ethylenediamine acetic acid, ethylenediamine tetrapropionic-acetic acid,
methyl glycine
diacetic acid, triethylenetetramine hexaacetic acid, ethylene glycol diether
diamine tetraacetic
acid, hydroxyethyliminodiacetic acid, cyclohexane-1,2-diaminotetraacetic acid,
djenkolic
acid, and salts thereof.
Examples of phosphoric acids include orthophosphoric acid, pyrophosphoric
acid,
tripolyphosphoric acid, metaphosphoric acid, hexametaphosphcric acid, phytic
acid, and other
condensed phosphoric acids, as well as salts thereof.
Examples of phosphonic acids include ethane-l,l-diphosphonic acid, ethane-
1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, derivatives
thereof,
1-hydroxyethane-1,1,2-triphosphonic acid, ethane- 1,2-dicarboxy- 1,2-
diphosphonic acid,
methane hydroxyphosphonic acid, aminotrimethylene phosphonic acid, and salts
thereof.
Examples of phosphonocarboxylic acids include 2-phosphonobutane-1,2-
dicarboxylic
acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, a-methylphosphonosuccinic
acid, and salts
thereof.
Examples of water-soluble macromolecular polymers include polyacrylic acid,
polymaleic acid, copolymers of acrylic acid and maleic acid, polyaconitic
acid,
poly-a-hydroxyacrylic acid, polymethacrylic acid, and salts thereof.
These metal chelating agents may be used in the form of acids or as partial or
complete salts. Examples of such salts include salts of potassium, sodium, and
other alkali
metals; monoalkanolamines, diethanolamine, triethanolamine, and other
alkanolamine salts;
and ammonium salts.
Hydroxycarboxylic acids, aminocarboxylic acids, alkali metal salts thereof,
and
alkanolamine salts are preferred among these metal chelating agents because of
considerations related to the impact on the environment, and hydroxycarboxylic
acids,
aminocarboxylic acids, and sodium salts thereof are even more preferred
because of
considerations related to economic efficiency.
The admixed amount of component (C) is selected from the range of 0.1 to 20
mass%
of the composition. A limited detergency improving effect will be produced if
this amount is
less than 0.1 mass%, and the detergency improving effect will reach
saturation, the
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composition will have poor storage stability, and the economic efficiency will
actually be low
if more than 20 mass% is admixed. The amount in which the metal chelating
agent is
admixed is preferably within a range of 1 to 20 mass%, based on the total mass
of the
composition, because of considerations related to detergency, and even more
preferably
within a range of 1 to 15 mass% because of considerations related to economic
efficiency.
Purified water, deionized water, soft water, distilled water, and tap water
can be cited
as examples of the water, or component (D), used in the present invention.
These types of
water may be used singly or as a combination of two or more types. Among
these, tap water
and deionized water are preferably used because of considerations related to
economic
efficiency and storage stability.
As used herein, the term "water" refers _to the sum of water provided from the
outside
and water contained as the aqueous solution or crystal water derived from the
components
that constitute the anti-soiling detergent composition of the present
invention. This water is
admixed in such a way that the entire anti-soiling detergent composition
constitutes 100%.
In the present invention, a thickener can also be admixed as component (E)
according
to need together with essential components (A) to (D). Component (E) is
admixed in order to
make the anti-soiling detergent composition of the present invention more
usable through a
thickening effect; particularly, to improve usability when spraying is
employed or when a
non-horizontal surface is cleaned, and hence to enhance detergency on non-
horizontal
surfaces.
Examples of the thickener that can be used as component (E) in the present
invention
include xanthan gum, carageenan, guar gum, gum arabic, locust bean gum,
alginate,
carboxymethylcellulose, and other thickening polysaccharides, as well as
carboxyvinyl
polymers, crosslinked polyacrylic acids, and salts thereof. In the present
invention, xanthan
gum and carboxyvinyl polymers are preferred among these because of
considerations related
to the stability of the composition.
The admixed amount of component (E) is selected from the range of 0.01 to 5
mass%
of the composition. An inferior anti-soiling effect will be produced if this
amount is less than
0.01 mass%, and the composition will become excessively viscous and difficult
to handle,
and the economic efficiency will actually be low if more than 5 mass% is
admixed. The
amount in which the thickener is admixed is preferably within a range of 0.05
to 2 mass%,
based on the total mass of the composition, because of considerations related
to the ease of
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operation, and even more preferably within a range of 0.05 to 1 mass% because
of
considerations related to economic efficiency.
Ihi the present invention, a water-soluble solvent may be admixed as component
(F)
according to need together with essential components (A) to (D). Component (F)
contributes
to further improvements in detergency, particularly, detergency in relation to
organic soil.
