U.S. patent application number 11/636471 was filed with the patent office on 2007-06-14 for coating composition and vehicle interior material.
This patent application is currently assigned to Nissin Chemical Industry Co., Ltd.. Invention is credited to Toshiaki Ihara, Kazuyuki Matsumura, Norio Nakamura, Harukazu Okuda, Ichiro Tanii, Akira Yamamoto.
Application Number | 20070135551 11/636471 |
Document ID | / |
Family ID | 38140296 |
Filed Date | 2007-06-14 |
United States Patent
Application |
20070135551 |
Kind Code |
A1 |
Okuda; Harukazu ; et
al. |
June 14, 2007 |
Coating composition and vehicle interior material
Abstract
A coating composition comprising 100 pbw as solids of a
synthetic resin emulsion and 1-300 pbw of a non-halogen flame
retardant in which P and N-containing non-halogen flame retardant
particles are surface coated with hydrophobic inorganic oxide fine
particles is applicable to vehicle interior materials.
Inventors: |
Okuda; Harukazu;
(Echizen-shi, JP) ; Tanii; Ichiro; (Echizen-shi,
JP) ; Nakamura; Norio; (Echizen-shi, JP) ;
Matsumura; Kazuyuki; (Annaka-shi, JP) ; Yamamoto;
Akira; (Annaka-shi, JP) ; Ihara; Toshiaki;
(Annaka-shi, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Nissin Chemical Industry Co.,
Ltd.
|
Family ID: |
38140296 |
Appl. No.: |
11/636471 |
Filed: |
December 11, 2006 |
Current U.S.
Class: |
524/415 ;
524/492 |
Current CPC
Class: |
C08K 3/32 20130101; C08K
5/31 20130101; C08K 5/34928 20130101; C08K 3/016 20180101; C08K
9/02 20130101; C09D 5/18 20130101 |
Class at
Publication: |
524/415 ;
524/492 |
International
Class: |
C08K 3/32 20060101
C08K003/32 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 12, 2005 |
JP |
2005-357289 |
Claims
1. A coating composition comprising 100 parts by weight as solids
of a synthetic resin emulsion and 1 to 300 parts by weight of at
least one non-halogen flame retardant in which phosphorus and
nitrogen-containing non-halogen flame retardant particles are
surface coated with hydrophobic inorganic oxide fine particles.
2. The coating composition of claim 1, wherein said synthetic resin
emulsion is selected from the group consisting of (meth)acrylate
resin base emulsions, styrene/acrylate copolymer base emulsions,
urethane resin base emulsions, ethylene/vinyl acetate copolymer
base emulsions, rubber base emulsions, and mixtures thereof.
3. The coating composition of claim 1, wherein the particulate
phosphorus and nitrogen-containing non-halogen flame retardant is
selected from the group consisting of guanidine phosphate, ammonium
phosphate, melamine phosphate, ammonium polyphosphate,
melamine-surface-treated ammonium polyphosphate, silicon
compound-surface-treated ammonium polyphosphate, and mixtures
thereof.
4. The coating composition of claim 3, wherein the particulate
phosphorus and nitrogen-containing non-halogen flame retardant is
ammonium polyphosphate.
5. The coating composition of claim 3, wherein the particulate
phosphorus and nitrogen-containing non-halogen flame retardant is
silicon compound-surface-treated ammonium polyphosphate.
6. The coating composition of claim 1, wherein the hydrophobic
inorganic oxide fine particles are hydrophobic silica fine
particles.
7. The coating composition of claim 1, wherein the coated
non-halogen flame retardant has an average particle size of 3 to 35
.mu.m.
8. The coating composition of claim 1, wherein the hydrophobic
inorganic oxide fine particles have an average particle size of
0.001 to 5 .mu.m.
9. A vehicle interior material coated with the composition of claim
1.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This non-provisional application claims priority under 35
U.S.C. .sctn.119(a) on Patent Application No. 2005-357289 filed in
Japan on Dec. 12, 2005, the entire contents of which are hereby
incorporated by reference.
TECHNICAL FIELD
[0002] This invention relates to coating compositions for vehicle
interior materials such as car seats, car mats, and ceiling
members, and vehicle interior materials coated therewith.
BACKGROUND ART
[0003] Most coating agents applied to vehicle interior materials
such as car seats, car mats, and ceiling members in the prior art
are halogenated flame retardants such as decabromodiphenyl ether
for imparting flame retardance. The recent concern about the
environment demands to replace conventional halogenated flame
retardants by non-halogen flame retardants. The non-halogen flame
retardants, however, have drawbacks of poor flame retardance and
poor water resistance, as compared with the halogenated flame
retardants.
