U.S. patent application number 10/589501 was filed with the patent office on 2007-08-16 for modifier for resin and resin composition using the same and formed article.
Invention is credited to Yasutaka Doi, Hideaki Makino, Yohei Miwa, Keiji Nakamura, Masahiro Osuka, Tsuneki Wakita.
Application Number | 20070191542 10/589501 |
Document ID | / |
Family ID | 34863470 |
Filed Date | 2007-08-16 |
United States Patent
Application |
20070191542 |
Kind Code |
A1 |
Wakita; Tsuneki ; et
al. |
August 16, 2007 |
Modifier for resin and resin composition using the same and formed
article
Abstract
A modifier for resin has an average particle size of 20 .mu.m or
more, wherein particles having an average particle size of 10 .mu.m
or less account for less than 30% by mass of the modifier, and
particles having an average particle size of 10 .mu.m or less
account for 30% by mass or more of the modifier after irradiating
the modifier with ultrasonic wave of 40 W for 5 minutes. Also a
resin composition comprises 1 to 40% by mass of the modifier for
resin and 99 to 60% by mass (the total amount of both components is
100% by mass) of a thermoplastic resin or a curable resin, and a
molded article is produced by molding the same.
Inventors: |
Wakita; Tsuneki; (Otake-shi,
JP) ; Nakamura; Keiji; (Otake-shi, JP) ;
Makino; Hideaki; (Toyohashi-shi, JP) ; Osuka;
Masahiro; (Kawasaki-shi, JP) ; Miwa; Yohei;
(Toyohashi-shi, JP) ; Doi; Yasutaka;
(Toyohashi-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
34863470 |
Appl. No.: |
10/589501 |
Filed: |
February 15, 2005 |
PCT Filed: |
February 15, 2005 |
PCT NO: |
PCT/JP05/02210 |
371 Date: |
January 16, 2007 |
Current U.S.
Class: |
525/70 ;
257/E23.119 |
Current CPC
Class: |
H01L 23/293 20130101;
C08L 51/003 20130101; C08L 51/085 20130101; C08L 33/04 20130101;
C08L 51/003 20130101; C08L 63/00 20130101; C08L 51/085 20130101;
C08L 2666/02 20130101; C08L 51/04 20130101; C08F 283/12 20130101;
C08L 33/04 20130101; C08L 51/04 20130101; H01L 2924/00 20130101;
H01L 2924/0002 20130101; C08L 2666/02 20130101; C08L 2666/02
20130101; C08F 265/04 20130101; C08F 279/02 20130101; H01L
2924/0002 20130101; C08L 2666/24 20130101 |
Class at
Publication: |
525/070 |
International
Class: |
C08L 51/00 20060101
C08L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 16, 2004 |
JP |
2004-037784 |
Apr 5, 2004 |
JP |
2004-110913 |
Claims
1. A modifier for resin having an average particle size of 20 .mu.m
or more, wherein particles having an average particle size of 10
.mu.m or less account for less than 30% by mass of the modifier,
and particles having an average particle size of 10 .mu.m or less
account for 30% by mass or more of the modifier after irradiating
the modifier with ultrasonic wave of 40 W for 5 minutes.
2. The modifier for resin according to claim 1, which is made of an
acrylic graft copolymer.
3. A resin composition comprising 1 to 40% by mass of the modifier
for resin according to claim 1 and 99 to 60% by mass (the total
amount of both components is 100% by mass) of a thermoplastic resin
or a curable resin.
4. A molded article which is produced by molding the resin
composition according to claim 3.
Description
TECHNICAL FIELD
[0001] The present invention relates to a modifier for resin, which
exhibits excellent dispersibility to a curable resin or a
thermoplastic resin.
BACKGROUND ART
[0002] Resin products are produced according to purposes such as
electric and electronic products, automobiles and building
materials. To exhibit performances required according to the
purposes, one or several kinds of resins and additives are added to
the molded articles. These resins often require high toughness and
a modifier for resin is added so as to impart impact strength
required to end uses of the resin products.
[0003] Usually, this modifier for resin is supplied in the form of
a powder. Therefore, dispersion of the modifier into a matrix resin
becomes very important element and, when poor dispersion occurs,
sufficient modification effect is not obtained and inclusion
composed of extraordinary substance of the modifier is formed in
appearance. Dispersion of the modifier for resin is particularly
important element in electric and electronic components, solder
pastes and coating materials. Particularly, it is necessary
condition for a modifier for semiconductor sealing material to
cause no poor dispersion due to the thinning and fine patterning of
a package with recent high degree of functioning and high degree of
integration of a semiconductor device.
[0004] As a method of imparting the strength to a semiconductor
sealing material, a method of adding a rubber such as MBS resin to
an epoxy resin has been proposed (see, for example, Patent
Documents 1 and 2).
[0005] Patent Document 1: Japanese Unexamined Patent Application,
First Publication No. 2000-7890
[0006] Patent Document 2: Japanese Unexamined Patent Application,
First Publication No. S62-22825
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0007] However, the modifier for resin is not insufficient in
dispersibility in a molding method in which processing is conducted
under low shear. For example, when the modifier is added to a
sealing epoxy resin, poor dispersion occurs and the resin itself
may be cracked or fractured by thermal stress produced during a
soldering treatment.
[0008] The present invention has been made so as to provide a
modifier for resin, which exhibits excellent dispersibility when
added to a thermoplastic resin or a curable resin, and also can
impart impact resistance, matting properties or thickening
properties.