The following are examples of the water-soluble solvent, or component (F):
(1) Alcohols such as ethanol, propanol, isopropanol, butanol, and other
monohydric
alcohols; ethylene glycol, diethylene glycol, isoprene glycol, propylene
glycol, and other
alkylene glycols; and glycerin, polyglycerin, 1,3-butanediol, and other
polyhydric alcohols
(2) Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol
dimethyl
ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
propylene glycol
monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl
ether,
propylene glycol monophenyl ether, diethylene glycol monomethyl ether,
diethylene glycol
monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol
monomethyl ether,
dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether,
triethylene glycol
monobutyl ether, tripropylene glycol dimethyl ether, and other alkylene glycol
(mono-, di-)
alkyl ethers
(3) Limonene, pinene, terpinolene, myrcene, terpinene, phenanthrene, and other
terpene-based hydrocarbon solvents
These water-soluble solvents may be used singly or as combinations of two or
more
components, and can be appropriately selected and used in accordance with
detergency on the
soil, damage to the material, ease of wiping, and other required performance
attributes.
Among these water-soluble solvents, lower alcohols with a carbon number of I
to 5,
glycol ethers, and terpene-based hydrocarbon solvents are preferred because of
considerations
related to detergency, and the following solvents are even more preferred
because of
considerations related to detergency, stability, and water solubility: lower
alcohols with a
carbon number of 1 to 5, propylene glycol monomethyl ether, propylene glycol
monobutyl
ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether,
dipropylene
glycol monobutyl ether, and limonene.
The admixed amount of component (F) is selected from the range of 0.1 to 20
mass%
of the composition. Detergency will be limited if this amount is less than 0.1
mass%, and the
increase in detergency will reach saturation, the economic efficiency will
actually decline, and
the composition will have unsatisfactory storage stability if more than 20
mass% is admixed.
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The amount in which the water-soluble solvent is admixed is preferably 1 to 15
mass%
because of considerations related to detergency and storage stability, and is
more preferably 1
to 10 mass% because of considerations related to economic efficiency, based on
the total
mass of the composition.
The stock solution for the anti-soiling detergent composition of the present
invention
is adjusted to a pH of 5 to 9, and preferably 6 to 8, taking into account the
absence of any
adverse effect on the material of the cleaning object, and biological and
environmental safety.
The pH can be adjusted using a substance that displays alkalinity and a
substance that
displays acidity.
Examples of alkaline substances that can be used for pH adjustment include
sodium
hydroxide, potassium hydroxide, and other alkali hydroxides; sodium carbonate,
potassium
carbonate, and other carbonates; sodium silicate, potassium silicate, and
other silicates;
monoethanolainine, diethanolamine, and other amines; and ammonia. Examples of
acidic
substances that can be used for pH adjustment include hydrochloric acid,
sulfuric acid, and
other inorganic acids, as well as citric acid, acetic acid, and other organic
acids.
If an organic acid that corresponds to component (C) is used as the pH
regulator, it
must be taken into account that component (C) should be admixed in a ratio
that does not fall
outside the range of 0.1 to 20 mass%.
Fragrances, dyes, pigments, bactericides, preservatives, and the like may also
be
admixed as needed in addition to the aforementioned components into the anti-
soiling
detergent composition of the present invention as long as the objects of the
present invention
are not compromised.
The anti-soiling detergent composition of the present invention can be used to
advantage for cleaning and desoiling hard surfaces that are in repeated
contact with tap water
and are prone to developing water stains; particularly, the hard surfaces of
restrooms,
washstands, baths, and the like. The materials of such cleaned surfaces
include plastics,
stainless steel, porcelain, tile, glass, ceramics, granite/terrazzo, and other
natural stone
materials.
The anti-soiling detergent composition of the present invention may be used
either as
a stock solution or after being diluted with water or warm water in accordance
with the degree
of soiling of the cleaned surface. The degree of dilution can be up to 50
times, based on
considerations related to detergency and anti-soiling effect.
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Examples of the cleaning methods in which the anti-soiling detergent
composition of
the present invention can be used include the following.
(1) A sponge or the like is impregnated with the anti-soiling detergent
composition of
the present invention, and a hard surface is scrubbed and rinsed.
(2) A cleaned surface is sprinkled with the anti-soiling detergent composition
of the
present invention, scrubbed with a sponge or the like, and rinsed.
(3) A cleaned surface is sprayed with the anti-soiling detergent composition
of the
present invention, allowed to stand for a while, and rinsed.
(4) In the case of a vertical surface, nonwoven fabric or the like is
impregnated with
the anti-soiling detergent composition of the present invention, affixed,
allowed to stand for a
while, and rinsed.
(5) A towel or duster is impregnated with the anti-soiling detergent
composition of the
present invention, the soil is wiped off, and the surface is wiped with a
moist towel.