[0004] To overcome these problems, an attempt was made to
encapsulate a water-soluble non-halogen flame retardant such as
ammonium polyphosphate with a coating agent. JP-A 9-13037 discloses
such a coating agent comprising a polyamide resin, acrylic resin or
styrene resin although the resulting flame retardant is still less
resistant to water.
[0005] JP-A 10-110083 and JP-A 2003-171878 disclose that ammonium
polyphosphate particles can be admixed with acrylic emulsions in a
stable manner when they are surface coated with melamine resins or
the like. The emulsion compatibility is improved. However, if the
coating agent has a low degree of curing, coatings applied and
dried to substrates, typically fabrics are not improved in water
resistance. For example, a problem has been pointed out that the
coating surface becomes slimy when contacted with water. On the
other hand, if the coating agent has a higher degree of curing, the
above problem is overcome, but formaldehyde is detectable, raising
an environmental problem.
[0006] In addition to the ammonium polyphosphate, the known
non-halogen flame retardants include metal hydroxides such as
aluminum hydroxide and magnesium hydroxide and phosphate esters,
which are considered less flame retardant than the halogenated
flame retardants.
[0007] There exists a need for coating compositions comprising
non-halogen flame retardants having physical properties comparable
to coating compositions comprising conventional halogenated flame
retardants.
SUMMARY OF THE INVENTION
[0008] An object of the present invention is to provide a coating
composition for use with vehicle interior materials such as car
seats, car mats, and ceiling members, comprising a non-halogen
flame retardant, which composition has physical properties
comparable to coating compositions comprising conventional
halogenated flame retardants. Another object is to provide a
vehicle interior material coated with the coating composition.
[0009] The inventors have found that when a certain amount of a
non-halogen flame retardant in which non-halogen flame retardant
particles are surface coated with hydrophobic inorganic oxide fine
particles is added to a synthetic resin emulsion, there is obtained
a novel coating composition comprising a non-halogen flame
retardant, which composition has physical properties comparable to
coating compositions comprising conventional halogenated flame
retardants. This coating composition is suitable to apply to
vehicle interior materials such as car seats, car mats, and ceiling
members.
[0010] Therefore, the present invention provides a coating
composition comprising a synthetic resin emulsion and one or more
non-halogen flame retardant in which phosphorus and
nitrogen-containing non-halogen flame retardant particles are
surface coated with hydrophobic inorganic oxide fine particles, the
coated non-halogen flame retardant being added in an amount of 1 to
300 parts by weight per 100 parts by weight as solids of the
synthetic resin emulsion. A vehicle interior material coated with
the composition is also contemplated.
BENEFITS OF THE INVENTION
[0011] The coating composition comprising a non-halogen flame
retardant according to the invention has physical and flame
retardant properties comparable to coating compositions comprising
conventional halogenated flame retardants and is thus suitable to
apply to vehicle interior members such as car seats, car mats and
ceiling members.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0012] The coating composition of the invention is defined as
comprising a synthetic resin emulsion and a non-halogen flame
retardant in which phosphorus and nitrogen-containing non-halogen
flame retardant particles are surface coated with hydrophobic
inorganic oxide fine particles, which retardant is simply referred
to as "coated non-halogen flame retardant," hereinafter. The coated
non-halogen flame retardant is added in an amount of 1 to 300 parts
by weight per 100 parts by weight of solids of the synthetic resin
emulsion.
Emulsion
[0013] The synthetic resin emulsions used herein include vinyl
chloride resin base emulsions, (meth)acrylate resin base emulsions,
styrene/acrylate copolymer base emulsions, urethane resin base
emulsions, silicone resin base emulsions, fluororesin base
emulsions, epoxy resin base emulsions, ethylene/vinyl acetate
copolymer base emulsions, and rubber base emulsions such as
styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber
(NBR) base emulsions. These emulsions may be used alone or in
admixture of two or more. Preference is given to (meth)acrylate
resin base emulsions, styrene/acrylate copolymer base emulsions,
urethane resin base emulsions, ethylene/vinyl acetate copolymer
base emulsions, and rubber base emulsions such as SBR and NBR. It
is noted that the term "(meth)acrylate resin" refers to acrylate or
methacrylate resins.
[0014] The above-listed synthetic resin emulsions may be
synthesized by emulsion polymerization. Instead, any of
commercially available synthetic resin emulsions may be used.