[0009] The gist of the present invention lies in a modifier for
resin having an average particle size of 20 .mu.m or more, wherein
particles having an average particle size of 10 .mu.m or less
account for less than 30% by mass of the modifier, and particles
having an average particle size of 10 .mu.m or less account for 30%
by mass or more of the modifier after irradiating the modifier with
ultrasonic wave of 40 W for 5 minutes.
[0010] Also the gist of the present invention lies in a resin
composition comprising 1 to 40% by mass of the modifier for resin
and 99 to 60% by mass (the total amount of both components is 100%
by mass) of a thermoplastic resin or a curable resin.
[0011] Also the gist of the present invention lies in a molded
article which is produced by molding the same.
EFFECTS OF THE INVENTION
[0012] The modifier for resin of the present invention is excellent
in dispersibility when added to a thermoplastic resin or a curable
resin and is excellent in appearance in the product, and also can
impart sufficient impact strength.
[0013] Also a resin composition prepared by mixing the modifier for
resin of the present invention with a thermoplastic resin or a
curable resin can be applied to IC sealing agents, solder pastes
and molded articles.
[0014] Furthermore, when the modifier for resin of the present
invention is mixed with a curable resin composition, gloss is not
increased even by friction and a matted coating film with excellent
adhesion of a recoated coating film can be formed. Also the
modifier for resin of the present invention exhibits excellent
thickening properties to a nonaqueous coating material.
BEST MODE FOR CARRYING OUT THE INVENTION
[0015] Although the structure of the modifier for resin of the
present invention is not specifically limited, a graft copolymer is
preferably used. The graft copolymer is not specifically limited as
far as it has a so-called core-shell type structure formed by using
a rubbery polymer as a trunk polymer and grafting the rubbery
polymer with a graft polymerizable vinyl-based monomer.
[0016] The rubbery polymer is not specifically limited and there
can be used those, which are commonly used, such as diene-based
rubber, acrylic rubber, silicone-based rubber or silicone-acrylic
composite rubber. Among these, an acrylic rubber is preferably used
because a modifier for resin having high dispersibility is
obtained.
[0017] The diene-based rubber can be obtained by polymerizing
1,3-butadiene and, if necessary, at least one vinyl-based monomer
copolymerizable with 1,3-butadiene. Examples of the vinyl-based
monomer include aromatic vinyl such as styrene or
.alpha.-methylstyrene; alkyl methacrylate ester such as methyl
methacrylate or ethyl methacrylate; alkyl acrylate ester such as
ethyl acrylate or n-butyl acrylate; unsaturated nitrile such as
acrylonitrile or methacrylonitrile; vinyl ether such as methyl
vinyl ether or butyl vinyl ether; vinyl halide such as vinyl
chloride or vinyl bromide; vinylidene halide such as vinylidene
chloride or vinylidene bromide; and vinyl-based monomer having a
glycidyl group, such as glycidyl acrylate, glycidyl methacrylate,
allyl glycidyl ether or ethylene glycol glycidyl ether.
[0018] Furthermore, it is possible to use in combination with
crosslinkable monomers, for example, aromatic polyfunctional vinyl
compound such as divinylbenzene or divinyltoluene; polyhydric
alcohol such as ethylene glycol dimethacrylate or 1,3-butanediol
diacrylate; trimethacrylate; triacrylate; allyl carboxylate ester
such as allyl acrylate or allyl methacrylate; and di- and triallyl
compounds such as diallyl phthalate, diallyl sebacate and
triallyltriazine.
[0019] One or more kinds of vinyl-based monomers and crosslinkable
monomers can be used. As a chain transfer agent,
t-dodecylmercaptan, n-octylmercaptan and .alpha.-methylstyrene can
be used. Preferably, t-dodecylmercaptan can be used.
[0020] As a method of polymerizing a butadiene-based rubber, an
emulsion polymerization method is preferably used. A polymerization
initiator is not specifically limited and there can be used a
redox-based initiator containing, as a component, a water soluble
persulfuric acid such as potassium persulfate, sodium persulfate or
ammonium persulfate, or a organic peroxide such as
diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene
hydroperoxide or t-butyl hydroperoxide, or a combination of the
peroxide and at least one reducing agent. The polymerization can be
appropriately conducted at a temperature within a range from about
40 to 80.degree. C., although it depends on the kind of the
polymerization initiator. As an emulsifier, known emulsifiers can
be appropriately used, and monostage or multistage seed
polymerization can be employed. According to circumstances,
soap-free polymerization may be employed. It is also possible to
prepare using a method of enlarging a rubber latex obtained in case
of controlling the particle size with an acid or a salt.
[0021] The acrylic rubber can be prepared by polymerizing one or
more kinds of alkyl(meth)acrylates with one or more kinds of
vinyl-based monomers copolymerizable with the
alkyl(meth)acrylates.
[0022] The alkyl(meth)acrylate is not specifically limited and
examples thereof include methyl acrylate, ethyl acrylate, n-propyl
acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl
acrylate, 2-ethylhexyl methacrylate, ethoxyethoxy ethyl acrylate,
methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate,
lauryl methacrylate and stearyl methacrylate.