The present invention will now be described in further detail through examples
and
comparative examples with reference to the anti-soiling detergent composition
of the present
invention, but the present invention is not limited thereby.
EXAMPLES 1 TO 28, COMPARATIVE EXAMPLES 1 TO 18
The anti-soiling detergent compositions shown in Tables 1 to 8 were prepared
and
subjected to various tests. The numerical values for the components in the
tables refer to the
content (mass%) of each component. The pH was adjusted as needed with the aid
of a pH
regulator such as acetic acid, sulfuric acid, or sodium hydroxide, and the sum
of
components (A) to (F), the pH regulator, and arbitrary components was 100
mass% total. In
Tables 1 to 8, the circle signs indicate cases in which a pH regulator was
used.
The anti-soiling detergent compositions thus obtained were evaluated for test
parameters such as pH, detergency, anti-soiling effect, sustainability of the
anti-soiling effect,
and storage stability by the test methods and in accordance with the grading
system described
below, and the results are presented as well in Tables 1 to 8 below.
(1) pH
A pH meter (pH METER F-12, manufactured by Horiba) was used to measure the pH
value of a prepared stock solution of an anti-soiling detergent composition at
25 C in
accordance with JIS Z-8808: 1984.
(2) Detergency Test 1: Simulated Restroom Soil
[Preparation of Simulated Restroom Soil]
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0.5 g of lanolin was dissolved in 5 mL of chloroform, 495 mL of ethanol was
added
for dilution, and an ethanol solution was prepared. A preparation obtained by
dissolving 10 g
of ferric chloride in 500 mL of water and adding the resulting solution to the
ethanol solution
was applied in the exact quantity of 1 mL to ceramic tile (SPKC-100/L00;
white; 10 cm x
10 cm; manufactured by INAX) whose surface had been pre-roughened with
sandpaper (No.
120, manufactured by Nippon Coated Abrasive) that was moved back and forth ten
times in
the longitudinal and transverse direction, and caused to make 201aps so that a
circle was
drawn. The coated tile was baked for 1 hour at 145 C and allowed to cool at
room
temperature, yielding a test piece.
[Test Method]
5 mL of a stock solution of each composition was fed dropwise onto the test
piece, a
sponge (4 cm x 8 cm) was moved back and forth 15 times with the aid of a
washability tester
(manufactured by Tester Sangyo), and a detergency test was performed.
Following testing,
the test piece was rinsed for 10 seconds with a certain amount of tap water
and dried at room
temperature. The whiteness of the test piece was measured before and after the
test, and the
cleaning ratio was determined using the formula shown below. The whiteness was
measured
using a color difference meter (Model CR-331, manufactured by Minolta).
Cleaning ratio (%) = (Whiteness after cleaning - Whiteness before
cleaning)/(Whiteness before soil deposition - Whiteness before cleaning) x 100
An evaluation was then performed based on the following grading system using
these
cleaning ratio values.
[Grading System]
CJ: Cleaning ratio of 80% or greater
0: Cleaning ratio of 60% or greater
A: Cleaning ratio of 40% or greater
x: Cleaning ratio of less than 40%
(3) Detergency Test 2: Simulated Soap Scum Soil
[Preparation of Simulated Soap Scum Soil]
A preparation obtained by dissolving 2.5 g of oleic acid, 2.5 g of triolein,
0.25 g of
albumin, and 4.75 g of calcium stearate in 60 g of chloroform was uniformly
applied in the
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exact quantity of 1 mL to slide glass (7.6 cm x 2.6 cm). The slide glass was
dried overnight
at room temperature and used as a test piece.
[Test Method]
A stock solution of each composition was fed dropwise onto the test piece, and
the
5 test piece was scrubbed with a Conradi T" stick wrapped in tissue paper (Kim
Wipe T '
manufactured by Crecia), which was moved back and forth 15 times to conduct
the
detergency test. Following testing, the test piece was rinsed for 10 seconds
with a certain
amount of tap water and dried at room temperature. The mass of the test piece
was measured
before and after the test, and the cleaning ratio was determined using the
formula shown
10 below.
Cleaning ratio (%) (Mass of soil removed by detergency test/Mass of soil
deposited
before detergency test) x 100
An evaluation was then performed based on the following grading system using
these
clcaning ratio values.
15 [Grading System]
O: Cleaning ratio of 80% or greater
0: Cleaning ratio of 60% or greater
A: Cleaning ratio of 40% or greater
x: Cleaning ratio of less than 40%
20 (4) Testing of Anti-soiling Effect
[Test Method]
Ceraniic tile (SPKC-100/L00; white; 10 cm x 10 cm; manufactured by INAX) was
cleaned using a sponge (4 cm x 8 em) with 2 mL of a stock solution of each
composition,
rinsed for 20 seconds with a certain amount of tap water, and dried at room
temperature to
obtain a test piece. Five drops of a solution obtained by dissolving I g of
ferric chloride in
100 g of water were dropped in spots onto the test piece by using a dropping
pipette, and the
test piece was then baked for 3 hours at 105 C and allowed to cool at room
temperature. The
soil was scrubbed off from the test piece with moistened tissue paper (Kim
Wipe,
manufactured by Crecia), and soil removal was visually evaluated.