Examples of commercially available synthetic resin emulsions
include, but are not limited to, (meth)acrylate resin base
emulsions such as Vinyblan 2598 by Nisshin Chemical Co., Ltd. and
Aron A-104 by Toa Synthesis Co., Ltd.; styrene/acrylate copolymer
base emulsions such as Vinyblan 2590 by Nisshin Chemical Co., Ltd.
and Movinyl 975A by Clariant Polymer Co., Ltd.; urethane resin base
emulsions such as Hydran HW-311 and HW-301 by Dainippon Ink &
Chemicals, Inc. and Permarine UA-150 by Sanyo Chemical Industry
Co., Ltd.; ethylene/vinyl acetate copolymer base emulsions such as
Sumikaflex 400 and 752 by Sumitomo Chemical Co., Ltd. and Panflex
OM-4000 by Kurare Co., Ltd.; and rubber base emulsions such as
Nalstar SR-100 and SR-112 by Nippon A&L Inc. and Nipol 1561 by
Nippon Zeon Co., Ltd.
[0015] When the foregoing synthetic resin emulsions are prepared by
emulsion polymerization, radical polymerization is generally
employed for synthesis. The starting monomers used are monomers
containing unsaturated groups having a radical polymerization
ability.
[0016] Examples of suitable unsaturated group-containing monomers
include ethylene and propylene; chlorine-containing monomers such
as vinyl chloride and vinylidene chloride; vinyl carboxylate
monomers such as vinyl acetate and vinyl propionate; aromatic vinyl
monomers such as styrene and .alpha.-methylstyrene; conjugated
diene monomers such as 1,3-butadiene and 2-methyl-1,3-butadiene;
ethylenically unsaturated monocarboxylic acid esters such as methyl
acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
and methyl methacrylate; ethylenically unsaturated dicarboxylic
acid esters such as dimethyl itaconate, diethyl maleate, monobutyl
maleate, monoethyl fumarate, and dibutyl fumarate; ethylenically
unsaturated monocarboxylic acids such as acrylic acid, methacrylic
acid and crotonic acid; ethylenically unsaturated dicarboxylic
acids such as itaconic acid, maleic acid, and fumaric acid; epoxy
group-containing monomers such as glycidyl methacrylate; alcoholic
hydroxyl group-containing monomers such as 2-hydroxyethyl
methacrylate; alkoxyl group-containing monomers such as
methoxyethyl acrylate; nitrile group-containing monomers such as
acrylonitrile; amide group-containing monomers such as acrylic
amide; amino group-containing monomers such as dimethylaminoethyl
methacrylate; and monomers having at least two ethylenically
unsaturated groups in a molecule such as divinyl benzene and allyl
methacrylate.
[0017] For the emulsion polymerization, any well-known emulsion
polymerization techniques may be employed. The foregoing monomers
and polymerization aids (e.g., emulsifiers such as alkyl sulfate
salts, polymerization initiators such as ammonium persulfate, chain
transfer agents such as mercaptans, pH regulators such as sodium
carbonate, antifoaming agents) may be added together at the
initial, or continuously over the course. Alternatively, some of
them may be added continuously or in divided portions during the
polymerization.
[0018] Suitable emulsifiers used in the emulsion polymerization
include surfactants of the following classes (1) to (4), which may
be used alone or in admixture of two or more. [0019] (1) Anionic
surfactants, such as alkyl sulfate ester salts, polyoxyethylene
alkyl ether sulfate ester salts, alkylbenzene sulfonate salts,
alkyldiphenylether disulfonate salts, alkyl naphthalene sulfonate
salts, fatty acid salts, dialkylsulfosuccinate salts,
alkylphosphate salts, polyoxyethylene alkylphenyl phosphate ester
salts. [0020] (2) Nonionic surfactants, such as polyoxyethylene
alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene
fatty acid esters, sorbitan fatty acid esters, polyoxyethylene
sorbitan fatty acid esters, polyoxyalkylene alkyl ethers,
polyoxyethylene derivatives, glycerin fatty acid esters,
polyoxyethylene hardened castor oil, polyoxyethylene alkyl amines,
alkyl alkanol amides, or acetylene alcohol, acetylene glycol and
ethylene oxide addition products thereof. [0021] (3) Cationic
surfactants, such as alkyl trimethylammonium chlorides, dialkyl
dimethylammonium chlorides, alkylbenzylammonium chlorides, and
alkylamine salts. [0022] (4) Polymerizable surfactants having a
double bond with a radical polymerization ability in a molecule,
such as alkylallylsulfosuccinic acid salts, methacryloyl
polyoxyalkylene sulfate ester salts, polyoxyethylene
nonylpropenylphenyl ether sulfate ester salts.