[0023] The monomer may include 20% by mass or less, and preferably
0.1 to 18% by mass of a monomer having two or more unsaturated
bonds in the molecule. The monomer having two or more unsaturated
bonds in the molecule serves as a crosslinking agent or a
graft-crosslinking agent, and examples of the crosslinking agent
include ethylene glycol dimethacrylate, propylene glycol
dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene
glycol dimethacrylate, divinylbenzene, and silicone such as
polyfunctional methacryl group-modified silicone. Examples of the
graft-crosslinking agent include allyl methacrylate, triallyl
cyanurate and triallyl isocyanurate. The allyl methacrylate can
also be used as the crosslinking agent. These crosslinking agents
and graft-crossing agents are respectively used alone or in
combination.
[0024] The monomer may contain, as a copolymer component, 30% by
mass or less of various vinyl-based monomers, for example, aromatic
alkenyl compound such as styrene, .alpha.-methylstyrene or
vinyltoluene, vinyl cyanide compound such as acrylonitrile or
methacrylonitrile, methacrylic acid-modified silicone and
fluorine-containing vinyl compound.
[0025] The acrylic rubber may have a single-layered, or two- or
multi-layered structure. Also the acrylic rubber may be a
polyalkyl(meth)acrylate-based composite rubber which contains two
or more kinds of components and has two or more glass transition
temperatures.
[0026] The polymerization method and the polymerization conditions
in case of polymerizing the acrylic rubber are not specifically
limited. The polymerization method to be employed is usually an
emulsion polymerization method, and preferably a soap-free emulsion
polymerization method. If necessary, a forced emulsion
polymerization may be employed.
[0027] The polymerization initiator is not specifically limited and
there can be used a redox-based initiator containing, as a
component, a water soluble persulfuric acid such as potassium
persulfate, sodium persulfate or ammonium persulfate, or a organic
peroxide such as diisopropylbenzene hydroperoxide, p-menthane
hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide, or a
combination of the peroxide and at least one reducing agent.
[0028] The emulsifier is not specifically limited and, if
necessary, one or more alkali metal salts of higher fatty acid such
as disproportionated rosin acid, oleic acid or stearic acid, and
one or more sulfonic acid alkali metal salts such as
dodecylbenzenesulfonic acid can be added.
[0029] It is also possible to prepare using a method of enlarging a
rubber latex obtained in case of controlling the particle size with
an acid or a salt.
[0030] The silicone-based rubber is not specifically limited and
polyorganosiloxane having a vinyl polymerizable functional group is
preferably used.
[0031] Examples of dimethylsiloxane used to prepare the
polyorganosiloxane include 3- to multi-membered ring
dimethylsiloxane-based cyclic compound, and 3 to 7-membered ring
compounds are preferable. Specific examples thereof include
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, and
these dimethylsiloxanes are used alone or in combination.
[0032] The vinyl polymerizable functional group-containing siloxane
has a vinyl polymerizable functional group and is capable of
bonding with the dimethylsiloxane via a siloxane bond, and various
alkoxysilane compounds having a vinyl polymerizable functional
group are preferable taking account of reactivity with the
dimethylsiloxane. Specific examples thereof include
methacryloyloxysilane such as .beta.-methacryloyloxy
ethyldimethoxymethylsilane, .gamma.-methacryloyloxy
propyldimethoxymethylsilane, .gamma.-methacryloyloxy
propylmethoxydimethylsilane, .gamma.-methacryloyloxy
propyltrimethoxysilane, .gamma.-methacryloyloxy propylethoxy
diethylsilane, .gamma.-methacryloyloxy propylethoxy
diethoxymethylsilane or .delta.-methacryloyloxybutyl
diethoxymethylsilane; vinylsiloxane such as tetramethyl
tetravinylcyclotetrasiloxane; vinylphenylsilane such as
p-vinylphenyl dimethoxymethylsilane; and mercaptosiloxane such as
.gamma.-mercaptopropyl dimethoxymethylsilane or
.gamma.-mercaptopropyl trimethoxysilane. These vinyl polymerizable
functional group-containing siloxanes can be used alone or in
combination.
[0033] As a siloxane-based crosslinking agent, there can be used
trifunctional or tetrafunctional silane-based crosslinking agent,
for example, trimethoxymethylsilane, triethoxyphenylsilane,
tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane.
[0034] The polyorganosiloxane can be prepared, for example, by
forming a latex, which is obtained by emulsifying a mixture of a
diorganosiloxane and a vinyl polymerizable functional
group-containing siloxane or a mixture further containing a
siloxane-based crosslinking agent optionally using an emulsifier
and water, into fine particles using a homomixer for forming into
fine particles through a shear force produced during high-speed
rotation or a homogenizer for forming into fine particles through a
jetting force produced by a pressure generator; polymerizing the
resulting fine particles at high temperature using an acid
catalyst; and neutralizing an acid with an alkali substance.
[0035] Examples of the method of adding an acid catalyst used in
the polymerization include a method of mixing a siloxane mixture,
an emulsifier and water and a method of adding dropwise a latex
obtained by forming a siloxane mixture into fine particles in an
aqueous acid solution at high temperature at a fixed rate. Taking
account of ease of controlling the particle size of
polyorganosiloxane, the method of adding dropwise a latex obtained
by forming a siloxane mixture into fine particles in an aqueous
acid solution at high temperature at a fixed rate is
preferable.
[0036] Examples of the method of mixing a siloxane mixture, an
emulsifier, water and/or an acid catalyst include a method of
mixing under high-speed stirring and a method of mixing using a
high-pressure emulsification apparatus such as homogenizer, and the
method of using a homogenizer is a preferable method because
particle size distribution of a polyorganosiloxane latex
decreases.