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[Grading System]
O: Soil was removed by light rubbing at all five locations
0: Soil was removed by forceful rubbing at all five locations
A: Soil was removed by forceful rubbing at four locations
x: Soil remained at two or more locations despite forceful rubbing
(5) Test 1 of Sustainability of Anti-soiling Effect
[Test Method]
A test was performed to determine the extent to which the anti-soiling effect
could be
sustained in actual applications involving the urinals, toilet bowls (both
Japanese- and
Western-style), and washstands at unisex restrooms cleaned once a day.
On the first day of the test, the urinals, toilet bowls, and washstands were
scrubbed
with a sponge by using a stock solution of each composition, and the scrubbed
surfaces were
then rinsed with running water. Starting on the next day for 6 days, the
surfaces were
scrubbed with a moistened sponge and merely rinsed with without using any
detergent.
During the cleaning on day 7, a stock solution of each composition was used in
the same
manner as on day 1, and the surfaces were scrubbed with a sponge and rinsed
with water.
The cleaning in which stock solutions of each composition were used was
continued
in this manner once a week for 1 month (4 cycles), the extent of soiling was
visually observed
1 month (4 cycles) after the start of the test, and the results were evaluated
based on the
following grading system.
[Grading System]
O: The same clean surfaces as a month prior, very little soil deposited, the
cleaning
time reduced
0: The surfaces unchanged from a month prior, but soil occasionally deposited
A: More soil than a month prior
x: Much more soil than a month prior
(6) Test 2 of Sustainability of Anti-soiling Effect
[Test Method]
A test was performed to determine the extent to which the anti-soiling effect
could be
sustained in actual applications involving the urinals, toilet bowls (both
Japanese- and
Western-style), and washstands at unisex restrooms cleaned once a day.
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On the first day of the test, the urinals, toilet bowls, and washstands were
scrubbed
with a sponge by using a stock solution of each composition, and the scrubbed
surfaces were
then rinsed with running water. Starting on the next day for 13 days, the
surfaces were
scrubbed with a moistened sponge and merely rinsed with without using any
detergent.
During the cleaning on day 14, a stock solution of each composition was used
in the same
manner as on day 1, and the surfaces were scrubbed with a sponge and rinsed
with water.
The cleaning in which stock solutions of each composition were used was
continued
in this manner once every 2 weeks for 1 month (2 cycles), the extent of
soiling was visually
observed 1 month (2 cycles) after the start of the test, and the results were
evaluated based on
the following grading system.
[Grading System]
O: The same clean surfaces as a month prior, very little soil deposited, the
cleaning
time reduced
0: The surfaces unchanged from a month prior, but soil occasionally deposited
0: More soil than a month prior
x: Much more soil than a month prior
(7) Storage Stability Test 1: High-temperature Stability
[Test Method]
Each composition was allowed to stand for 3 months in an incubator set to 50 C
(model IS82, manufactured by Yamato Scientific), and the presence or absence
of
precipitation, color changes, or separation was visually observed. An
evaluation was made
based on the following grading system.
[Grading System]
0: No precipitation, color changes, or separation observed in the composition
at all
0: Slight precipitation, color changes, or separation observed in the
composition
0: Precipitation, color changes, or separation could clearly be seen occurring
in the
composition
x: Pronounced precipitation, color changes, or separation observed in the
composition
(8) Storage Stability Test 2: High-temperature Stability
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[Test Method]
Each composition was placed overnight in an incubator set to -15 C (model HRF-
90P,
manufactured by Hoshizaki), allowed to freeze, and then caused to thaw at room
temperature.
This cycle was repeated five times, and the condition of the composition after
8 hours had
elapsed since the start of thawing was visually observed. An evaluation was
made based on
the following grading system.
[Grading System]
0: No precipitation, color changes, or separation observed in the composition
after
5 cycles of freezing/thawing
0: No precipitation, color changes, or separation observed in the composition
after
4 cycles of freezing/thawing, but some precipitation, color changes, or
separation observed during cycle 5
A: No precipitation, color changes, or separation observed in the composition
after
3 cycles of freezing/thawing, but some precipitation, color changes, or
separation observed during cycle 4
x: Precipitation, color changes, or separation observed in the composition
before
3 cycles of freezing/thawing
Details of the components shown in Tables 1 to 8 below are as follows.