[0023] These surfactants are generally used in amounts of 0.3 to
20% by weight, preferably 0.5 to 10% by weight based on the weight
of the monomers.
[0024] Examples of the polymerization initiator used for the
emulsion polymerization include persulfates such as ammonium
persulfate, potassium persulfate; azo compounds such as
2,2'-diamidino-2,2'-azopropane dihydrogen chloride salt and
azobisisobutyronitrile; and peroxides such as cumene hydroperoxide,
benzoyl peroxide and hydrogen peroxide. Well-known redox initiators
such as potassium persulfate and sodium hydrogen sulfite are also
useful. The amount of the polymerization initiator used is
generally 0.1 to 5% by weight, preferably 0.2 to 2% by weight based
on the weight of the monomers.
[0025] The emulsion polymerization is generally conducted at a
temperature of 10 to 90.degree. C., desirably 50 to 80.degree. C.
and for a time of about 3 to about 20 hours. This polymerization is
desirably conducted in an atmosphere of an inert gas such as
nitrogen gas.
Flame Retardant
[0026] The flame retardant used in the coating composition of the
invention is a non-halogen flame retardant in which phosphorus and
nitrogen-containing non-halogen flame retardant particles are
surface coated with hydrophobic inorganic oxide fine particles.
[0027] Flame retardants containing only phosphorus include, for
example, phosphoric acid esters, but are less flame retardant than
the halogenated flame retardants. The inventors select as the flame
retardant component a flame retardant containing both phosphorus
and nitrogen for achieving an improved flame retardant effect.
[0028] Examples of the phosphorus and nitrogen-containing
non-halogen flame retardant include guanidine phosphate, ammonium
phosphate, melamine phosphate, ammonium polyphosphate, ammonium
polyphosphate surface treated with melamine, and ammonium
polyphosphate surface treated with silicon compounds, which may be
used alone or in admixture of two or more. Inter alia, ammonium
polyphosphates are preferred. Useful ammonium polyphosphates are
commercially available. These flame retardants are in the form of
particles, preferably having an average particle size of 3 to 25
.mu.m, especially 5 to 18 .mu.m. It is noted that the average
particle size is determined as a weight average value or median
diameter, for example, using a particle size distribution analyzer
relying on the laser light diffraction technique. The silicon
compound-surface-treated ammonium polyphosphate is preferably
obtained by treating or coating surfaces of ammonium polyphosphate
particles with an alkoxysilane containing a functional group such
as carboxyl or amino group or a partial hydrolyzate thereof, using
an in-liquid drying process.
[0029] It has been found that excellent water repellency is exerted
by coating surfaces of phosphorus and nitrogen-containing
non-halogen flame retardant particles with hydrophobic inorganic
oxide fine particles.
[0030] The hydrophobic inorganic oxide fine particles used herein
are not particularly limited as long as they are hydrophobic
inorganic oxides (i.e., having hydrophobic groups). Examples
include, but are not limited to, hydrophobic silicon oxide,
titanium oxide, zinc oxide, aluminum oxide, and cerium oxide. Inter
alia, hydrophobic silicon oxide or silica is best suited from the
cost and performance aspects.
[0031] The silica which can be used herein is generally divided
into two types: dry silicas which are typically obtained by
decomposition of silicon halides or by heat reduction of silica
sand followed by oxidation in air; and wet silicas which are
typically obtained by direct decomposition of sodium silicate with
mineral acids such as sulfuric acid. Silica produced by a sol-gel
method involving hydrolysis of alkoxysilanes is also acceptable.
Any type of silica is useful as long as it has been provided with
hydrophobic groups such as alkyl groups, typically methyl, by
treating with hydrophobic surface-treating agents including
organosilazanes such as hexamethyldisilazane, organoalkoxysilanes
such as methyltrimethoxysilane, and organopolysiloxanes such as
organohydrogenpolysiloxanes.
[0032] A measure of hydrophobicity is preferably represented by a
degree of hydrophobicity, which is at least 45, preferably 50 to
70. The degree of hydrophobicity is determined by a methanol
titration test of adding silica fine particles to a methanol/water
mixture for wetting the fine particles, and determining the
percentage of methanol in the methanol/water mixture, as shown
below.