[0037] The emulsifier used in the preparation of polyorganosiloxane
is preferably an anionic emulsifier, and an emulsifier selected
from among sodium alkylbenzenesulfonate, sodium
polyoxyethylenenonylphenylether sulfate, and the like is used.
Particularly, sodium alkylbenzenesulfonate and sodium lauryl
sulfate are preferable.
[0038] Examples of the acid catalyst used in the polymerization of
the polyorganosiloxane include sulfonic acids such as aliphatic
sulfonic acid, aliphatic substituted benzenesulfonic acid and
aliphatic substituted naphthalenesulfonic acid, and mineral acids
such as sulfuric acid, hydrochloric acid and nitric acid. These
acid catalysts can be used alone or in combination.
[0039] The polymerization can be terminated by cooling the reaction
solution and neutralizing the latex with an alkali substance such
as sodium hydroxide, potassium hydroxide or sodium carbonate.
[0040] In the present invention, a silicone/acrylic composite
rubber obtained by combining the silicone rubber with an alkyl
(meth)acrylate rubber can also be used. The silicone/acrylic
composite rubber can be prepared by adding an alkyl (meth)acrylate
component in a latex of a polyorganosiloxane component and
polymerizing the mixture in the presence of a conventional radical
polymerization initiator. Examples of the method of adding the
alkyl(meth)acrylate include a method of mixing with a latex of a
polyorganosiloxane component at a time and a method of adding
dropwise in a latex of a polyorganosiloxane component at a fixed
rate. Taking account of impact resistance of the resulting resin
composition containing a graft copolymer, the method of mixing with
a latex of a polyorganosiloxane component at a time is
preferable.
[0041] Examples of the alkyl(meth)acrylate include alkyl acrylate
such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl
acrylate or 2-ethylhexyl acrylate, and alkyl methacrylate such as
hexyl methacrylate, 2-ethylhexyl methacrylate or n-lauryl
methacrylate, and these alkyl (meth)acrylates can be used alone or
in combination. Taking account of impact resistance and molding
gloss of the resin composition containing the graft copolymer,
n-butyl acrylate is particularly preferably.
[0042] Examples of the polyfunctional alkyl (meth)acrylate include
allyl methacrylate, ethylene glycol dimethacrylate, propylene
glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,4-butylene glycol dimethacrylate, triallyl cyanurate and triallyl
isocyanurate, and these polyfunctional alkyl(meth)acrylates can be
used alone or in combination.
[0043] The radical polymerization initiator used in the
polymerization is a peroxide, an azo-based initiator, or a
redox-based initiator comprising an oxidizing agent and a reducing
agent. Among these radical polymerization initiators, a redox-based
initiator is preferable and an initiator comprising ferrous
sulfate, disodium ethylenediaminetetraacetate, Rongalite and
hydroperoxide is preferable.
[0044] The graft copolymer latex used in the modifier for resin of
the present invention is obtained by adding one or more kinds of
copolymerizable vinyl-based monomers in the presence of a rubber
polymer latex containing one or more kinds of components selected
from among the diene-based rubber, the acrylic rubber, the
silicone-based rubber and the silicone-acrylic composite rubber,
followed by graft polymerization.
[0045] In the present invention, the monomer used in the graft
polymerization is not specifically limited as far as it is
copolymerizable with a rubber polymer. For example, there can be
used a monomer mixture of aromatic vinyl such as styrene,
a-methylstyrene, or various halogen-substituted and
alkyl-substituted styrenes; alkyl methacrylate ester such as methyl
methacrylate or ethyl methacrylate; alkyl acrylate ester such as
ethyl acrylate or n-butyl acrylate; unsaturated nitrile such as
acrylonitrile or methacrylonitrile; vinyl-based monomer having a
glycidyl group, such as glycidyl acrylate, glycidyl methacrylate,
allyl glycidyl ether or ethylene glycol glycidyl ether; and
vinyl-based monomer having a hydroxy group such as
hydroxymethacrylate, with the above-mentioned crosslinkable monomer
and/or a chain transfer agent. If necessary, these monomer mixtures
can be subjected to monostage, or two- or multistage graft
polymerization according to balance between dispersibility and
impact strength.
[0046] In the graft copolymer used in the modifier for resin of the
present invention, when the sum of the total amount of the monomers
used in the graft polymerization and the amount of the rubber
polymer is 100% by mass, the total amount of the monomers used in
the graft polymerization is preferably from 5 to 50% by mass. When
the total amount of the monomers used in the graft polymerization
is more than 50% by mass, the resulting product tends to be
inferior in impact resistance. On the other hand, when the total
amount is less than 5% by mass, the resulting product tends to be
inferior in dispersibility.
[0047] The graft copolymer used in the modifier for resin of the
present invention is preferably a graft copolymer in which a glass
transition temperature (Tg) of a core component is preferably
within a range from -150 to 10.degree. C., and more preferably from
-70 to -20.degree. C., in view of an improvement in impact
strength. In view of dispersibility, it is preferred to use a graft
copolymer in which Tg of a shell component is within a range from
30 to 150.degree. C., and more preferably from 40 to 130.degree. C.
As used herein, Tg of the polymer is measured as a transition point
of Tan .delta. as measured by a dynamic mechanical property
analyzer (hereinafter abbreviated to DMA).
[0048] The graft copolymer used in the modifier for resin of the
present invention is recovered by spray drying of a latex obtained
by the polymerization. At this time, a graft polymer having an
average particle size of 200 nm or more in the latex obtained
finally so as to improve dispersibility in a thermoplastic resin
and a curable resin. When the average particle size is less than
200 nm, primary particles of the resulting modifier for resin are
fused and good dispersibility cannot be exhibited. Similarly, in
view of control of powder dispersibility, particle size
distribution of latex particles is preferably narrowed as possible.