* Organopolysiloxane 1: A polyetheramide-modified organopolysiloxane expressed
by the chemical formula
[Chemical Formula 20]
~HU i CHO GHS IH8
UHa--I i{3( `i(J)~a ( iit~)aa ~ 1--k~i'a
CH,q CHg G ~ CHa
(In the formula G7 is (CH2)3NHCOCH2O(CH2CH2O)4C12H25.)
* Organopolysiloxane 2: A polyetheramide-modified organopolysiloxane expressed
by the chemical formula
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[Chemical Formula 21]
' Hg IC H3 C I Ha I C Ha
CHa-~ iC~(~afJ)a6o (~iC~)is i 3--CHa
CHs CH3 G, CH$
(In the formula G8 is (CH2)3NHCOCH2O(CH2CH2O)5C12H25.)
* Organopolysiloxane 3: A polyetheramide-modified organopolysiloxane expressed
by the chemical formula
[Chemical Formula 22]
C:iHg CH3 CHg CH3 CH3 CH3
CH3-- Si.C7 (SIC?) jsa (s io) 8 (30 3 ( l iC3) i '.)i--CHe
CH`~ CA-13 G$ Gi Gis CHs
(In the formula G9 is (CH2)30(CH2CH2O)10C12H25, G10 is (CH2)3NH2, and G" is
(CH2)3NHCOCH2O(CH2CH2O)5C 12H2s =)
* Organopolysiloxane 4: A polyetheramide-modified organopolysiloxane expressed
by the chemical formula
[Chemical Formula 23]
C~:~ + i H3 ~ Ha ~ H~, jH3
CHs--SiO (SiO) 200 (SiO)1o (Si+D),.Si--CH3
i I I I I
CHS CHa G" Gi. CIH3
(In the formula G12 is (CH2)30(CHZCH2O)8C12H2$, and G13 is
(CH2)3NHCOCH2O(CH2CH2O)4C12H25.)
* Organopolysiloxane 5: Amino-modified organopolysiloxane
(Registered trade name: SF8417, manufactured by Toray Dow Coming Silicone)
* Organopolysiloxane 6: Polyether-modified organopolysiloxane
(Registered trade name: KF-601 l, manufactured by Shin-Etsu Silicones)
* Organopolysiloxane 7: Polydimethylsiloxane
(Registered trade name: BY22-007, manufactured by Toray Dow Coming Silicone)
* Nonionic surfactant 1: Alkyl polyglucoside
(Registered trade name: 215CSUP, manufactured by Cognis Japan)
* Nonionic surfactant 2: Polyoxyethylene alkyl ether
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(Registered trade name: NaroaktyTM -ID 70, manufactured by Sanyo Chemical
Industries)
* Nonionic surfactant 3: Polyoxyethylene alkyl ether
(Registered trade name: Lutensol T ' T08, manufactured by BASF)
5 * Amphoteric surfactant 1: Alkylamidopropyl betaine
(Registered trade name: TegoBetain T" L I OS, manufactured by Goldschmidt)
* Amphoteric surfactant 2: Alkylamine oxide
(Registered trade name: Barlox' 12, manufactured by Lonza)
*Cationic surfactant 1: Benzalkonium chloride
10 (Registered trade name: Cation G-50TM, manufactured by Sanyo Chemical
Industries)
*Cationic surfactant 2: Didecyldimethylaimnonium chloride
(Registered trade name: Bardac 2280, manufactured by Lonza)
*Anionic surfactant 1: Sodium alkyl ether sulfonate
(Registered trade name: Alscoap TM TH-330, manufactured by Toho Chemical
Industry)
15 *Anionic surfactant 2: Sodium alkylbenzenesulfonate
(Registered trade name: Taycapower' LN2450, manufactured by Tayca)
*Thickener 1: Carboxyvinyl polymer
(Registered trade name: Hiviswako TM 105, manufactured by Wako Pure Chemical
Industries)
20 *Thickener 2: Xanthan gum (registered trade name: KelzanTM, manufactured by
Kelco)
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[Table 1]
Admixed components Examples
1 2 3 4 5 6
A Organopolysiloxane 1 1.0 4.0 10.0 2.0 0.5
Organopolysiloxane 2 4.0 0.5
Organopolysiloxane 3
Organopolysiloxane 4
Organopolysiloxane 5
B Nonionic surfactant 1 3.0 10.0 29.0 2.0 2.0
Nonionic surfactant 2 1.0
Nonionic surfactant 3
Amphoteric surfactant 1 4.8 1.0
Amphoteric surfactant 2 2.0
Cationic surfactant 1 0.2 0.2 1.0 0.2 1.0
Cationic surfactant 2
C NTA - 3Na 20.0 15.0 4.0 4.0
Sodium citrate 4.0
Citri.c acid 4.0 1.0 1.0
EDTA = 4H 4.0
D Deionized water Balance Balance alance Balance Balance Balance