[Measurement of Hydrophobicity]
[0033] (1) Charge 0.2 g of sample to a 500 ml-flask. [0034] (2) Add
50 ml of deionized water thereto and agitate the mixture with a
stirrer. [0035] (3) Drop methanol to the mixture from a buret while
agitating, and read the dropping amount of methanol when sample is
wholly dispersed to deionized water. [0036] (4) Calculate
hydrophobicity from the following equation.
Hydrophobicity=A.times.100/(A+B) wherein
[0037] A is titer of methanol (ml)
[0038] B is amount of deionized water (ml)
[0039] Lager values indicate higher hydrophobicity whereas smaller
values indicate higher hydrophillicity.
[0040] The hydrophobic inorganic oxide fine particles, typically
hydrophobic silica fine particles have an average particle size
sufficient to deposit on the phosphorus and nitrogen-containing
non-halogen flame retardant particles, preferably from 0.001 to 5
.mu.m. An average particle size of 0.001 to 2 .mu.m is more
preferred. The shape of fine particles is not particularly limited
and may be spherical or irregular.
[0041] Surfaces of the non-halogen flame retardant particles can be
coated with the hydrophobic inorganic oxide fine particles by
feeding 100 parts by weight of non-halogen flame retardant
particles and 0.1 to 20 parts by weight, preferably 1 to 10 parts
by weight of hydrophobic inorganic oxide fine particles to a
suitable mixer such as a ball mill, V-type mixer, ribbon mixer, or
screw mixer, equipped with a high-speed agitation means having a
revolution capability of about 100 to 5,000 rpm where they are
agitated and mixed. Then the hydrophobic inorganic oxide fine
particles deposit on and adhere to surfaces of the non-halogen
flame retardant particles, yielding a coated non-halogen flame
retardant.
[0042] The coated non-halogen flame retardant preferably has an
average particle size of 3 to 35 .mu.m, especially 5 to 20 .mu.m.
In the practice of the invention, one or more coated non-halogen
flame retardants may be used.
[0043] The synthetic resin emulsion and the coated non-halogen
flame retardant (i.e., phosphorus and nitrogen-containing
non-halogen flame retardant particles surface coated with
hydrophobic inorganic oxide fine particles) are mixed in such a
proportion that 1 to 300 parts by weight, preferably 5 to 200 parts
by weight of the coated non-halogen flame retardant is present per
100 parts by weight as solids of the synthetic resin emulsion. Less
than 1 part of the flame retardant provides an insufficient flame
retardant effect whereas more than 300 parts of the flame retardant
fails to provide a coating with a practical strength and increases
the cost.
[0044] In addition to the above-mentioned components, the coating
composition of the invention may contain additives, for example,
cellulosic water-soluble polymers such as hydroxymethyl cellulose,
hydroxyethyl cellulose, carboxymethyl cellulose and methyl
cellulose; synthetic water-soluble polymers such as fully
saponified polyvinyl alcohol, partially saponified polyvinyl
alcohol, polyacrylic acid and salts thereof, polymethacrylic acid
and salts thereof, polyacrylamide, and alkali viscosity buildup
type acrylic emulsions; bases such as ammonia, triethylamine, and
sodium hydroxide; polyethylene wax, anti-foaming agents, leveling
agents, tackifiers, preservatives, anti-bacterial agents, and
anti-rusting agents as long as they do not compromise the objects
of the invention.
[0045] The coating composition of the invention is prepared by
intimately mixing predetermined amounts of the foregoing components
in a conventional manner. The coating composition thus obtained
should preferably have a solids content of 30 to 70% by weight,
more preferably 40 to 60% by weight.
[0046] The coating composition thus obtained is advantageously
applicable to various substrates which must be rendered flame
retardant, for example, vehicle interior materials such as car
seats, car mats and ceiling members.
[0047] In applying the coating composition to substrates, any of
well-known applicators, such as gravure roll coaters, knife
coaters, and reverse roll coaters may be used. The substrates
include woven fabrics and knitted goods of polyester, nylon or the
like and non-woven fabrics of polyester, polypropylene or the
like.
[0048] In applying the coating composition to substrates, the
composition may be used as such or after thickening with
commercially available thickeners such as alkali viscosity buildup
type acrylic emulsions. On use, the coating composition should
preferably be adjusted to a viscosity of 10,000 to 50,000 mPas at
25.degree. C., more preferably 20,000 to 40,000 mPas at 25.degree.
C., as measured by a Brookfield viscometer.
[0049] The coating weight of the coating composition is generally
30 to 600 g/m.sup.2, desirably 50 to 500 g/m.sup.2, in a dry state.