Although no problem arise when particles having an average particle
size of 150 nm or less are present, the content is preferably small
as possible.
[0049] If necessary, proper antioxidants and additives can be
previously added to the graft copolymer latex.
[0050] The resulting copolymer latex is powderized by drying using
a spray drying method. The spray drying method comprises the steps
of spraying a latex to form minute droplets and drying the minute
droplets with blowing hot blast. The apparatus to be used is not
specifically limited and, as a method of forming droplets, for
example, there can be used any of rotary disk type, pressure nozzle
type, two fluid nozzle type and pressure two fluid nozzle type
apparatuses. Capacity of the dryer is not specifically limited and
a small scale of a dryer used in a laboratory or a large scale
dryer for industrial use can be used.
[0051] The position of an inlet portion as a portion for supplying
a heating gas for drying in the dryer, and the position of an
outlet portion as a port for discharging the heating gas for drying
and a dry powder may be the same as those in a spray dryer used
conventionally, and are not specifically limited. The temperature
of hot blast to be introduced into the dryer (hot-air inlet
temperature), that is, maximum temperature of hot blast which can
be contacted with the graft copolymer is preferably 200.degree. C.
or lower, and particularly preferably from 120 to 180.degree.
C.
[0052] In case of spray drying, the graft polymer latex may be used
alone or a mixture of plural latexes may also be used. Furthermore,
spray drying can be conducted by adding inorganic filler (for
example, silica, talc and calcium carbonate), polyacrylate,
polyvinyl alcohol and polyacrylamide so as to improve powder
properties such as blocking, and bulk specific gravity on spray
drying. Spray drying can also be conducted by adding proper
antioxidants and additives to a latex to be sprayed.
[0053] In the modifier for resin obtained under the above spraying
conditions, particles having an average powder particle size of 20
.mu.m or more and 10 .mu.m or less account for less than 30% by
mass. Particles having an average powder particle size of 10 .mu.m
or less preferably account for 20% by mass, and most preferably 10%
by mass or less in view of handling property. The average particle
size of the modifier for resin is preferably 200 .mu.m or less.
[0054] The modifier for resin of the present invention has a
structure that primary particles in the graft copolymer latex are
coagulated without being completely fused and particles having an
average particle size of 10 .mu.m or less account for 30% by mass
or more of the modifier after irradiating the modifier with
ultrasonic wave of 40 W for 5 minutes. A modifier for resin in
which particles having an average particle size of 10 .mu.m or less
account for 40% by mass or more of the modifier after irradiating
the modifier with ultrasonic wave of 40 W for 5 minutes is
preferable, and a modifier for resin in which particles having an
average particle size of 10 .mu.m or less account for 50% by mass
or more of the modifier after irradiating the modifier with
ultrasonic wave of 40 W for 5 minutes is most preferable.
[0055] Irradiation with ultrasonic wave is conducted after diluting
the resulting powder with distilled water. For example, after
irradiating with ultrasonic wave (40 W) for 5 minutes using a laser
diffraction scattering type particle size distribution measuring
apparatus (manufactured by NIKKISO CO., LTD. under the trade name
of Microtrac MT3000, concentration range is automatically
calculated by an apparatus), the proportion (% by weight) of
particles having a particle size of 10 .mu.m or less is
measured.
[0056] The curable resin and the thermoplastic resin used in the
resin composition of the present invention are not specifically
limited and any resins can be used as far as they are known resins.
The curable resin includes a thermosetting resin and a photocurable
resin. Examples of the thermosetting resin include epoxy-based
resin, phenolic resin, unsaturated polyester-based resin, melamine
resin and urea resin. These resins can be used after mixing. The
modifier for resin of the present invention is preferably used in
an epoxy-based resin among these thermosetting resins.
[0057] As the epoxy resin, various known resins can be used and the
molecular structure and molecular weight are not specifically
limited if the epoxy resin has at least two epoxy bonds in the
molecule. For example, various epoxy resins such as
dicyclopentadiene type, cresol novolak type, phenol novolak type,
bisphenol type and biphenyl type epoxy resins can be used alone or
in combination. Examples of the curing agent include phenolic
curing agent (for example, phenol novolak resin or cresol novolak
resin), amine-based curing agent and acid anhydride curing agent.
These curing agents may be used in combination. The amount of the
curing agent to be added is not specifically limited, but must be a
stoichiometric amount for curing of an epoxy resin.
[0058] As the phenol resin, various known phenol resins can be used
and examples thereof include resol type or novolak type phenol
resins which are derived from various phenols and formaldehyde or
aldehyde having at least two carbon atoms. These phenol resins may
be modified with drying oil, xylene resin or melamine resin. In
case of the novolak type phenol resin, a polyamine such as
hexamine, and a curing agent such as epoxy resin, isocyanate
compound, polyformaldehyde compound or resol type phenol resin is
further used in combination.