E Thickener 1
Thickener 2
F Diethylene glycol monobutyl 15.0 20.0
ether
Ethanol 10.0
Limonene
Acetic acid (pH adjustment) 0 0 0 O O
Sulfuric acid (pH adjustment)
Sodium hydroxide (pH adjustment) 0
pH 7 7 7 7 7 7
Detergency 1 O O O O 0 O
Detergency 2 O O O O 0 O
Anti-soiling effect O O O O O 0
Sustainability of anti- O O O O O 0
Evaluation
soiling effect 1
Sustainability of anti- 0 0 0 0 0 0
soiling effect 2
Storage stability 1 O O 0 O 0 0
Storage stability 2 O O O O O 0
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[Table 2]
Admixed components Examples
7 8 9 10 11 12
A Organopolysiloxane 1 1.0 1.0 2.0 2.0
Organopolysiloxane 2 1.0
Organopolysiloxane 3
Organopolysiloxane 4
Organopolysiloxane 5 1.0 1.0
B Nonionic surfactant 1 3.0 3.0 3.0 3.0
Nonionic surfactant 2 2.5
Nonionic surfactant 3 0.5
Amphoteric surfactant 1 1.0 1.0 1.0 1.0 1.0 3.0
Amphoteric surfactant 2
Cationic surfactant 1 0.2 0.2 0.2 0.2
Cationic surfactant 2 0.2
C NTA = 3Na 4.0 4.0 4.0 4.0 2.0 4.0
Sodium citrate 2.0
Citric acid 0.7 0.7 0.7 1.0
EDTA = 4H
D Deionized water Balance Balance alance Balance Balance Balance
E Thickener 1 0.4 0.4 0.4 1.0 0.4
Thickener 2 2,0
F Diethylene glycol monobutyl
ether
Ethanol
Limonene
Acetic acid (pH adjustment) 0 O O O O
Sulfuric acid (pH adjustment) O
Sodium hydroxide (pH adjustment)
pH 7 7 7 7 7 7
Detergency 1 0 0 O 0 O 0
Detergency 2 O O O O O O
Anti-soiling effect O O 0 O O O
Evaluation Sustainability of anti- O O O O O 0
soiling effect 1
Sustainability of anti- 0 0 0 0 O 0
soiling effect 2
Storage stability 1 O O O O O O
Storage stability 2 O O 0 0
O O
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[Table 3]
Examples
Admixed components
13 14 15 16 17 18
A Organopolysiloxane 1 0.1 2.0
Organopolysiloxane 2 0.05
Organopolysiloxane 3 0.2
Organopolysiloxane 4 5.0
Organopolysiloxane 5 0.1
B Nonionic surfactant 1 0.5 3.0 3.0 0.08 10.0 3.0
Nonionic surfactant 2
Nonionic surfactant 3
Amphoteric surfactant 1 0.3 1.0 1.0 4.8 1.0
Amphoteric surfactant 2
Cationic surfactant 1 0.2 0.2 0.2 0.02 0.2
Cationic surfactant 2 0.2
C NTA = 3Na 4.0 4.0 4.0 1.0 4.0
Sodium citrate
Citric acid 0.6 0.6 0.6
EDTA = 4H 0.1
D Deionized water Balance Balance alance Balance Balance Balance
E Thickener 1 0.4 0.4 5.0
Thickener 2 0.05 0.01
F Diethylene glycol monobutyl 0.1 3.0
ether
Ethanol
Limonene 1.0
Acetic acid (pH adjustment) 0 0 0
Sulfuric acid (pH adjustment) 0
Sodium hydroxide (pH adjustment) 0
O
---- pH --- - 7 7 7 7 7 7
Detergency 1 O O O O O O
Detergency 2 O O O 0 O O
Anti-soiling effect 0 0 0 O O O
Sustainability of anti-soiling 0 0 0 0 O 0
Evaluation
effect 1
Sustainability of anti-soiling 0 0 0 O 0 0
effect 2
Storage stability 1 O O O O O O
Storage stability 2 O 0 O O O O
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[Table 41
Admixed components Examples
19 20 21 22 23 24
A Organopolysiloxane 1 1.0
Organopolysiloxane 2 5.0
Organopolysiloxane 3 1.0 2.0 2.0 2.0
Organopolysiloxane 4
Organopolysiloxane 5
B Nonionic surfactant 1 8.0 3.0 2.0 3.0 1.0
Nonionic surfactant 2 2.0
Nonionic surfactant 3 2.0 1.0 2.0
Amphoteric surfactant 1 1.0 1.0 1.0
Amphoteric surfactant 2 1.0 1.0 1.0
Cationic surfactant 1 0.2 0.2 0.2 0.2 0.2
Cationic surfactant 2 0.2
C NTA = 3Na 4.0 12.0 4.0 1.0
Sodium citrate 2.0
Citric acid 0.7 2.0 0.7 5.0
EDTA . 4H 1.0
D Deionized water Balance Balance Balance Balance Balance Balance
E Thickener 1 0.4 0.4
Thickener 2 0.4
F Diethylene glycol monobutyl 2.0
ether
Ethanol 1.0
Limonene
Acetic acid (pH adjustment) 0 0
Sulfuric acid (pH adjustment) O
Sodium hydroxide (pH adjustment) 0 0