After application, the coating is desirably dried at a temperature
of about 100 to 180.degree. C. for about 1 to 10 minutes.
[0050] Typical vehicle interior materials are car seats, car mats
and ceiling members, for which not only flame retardance, but also
texture are key features. The texture is measured by the 45 degree
cantilever method of JIS L1079 and expressed by stiffness. The
texture requirement differs depending on the identity of vehicle
interior material. In the case of car seats, a soft texture is
required as expressed by a stiffness less than or equal to 100. In
the case of car mats and ceiling members, on the other hand, a hard
texture is required as expressed by a stiffness of greater than
100. In general, the coating weight of the coating composition is
desirably 30 to 200 g/m.sup.2 in a dry state in the case of car
seats, and the coating weight is desirably 300 to 600 g/m.sup.2 in
a dry state in the case of car mats and ceiling members.
EXAMPLE
[0051] Preparation Examples (PE), Examples (EX), and Comparative
Examples (CE) are given below for further illustrating the
invention although the invention is not limited to these Examples.
All parts and % are by weight.
Preparation Example 1
[0052] A 3-L glass container equipped with a stirrer, reflux
condenser and thermometer was thoroughly purged of air with
nitrogen. To the glass container were added 1,000 parts of
deionized water, 20 parts of Emal 0 (Kao Co., Ltd., sodium
laurylsulfate), and 30 parts of DKSNL-600 (Daiichi Kogyo Seiyaku
Co., Ltd., polyoxyethylene lauryl ether). Stirring was started.
[0053] The internal temperature of the container was raised to
80.degree. C., whereupon a mixture of 580 parts butyl acrylate, 300
parts ethyl acrylate, 100 parts acrylonitrile and 20 parts acrylic
acid was continuously fed over 4 hours and then a mixture of 4
parts ammonium persulfate and 50 parts water continuously fed over
4 hours. Thereafter, reaction was effected at 80.degree. C. for one
hour. The reaction solution was cooled to 30.degree. C., yielding
an acrylate resin base emulsion having a solids content of
49.5%.
Preparation Examples 2 to 4
[0054] Several emulsions were obtained by effecting emulsion
polymerization as in Preparation Example 1. The composition of the
emulsions of Preparation Examples 1 to 4 and a commercial synthetic
resin emulsion is shown in Table 1.
Preparation Example 5
[0055] To a ribbon mixer were fed 100 parts of ammonium
polyphosphate (Pecoflame TC204P by Clariant, average particle size
8 .mu.m) and 10 parts of hydrophobic silica (degree of
hydrophobicity 45, average particle size 1.6 .mu.m) which had been
hydrophobized by contacting dry silica having a specific surface
area of 120 m.sup.2/g with dimethyldichlorosilane diluted with
nitrogen and steam at 500.degree. C. such that a carbon content per
unit surface area fell in the range of 6.0 to 7.0.times.10.sup.-5
g/m.sup.3. The mixer was operated at a high speed of 1,000 rpm for
one minute for agitation mixing. This operation yielded
silica-coated ammonium polyphosphate. The coated ammonium
polyphosphate was observed under a scanning electron microscope
(SEM), finding that silica fines adhered to surfaces of ammonium
polyphosphate particles to provide a dense and tight coverage.
Preparation Example 6
[0056] To a ribbon mixer were fed 100 parts of ammonium
polyphosphate surface treated with amino-containing silicone
oligomer (FRX-304 by Shin-Etsu Chemical Co., Ltd., average particle
size 8 .mu.m) and 10 parts of hydrophobic silica (degree of
hydrophobicity 45, average particle size 1.6 .mu.m) which had been
hydrophobized by contacting dry silica having a specific surface
area of 120 m.sup.2/g with dimethyldichlorosilane diluted with
nitrogen and steam at 500.degree. C. such that a carbon content per
unit surface area fell in the range of 6.0 to 7.0.times.10.sup.-5
g/m.sup.3. The mixer was operated at a high speed (1,000 rpm) for
one minute for agitation mixing. This operation yielded
silica-coated, organosilicon resin surface treated ammonium
polyphosphate. The coated ammonium polyphosphate was observed under
a SEM, finding that silica fines adhered to surfaces of
organosilicon resin surface treated ammonium polyphosphate
particles to provide a dense and tight coverage.