[0059] As the unsaturated polyester resin, various known
unsaturated polyester resins can be used. For example, it is
obtained by reacting a saturated dibasic acid such as isophthalic
acid, ortho-phthalic acid, phthalic anhydride, succinic acid,
adipic acid, sebacic acid, or endomethylenetetrahydrophthalic
anhydride; a polyhydric alcohol such as ethylene glycol dipropylene
glycol, 1,3-butanediol, hydrogenated bisphenol A, neopentyl glycol,
isopentyl glycol or 1,6-hexanediol, and unsaturated dibasic acid
such as maleic acid, maleic anhydride, fumaric acid or itaconic
acid at a temperature within a range from 180 to 250.degree. C. As
the copolymerizable monomer, for example, there can be used a
monomer, which is copolymerizable with an unsaturated polyester
resin such as styrene, t-butylstyrene, chlorostyrene,
divinylbenzene, diallyl phthalate, vinyltoluene or acrylate esters
and also has an unsaturated group, or a prepolymer thereof.
[0060] If necessary, the curable resin composition can be used in
combination with various known additives. For example, there can be
used various curing accelerators; releasants such as silicone oils,
natural waxes, and synthetic waxes, and metal salts, acid amides
and esters of a linear fatty acid, and paraffins; powders such as
crystalline silica, fused silica, calcium silicate, alumina,
calcium carbonate, talc and barium sulfate, inorganic fillers such
as glass fiber and carbon fiber, flame retardants such as
chlorinated paraffin, bromotoluene, hexabromobenzene and antimony
trioxide, colorants such as carbon black and iron red, and silane
coupling agents.
[0061] The method of preparing a curable resin composition is not
specifically limited and a known technique can be used. For
example, the composition is mixed in a solution state or melt-mixed
using a mixing roll or a kneader, ground or compressed and then
molded by a transfer molding, a sheet a compound molding or a bulk
molding method. Furthermore, the resulting product can be used as a
coating material and an adhesive composition.
[0062] Examples of the molded article obtained by using the curable
resin composition of the present invention include electric and
electronic molding materials including an IC sealing materials,
automotive molding materials and molding materials for building
materials, and also include coating materials, adhesives, and
solder pastes for circuit board protective film. The modifier for
resin of the present invention exhibits excellent thickening
properties to a nonaqueous coating material.
[0063] The modifier for resin of the present invention may be added
to the coating material in the process of kneading a pigment, or
may be added after preparing a coating material. The addition
temperature is not specifically limited and a disperser used
commonly in the preparation of the coating material can be
used.
[0064] The use of the modifier for resin of the present invention
makes it possible to cope with requirements such as sag resistance
and promotion of efficiency of the step of preparing a
corrosion-resistant coating material such as epoxy coating material
or an urethane coating material.
[0065] Examples of the thermoplastic resin used in the present
invention include polycarbonate-based resin, crystalline or
noncrystalline polyester-based resin, polyamide-based resin,
polyacetal-based resin, polyphenylene ether-based resin, polyvinyl
chloride-based resin, polystyrene-based resin, polymethyl
methacrylate-styrene-based resin, polyalkyl(meth)acrylate-based
resin, polyacrylonitrilestyrene-based resin,
polyacrylonitrile-butadiene-styrene-based resin and
polyolefin-based resin. These thermoplastic resins can be used
alone or in combination.
[0066] To the thermoplastic resin composition, stabilizer to heat
or light, for example, phenol-based, phosphite-based and
sulfur-based stabilizers, ultraviolet absorbers, amine-based
photostabilizers may be added. Also hydrolysis-resistant modifiers
such as epoxy-based modifiers may be added. Furthermore, known
flame retardants, fillers such as titanium oxide and talc, dyes and
pigments, and plasticizer can be added, if necessary.
[0067] The method is not specifically limited and examples thereof
include various known methods, for example, a method of mixing
powders and granules using a Henschel mixer or a tumbler and
melt-mixing using an extruder, a kneader or a mixer, a method of
successively mixing other components with a component melted
previously, and a method of directly molding a mixture using an
injection molding machine. In addition to injection molding,
calender molding, blow molding, extrusion molding, thermomolding,
foam molding and melt spinning can be exemplified.
EXAMPLES
[0068] The present invention will now be described in more detail
by way of examples, but the present invention is not limited
thereto. In the descriptions, parts and percentages are by mass
unless otherwise specified.
[0069] In the following examples, a latex particle size and a glass
transition point (Tg) were measured by the following
procedures.
1) Particle Size of Latex
[0070] The resulting latex was diluted with distilled water and a
50 volume % average particle size was measured using a laser
diffraction scattering type particle size distribution measuring
apparatus (LA-910, manufactured by HORIBA, Ltd.).
2) Glass Transition Point of Powder
[0071] A test piece measuring 3 mm in thickness.times.10 mm in
width.times.12 mm in length was made from a modifier for resin and
a Tan .delta. curve was measured by a dynamic viscoelasticity
measuring apparatus (DMA983, manufactured by TA Instruments Co.)
under the conditions of a temperature rise rate of 2.degree.
C./min, and then the temperature corresponding to the transition
point was determined as a glass transition temperature.
3) Average Particle Size of Powder
[0072] The resulting powder was diluted with distilled water and a
50 volume % average particle size was measured using a laser
diffraction scattering type particle size distribution measuring
apparatus (Microtrac MT3000, manufactured by NIKKISO CO.,
LTD.).
4) Disintegration Property of Powder
[0073] The resulting powder was distilled with distilled water and
irradiated with ultrasonic wave (40 W.times.300 sec) using a laser
diffraction scattering type particle size distribution measuring
apparatus (Microtrac MT3000, manufactured by NIKKISO CO., LTD.) and
then the content of particles having a particle size of 10 .mu.m or
less was measured.