pH 7 7 7 7 7 7
Detergency 1 O O O O O O
Detergency 2 O O O O O
Anti-soiling effect O O 0
O O
Evaluation Sustainability of anti- O O O O O O
soiling effect 1
Sustainability of anti- 0 0 0 0
O O
soiling effect 2
Storage stability 1 0
O O O O O
Storage stability 2 0
O O O O O
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[Table 51
Admixed components Examples
25 26 27 28
A Organopolysiloxane 1
Organopolysiloxane 2 0.5
Organopolysiloxane 3 5.0 1.5 1.5
Organopolysiloxane 4 2.0 0.5
Organopolysiloxane 5
B Nonionic surfactant 1 10.0 3.0 3.0 3.0
Nonionic surfactant 2 2.0
Nonionic surfactant 3
Amphoteric surfactant 1 3.0 1.0 1.0 1.0
Amphoteric surfactant 2
Cationic surfactant 1 0.2 0.2 0.2
Cationic surfactant 2
C NTA = 3Na 4.0 4.0 4.0
Sodium citrate
Citric acid 0.7 0.7 0.7
EDTA = 4H 1.0
D Deionized water Balance Balance Balance Balance
E Thickener 1 0.4 0.4 0.4
Thickener 2
F Diethylene glycol monobutyl
ether
Ethanol
Limonene
Acetic acid (pH adjustment) O O 0
Sulfuric acid (pH adjustment)
Sodium hydroxide (pH adjustment) 0
pH 7 7 7 7
Detergency 1 O O 0 0
Detergency 2 O O 0 O
Anti-soiling effect O O 0 O
Evaluation Sustainability of anti- O O O O
soiling effect 1
Sustainability of anti- O O 0
O
soiling effect 2
Storage stability 1 O O O O
Storage stability 2 O O O O
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[Table 6]
Admixed components Comparative examples
1 2 3 4 5 6
A Organopolysiloxane 1
Organopolysiloxane 2
Organopolysiloxane 3
Organopolysiloxane 4
Organopolysiloxane 5
Organopolysiloxane 6 2.0 0.5
Organopolysiloxane 7 1.5 3.0 0.5
B Nonionic surfactant 1 3.0 3.0 3.0 3.0
Nonionic surfactant 2 5.0
Nonionic surfactant 3
Amphoteric surfactant 1 1.0 1.0 1.0 1.0 8.0
Amphoteric surfactant 2
Cationic surfactant 1 0.2 0.2 0.2
Cationic surfactant 2
7Anionic surfactant 1
Anionic surfactant 2 7,0
C NTA = 3Na 4.0 4.0 4.0 4.0
Sodium citrate
Citric acid 0.5 0.5 0.5 0.5 5.0
EDTA = 4H 1.0
D Deionized water Balance Balance Balance Balance Balance Balance
E Thickener 1 0.4 0.4 0.4 0.4
Thickener 2
F Diethylene glycol 3.0 6.0 1.0
monobutyl ether
Ethanol 2.0
Limonene
Acetic acid (pH adjustment) 0 0 0 0
Sulfuric acid (pH adjustment)
Sodium hydroxide (pH adjustment) 0 0
pH 7 7 7 7 7 7
Detergency 1 O O O O O O
Detergency 2 O O O O O O
Anti-soiling effect x x x x x x
Evaluation Sustainability of anti- x x x x x x
soiling effect 1
Sustainability of anti- x x x x x x
soiling effect 2
Storage stability 1 O O O O O O
Storage stability 2 O O 0
O O O
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[Table 7)
Admixed components Comparative examples
7 8 9 10 11 12
A Organopolysiloxane 1 0.01 10.0 1.0
Organopolysiloxane 2 10.0
Organopolysiloxane 3 1.0
Organopolysiloxane 4
Organopolysiloxane 5 20.0 1.0
Organopolysiloxane 6
Organopolysiloxane 7
B Nonionic surfactant 1 3.0 3.0 3.0 0.05 30.0
Nonionic surfactant 2
Nonionic surfactant 3
Amphoteric surfactant 1 1.0 1.0 1.0
Amphoteric surfactant 2
Cationic surfactant 1 0.2 0.2 5.0
Cationic surfactant 2 0.2
Anionic surfactant 1
Anionic surfactant 2
C NTA = 3Na 4.0 4.0 4.0
Sodium citrate 4.0 4.0
Citric acid 0.6 0.6 0.6
EDTA - 4H 4.0
D Deionized water Balance Balance Balance Balance Balance Balance
E Thickener 1 0.4 0.4 0.4 0.4 0.4 0.4
Thickener 2
F Diethylene glycol 3.0 3.0
monobutyl ether
Ethanol 3.0 3.0
Limonene 1.0
Acetic acid (pH adjustment) O O O
Sulfuric acid (pH adjustment) 0 0
Sodium hydroxide (pH adjustment) O
pH 7 7 7 7 7 7
Detergency 1 O O O A p
Detergency 2 0 0 x x O
Anti-soiling effect p O 0 0 A
Evaluation Sustainability of anti- x O O e e 4
soiling effect 1
Suatainability of anti- x 0 0 x x x