Preparation Example 7
[0057] To 100 parts of ammonium polyphosphate (FR CROS S 10 by
Budenheim, average particle size 8 .mu.m) were added 5 parts of a
linear silicone fluid (KF-96H by Shin-Etsu Chemical Co., Ltd.) and
100 parts of toluene. The mixture was agitated for 30 minutes, and
the toluene was removed under reduced pressure. The residue was
ground on a grinder, yielding silicone-treated ammonium
polyphosphate having an average particle size of 10 .mu.m.
Examples 1 to 7 and Comparative Examples 1 to 8
[0058] To a stainless steel container was added 100 parts of each
of the emulsions of Preparation Examples 1 to 4 or a commercial
emulsion. Agitation was started. With agitation continued, a
predetermined amount of a dispersion liquid (solids 60%) of each of
the treated ammonium polyphosphates of Preparation Examples 5 to 7
or commercial ammonium polyphosphate in water with the aid of a
surfactant Latemul ASK (by Kao Corp.) was added, followed by one
hour of agitation. Thereafter, deionized water was added for
adjusting the solids content to 50.+-.1%. Then a thickener Boncoat
V (by Dainippon Ink & Chemicals, Inc., alkali viscosity buildup
type acrylic emulsion) and 25% aqueous ammonia were added to the
dispersion for thickening, yielding a coating composition having an
increased viscosity of 30,000.+-.3,000 mPas as measured at
25.degree. C. by a Brookfield viscometer. The formulation of these
coating compositions is shown in Tables 2 and 3.
[0059] A predetermined amount of each coating composition was
applied to a commercial polyester woven fabric with a weight of 400
g/m.sup.2 and a commercial polypropylene non-woven fabric with a
weight of 700 g/m.sup.2, and dried at 130.degree. C. for 5 minutes,
completing samples.
[0060] The samples of Examples and Comparative Examples were
examined for sew line fatigue, flame retardance, water resistance,
stiffness, formaldehyde emission, and heat resistance. The samples
of polyester woven fabric with a weight of 400 g/m.sup.2 were used
as car seats and examined for sew line fatigue, flame retardance,
water resistance, stiffness, formaldehyde emission, and heat
resistance, with the results shown in Table 4. The samples of
polypropylene non-woven fabric with a weight of 700 g/m.sup.2 were
used as car mats and examined for flame retardance, water
resistance, stiffness, formaldehyde emission, and heat resistance,
with the results shown in Table 5.
[0061] The test methods and evaluation criteria are described
below.
1. Sew Line Fatigue
[0062] Two pairs of pieces of 10 cm wide and 10 cm long were cut
out from each of warp and weft directions. To the back surface of
each piece, a urethane foam slab (density 0.02 g/cm.sup.3,
thickness 5 mm) and a backing fabric (nylon spun-bonded fabric, 40
g/m.sup.2) of the same size were laid to form a laminate. Two
laminates were laid with their front surfaces mated each other.
Using a sewing machine, the assembly was sewed at 1 cm inside from
the side edge. In this way, two sets of specimens were prepared for
each of warp and weft directions. The specimen was mounted on a sew
line fatigue testing machine (Yamaguchi Chemical Industry Co.,
Ltd.) which was operated under a load of 3 kg over 2,500 cycles.
With the load of 3 kg kept applied, the sew line fatigue of the
specimen was observed through a scale magnifier.
[0063] The term "sew line fatigue" refers to the distance between
the sewing thread moved in the loading direction by repeated
fatigue and the thread within fabric located nearest thereto,
measured in unit 0.1 mm. An average of measurements at two
locations is the sew line fatigue of the test specimen.
[0064] Rating Criterion [0065] .largecircle.: moving
distance.ltoreq.2.2 mm [0066] .times.: moving distance>2.2 mm 2.
Flame Retardance
[0067] Examined by the test method of US Federal Motor Vehicle
Safety Standard FMVS S-302.
[0068] Rating Criterion for Car Seat [0069] .largecircle.: burnt
distance.ltoreq.38 mm [0070] .times.: burnt distance>38 mm
[0071] Rating Criterion for Car Mat [0072] .largecircle.: burnt
distance.ltoreq.38 mm+burning time.ltoreq.60 sec or burning
rate.ltoreq.10 cm/min [0073] .times.: burnt distance>38
mm+burning time>60 sec+burning rate>10 cm/min 3. Water
Resistance
[0074] A water droplet having a diameter of 5 mm was dropped on the
coated surface of fabric. It was examined whether or not the coated
surface became slimy.