Preparation Example 1
Preparation of Modifier for Resin (IM-1)
[0074] In a 5 liter flask, 45 parts of pure water, 2.5 parts of
butyl acrylate and 0.065 parts of allyl methacrylate were charged
and heated to 80.degree. C. while stirring at 250 rpm in a nitrogen
atmosphere.
[0075] A previously prepared solution of 0.10 parts of potassium
persulfate and 5.2 parts of pure water was charge at a time and the
first stage soap-free emulsion polymerization was conducted while
maintaining for 60 minutes. Then, a mixed solution of 67.5 parts of
butyl acrylate, 1.695 parts of allyl methacrylate, 0.6 parts of
sodium di 2-ethylhexylsulfosuccinate (manufactured by Kao
Corporation under the trade name of PELEX OT-P) and 34.0 parts of
pure water was added dropwise over 180 minutes and the second stage
emulsion polymerization was conducted while maintaining for one
hour to obtain an acrylic rubber polymer latex (R-1). To the
resulting latex (R-1), a mixed solution of 29.4 parts of methyl
methacrylate, 0.6 parts of ethyl acrylate, 0.4 parts of sodium di
2-ethylhexyl sulfosuccinate and 15.6 parts of pure water was added
dropwise over 100 minutes and, after maintaining for one hour, the
emulsion polymerization was terminated to obtain a graft copolymer
(G-1) latex. The resulting latex had a particle size of 900 nm. The
resulting graft copolymer latex was sprayed by a pressure nozzle
type using a spray dryer and the resulting microdroplets were dried
at a hot-air inlet temperature of 180.degree. C. to obtain a
modifier for resin (IM-1).
[0076] The resulting powder had an average particle size of 43
.mu.m. The powder particles had a disintegration property of 64%.
The rubber moiety had a glass transition point of -23.degree. C.
and the graft moiety had a glass transition point of 86.degree.
C.
Preparation Example 2
Preparation of Modifier for Resin (IM-2)
[0077] In a 5 liter flask, 88 parts of pure water, 5 parts of butyl
acrylate and 0.125 parts of allyl methacrylate were charged and
heated to 80.degree. C. while stirring at 250 rpm in a nitrogen
atmosphere. A previously prepared solution of 0.10 parts of
potassium persulfate and 5.2 parts of pure water was charge at a
time and the first stage soap-free emulsion polymerization was
conducted while maintaining for 60 minutes. Then, a mixed solution
of 65 parts of butyl acrylate, 1.625 parts of allyl methacrylate,
0.6 parts of sodium di 2-ethylhexylsulfosuccinate and 34.0 parts of
pure water was added dropwise over 180 minutes and the second stage
emulsion polymerization was conducted while maintaining for one
hour to obtain an acrylic rubber polymer latex (R-2). To the
resulting latex (R-4), a mixed solution of 25.4 parts of methyl
methacrylate, 0.6 parts of ethyl acrylate, 4 parts of glycidyl
methacrylate, 0.4 parts of sodium di 2-ethylhexyl sulfosuccinate
and 15.6 parts of pure water was added dropwise over 100 minutes
and, after maintaining for one hour, the emulsion polymerization
was terminated to obtain a graft copolymer (G-2) latex. The
resulting latex had a particle size of 600 nm. The resulting graft
copolymer latex was sprayed by a pressure nozzle type using a spray
dryer and the resulting microdroplets were dried at a hot-air inlet
temperature of 180.degree. C. to obtain a modifier for resin
(IM-2). The resulting powder had an average particle size of 38
.mu.m. The powder particles had a disintegration property of 57%.
The rubber moiety had a glass transition point of -25.degree. C.
and the graft moiety had a glass transition point of 83.degree.
C.
Preparation Example 3
Preparation of Modifier for Resin (IM-3)
[0078] To the resulting latex (R-2) obtained in Preparation Example
2, a mixed solution of 28.4 parts of methyl methacrylate, 0.6 parts
of ethyl acrylate, 0.75 parts of allyl methacrylate, 1 part of
glycidyl methacrylate, 0.4 parts of sodium di 2-ethylhexyl
sulfosuccinate and 15.6 parts of pure water was added dropwise over
100 minutes and, after maintaining for one hour, the emulsion
polymerization was terminated to obtain a graft copolymer (G-3)
latex. The resulting latex had a particle size of 610 nm. The
resulting graft copolymer latex was sprayed by a pressure nozzle
type using a spray dryer and the resulting microdroplets were dried
at a hot-air inlet temperature of 180.degree. C. to obtain a
modifier for resin (IM-3). The resulting powder had an average
particle size of 60 .mu.m. The powder particles had a
disintegration property of 55%. The rubber moiety had a glass
transition point of -25.degree. C. and the graft moiety had a glass
transition point of 88.degree. C.
Preparation Example 4
Preparation of Modifier for Resin (IM-4)
[0079] In an autoclave, 80 parts of 1,3-butadiene, 20 parts of
styrene, 4.5 parts of divinylbenzene, 3 parts of semihardened beef
tallow fatty acid potassium, 0.2 parts of anhydrous sodium sulfate,
0.3 parts of cumene hydroperoxide, 0.2 parts of dextrose, 0.003
parts of ferrous sulfate, 0.3 parts of sodium pyrophosphate
decahydrate and 220 parts of distilled water were charged and
reacted at 52.degree. C. while stirring for 8 hours to obtain a
rubber polymer latex (R-3). 65 Parts of the resulting rubber
copolymer latex (R-3), 0.3 parts of potassium alkenyl succinate,
0.3 parts of Rongalite and distilled water were charged in a flask
in which the atmosphere was replaced by nitrogen and, after
maintaining the inner temperature at 70.degree. C., a mixture of
30.6 parts of methyl methacrylate, 5.4 parts of ethyl acrylate and
0.375 parts of t-butyl hydroperoxide was added dropwise over 50
minutes, followed by maintaining for one hour in the first stage.