soiling effect 2
Storage stability 1 O x x x x
Storage stability 2 O _r_X__
x x x IX
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[Table 81
Comparative examples
Admixed components
13 14 15 16 17 18
A Organopolysiloxane 1 2.0 1.0 1.0
Organopolysiloxane 2 1.0 1.0
Organopolysiloxane 3
Organopolysiloxane 4
Organopolysiloxane 5 0.5
Organopolysiloxane 6
Organopolysiloxane 7
B Nonionic surfactant 1 1.0 3.0 3.0 3.0
Nonionic surfactant 2 0.05
Nonionic surfactant 3
Amphoteric surfactant 1 1.0 1.0 1.0 1.0
Amphoteric surfactant 2
Cationic surfactant 1 0.2 0.2 0.2 0.2
Cationic surfactant 2
Anionic surfactant 1 1.0
Anionic surfactant 2 0.4
C NTA = 3Na 4.0 0.05 30.0
Sodium citrate
Citric acid 0.6 7.0
EDTA = 4H 4.0
D Deionized water Balance Balance Balance Balance Balance Balance
E Thickener 1 0.4
Thickener 2
F Diethylene glycol 20.0 3.0 3.0 3.0
monobutyl ether
Ethanol
Limonene
Acetic acid (pH adjustment) 0 0 0 0 0
Sulfuric acid (pH adjustment)
Sodium hydroxide (pH adjustment) 0
pH 7 7 7 7 7 7
Detergency 1 O O x x x 0
Detergency 2 O 0 p x A 0
Anti-soiling effect p p 0 0 0 0
O
Evaluation Sustainability of anti- p p 0 0 0
soiling effect 1
Sustainability of anti- x x 0 0 0 0
soiling effect 2
Storage stability 1 0 0 0 x 0 0
Storage stability 2 0 O O x 0 x
Based on the above results, it can be seen that the compositions of examples 1
to 28
deliver satisfactory performance in terms of test items such as detergency,
anti-soiling effect,
sustainability of the anti-soiling effect, and storage stability. By contrast,
an inferior and
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poorly sustainable anti-soiling effect is provided by the compositions of
comparative
examples 1 to 6, which are devoid of the polyetheramide-modified
organopolysiloxane and/or
amino-modified organopolysiloxane of component (A), or by the composition of
comparative
example 7, in which the content of component (A) is too low. Inferior storage
stability is
exhibited by the compositions of comparative examples 8 and 9, in which more
than
mass% of component (A) is admixed.
Low detergency, a poorly sustainable anti-soiling effect, and inferior storage
stability
are exhibited by the composition of comparative example 10, which is devoid of
the
surfactant of component (B), or by the composition of comparative example 11,
in which too
10 little of component (B) is admixed. Inferior storage stability and a low
and poorly sustainable
anti-soiling effect are exhibited by the composition of comparative example
12, in which
more than 30 mass% of component (B) is admixed. Inferior and poorly
sustainable anti-
soiling effect is exhibited by the compositions of comparative examples 13 and
14, which
contain an anionic surfactant as component (B).
Inferior detergency is exhibited by the compositions of comparative examples
15 and
16, which are devoid of the metal chelating agent of component (C), or by the
composition of
comparative example 17, in which too little of component (C) is admixed. It
can also be seen
that inferior storage stability is exhibited by the composition of comparative
example 18, in
which more than 20 mass% of component (C) is admixed.
The compositions of examples 7 to 11, 12, and 26 to 28 were used to clean
restrooms,
washstands, and mirrors in stores, offices, residences, and the like in the
same manner as in
the tests of sustainability of the anti-soiling effect, and it was found that
adequate detergency
was exhibited and that satisfactory results were obtained in terms of
sustainability of the anti-
soiling effect as well.