[0075] Rating Criterion [0076] .circleincircle.: not slimy, no
penetration of water into coated surface [0077] .largecircle.: not
slimy [0078] .DELTA.: somewhat slimy [0079] .times.: heavily slimy
4. Stiffness
[0080] Examined by the 45.degree. cantilever method of JIS L1079
(5.17 A method). The higher the stiffness, the harder felt was the
sample.
[0081] Rating Criterion for Car Seat [0082] .largecircle.:
stiffness.ltoreq.100 [0083] .times.: stiffness>100
[0084] Rating Criterion for Car Mat [0085] .largecircle.:
stiffness>100 [0086] .times.: stiffness.ltoreq.100 5.
Formaldehyde Emission
[0087] A 2-L Tedlar.RTM. Bag (Dupont) was charged with 50 cm.sup.2
of a sample, purged with nitrogen and sealed. The bag was held at
65.degree. C. for 2 hours. Using a gas detector 91L (Gas Tech Co.,
Ltd.), formaldehyde was detected.
[0088] Rating Criterion [0089] .largecircle.: no formaldehyde
[0090] .times.: formaldehyde detected 6. Heat Resistance
[0091] The samples of polyester woven fabric and polypropylene
non-woven fabric coated with different coating compositions were
heat treated at 150.degree. C. for one hour, after which a change
of color on the coating surface was visually examined. [0092]
Rating A: no color change [0093] Rating B: yellowed
[0094] Rating C: materially yellowed TABLE-US-00001 TABLE 1 Resin
emulsion Composition solids (%) Solids St MMA BA EA AN AA GMA (%)
Preparation 58 30 10 2 49.5 Example 1 Preparation 20 72 5 3 50.3
Example 2 Preparation 80 18 2 50.5 Example 3 Preparation 65 32 3
49.8 Example 4 Hydran HW-301 urethane resin base emulsion, 45
Dainippon Ink & Chemicals, Inc. Sumikaflex 752 ethylene/vinyl
acetate resin base emulsion, 50 Sumitomo Chemical Co., Ltd. Nalstar
SR-112 SBR base emulsion, Nippon A&L Inc. 50 St: styrene MMA:
methyl methacrylate BA: butyl acrylate EA: ethyl acrylate AN:
acrylonitrile AA: acrylic acid GMA: glycidyl methacrylate
[0095] TABLE-US-00002 TABLE 2 Coating composition for car seat
Amount of composition, as solids (pbw) Example Comparative Example
1 2 3 1 2 3 4 5 Preparation 100 100 100 100 Example 1 Preparation
100 100 100 Example 2 Hydran 100 HW-301 Preparation 150 150 0.5
Example 5 Preparation 150 400 Example 6 Preparation 150 Example 7
Terrages 100 C-30 Terrages 100 C-60 Terrages C-30: Chisso Corp.,
melamine-coated ammonium polyphosphate Terrages C-60: Chisso Corp.,
melamine/formaldehyde-coated ammonium polyphosphate
[0096] TABLE-US-00003 TABLE 3 Coating composition for car mat
Amount of composition, as solids (pbw) Example Comparative Example
4 5 6 7 6 7 8 Preparation 100 50 100 100 Example 3 Preparation 100
100 Example 4 Sumikaflex 752 50 Nalstar SR-112 100 Preparation 50
50 Example 5 Preparation 50 70 0.5 Example 6 Terrages C-30 10
Terrages C-60 15
[0097] TABLE-US-00004 TABLE 4 Test results of car seats Example
Comparative Example 1 2 3 1 2 3 4 5 Dry coating 140 120 100 100 110
160 140 110 weight (g/m.sup.2) Sew line .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. X fatigue Flame .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. X
.largecircle. retardance Water .circleincircle. .circleincircle.
.circleincircle. .DELTA./X .DELTA./X .largecircle. .largecircle.
.largecircle. resistance Stiffness .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Formaldehyde .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. X
.largecircle. .largecircle. Heat A A A A C C B A resistance
[0098] TABLE-US-00005 TABLE 5 Test results of car mats Example
Comparative Example 4 5 6 7 6 7 8 Dry coating 360 380 380 430 420
420 460 weight (g/m.sup.2) Flame .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. X
retardance Water .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .DELTA./X .largecircle. .largecircle. resistance
Stiffness .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Formaldehyde
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. X .largecircle. Heat A A A A B B B resistance
[0099] Japanese Patent Application No. 2005-357289 is incorporated
herein by reference.
[0100] Although some preferred embodiments have been described,
many modifications and variations may be made thereto in light of
the above teachings. It is therefore to be understood that the
invention may be practiced otherwise than as specifically described
without departing from the scope of the appended claims.
* * * * *