In the presence of the polymer obtained in the above stage, a
mixture of 44 parts of styrene and 0.375 parts of t-butyl
hydroperoxide was continuously added over one hour, followed by
maintaining for 100 minutes in the second stage. In the presence of
the polymers obtained in the first and second stages, a mixture of
20 parts of methyl methacrylate and 0.375 parts of t-butyl
hydroperoxide was continuously added dropwise over 15 minutes and,
after maintaining for 90 minutes, the polymerization was terminated
to obtain a graft copolymer latex (G-4) in the third stage. The
resulting latex had an average particle size of 95 nm. The graft
copolymer latex was coagulated by adding dropwise in hot water of
aluminum sulfate, separated, washed and then dried at 75.degree. C.
for 16 hours to obtain a powder. The resulting powder was freeze
ground into fine powders with liquid nitrogen and particles having
a particle size of more than 250 .mu.m were removed by screening to
obtain a modifier for resin (IM-4). The resulting powder had an
average particle size of 92 .mu.m. The powder particles had a
disintegration property of 2%. The rubber moiety had a glass
transition point of -41.degree. C. and the graft moiety had a glass
transition point of 81.degree. C.
[0080] The measurement results of the average particle size of the
latex use in the preparation of the resulting modifiers for resin
(IM1 to 4), the average particle size of the modifier for resin
powder before and after irradiation with ultrasonic wave, the
content of particles having an average particle size of 10 .mu.m or
less and the glass transition point are shown in Table 1.
TABLE-US-00001 TABLE 1 Average particle size of powder Average
Before irradiation with After irradiation with ultrasonic particle
ultrasonic wave wave (40 W .times. 300 sec) Glass transition size
of Content of particles Average Content of particles Average point
[.degree. C.] latex having an average size particle having an
average size particle Rubber Shell [nm] of 10 .mu.m or less [%]
size [.mu.m] of 10 .mu.m or less [%] size [.mu.m] moiety moiety
IM-1 900 1 43 64 4 -23 86 IM-2 600 3 38 57 7 -25 88 IM-3 610 0 60
55 8 -25 88 IM-4 95 0 92 2 75 -41 81
Examples 1 to 5 and Comparative Examples 1 to 2
[0081] 100 parts by mass of a curable resin was mixed with each
modifier for resin in the amount shown in Table 2 to obtain
sheet-like formed test pieces. Using the resulting test pieces,
Izod impact strength and dispersibility of the modifier were
evaluated.
[0082] In these examples, 100 parts of a bisphenol A type epoxy
resin (ADEKA RESIN EP-4100E, manufactured by Asahi Denka Co.,
Ltd.), 85 parts of tetrahydromethylphthalic anhydride (ADEKA
HARDENER EH-3326, manufactured by Asahi Denka Co., Ltd.) and a
modifier for resin in the amount described in Table 2 were stirred
at 60.degree. C. using a stirrer at 150 rpm for 90 minutes and then
1 part of N-benzyl-2-methylimidazole was added. After mixing with
stirring, the resulting composition was filled in a mold and heated
at 80.degree. C. for 2 hours, then at 120.degree. C. for 6 hours to
obtain test pieces. Evaluation was conducted by the following
procedures.
(1) Impact Strength
[0083] A sheet-like test piece was formed, cut and then evaluated
in accordance with ASTM D256. (Thickness: 1/4 inch, Unit: J/m)
(2) Dispersibility
[0084] Dispersion state (coagulation state) of a modifier for resin
on the surface of a sheet-like test piece was visually
evaluated.
[0085] B: Coagulate of rubber is not observed.
[0086] D: Coagulate of rubber is observed. TABLE-US-00002 TABLE 2
Comparative Examples Examples 1 2 3 4 5 1 2 Curable Epoxy 100 100
100 100 100 100 100 resin resin Modifier IM-1 -- -- -- -- 10 -- --
IM-2 5 10 20 30 -- -- -- IM-3 -- -- -- -- -- -- -- IM-4 -- -- -- --
-- -- 10 Physical Izod 19 22 29 34 28 11 14 properties impact
strength [J/m] Dispersi- B B B B B -- D bility
Examples 6 to 11 and Comparative Example 3
[0087] 30 parts of a bisphenol A type epoxy resin (manufactured by
Japan Epoxy Resins Co., Ltd. under the trade name of EPIKOTE 828),
40 parts of a bisphenol A type epoxy resin (EPIKOTE 1002,
manufactured by Japan Epoxy Resins Co., Ltd.), 30 parts of an
oxazolidone ring-containing epoxy resin (manufactured by Asahi
Kasei Corporation under the trade name of AER4152), 5 parts of
dicyandiamide (DICY, manufactured by Japan Epoxy Resins Co., Ltd.),
4 parts of 3,4-dichlorophenyl-N,N-dimethylurea (DCMU, manufactured
by Hodogaya Chemical Co., Ltd.) and each modifier for resin in the
amount show in Table 3 were mixed in a flask using Three-One Motor
and a stirring bar to obtain epoxy resin compositions. The
resulting Compositions were evaluated by the following
procedures.
(1) Measurement of Energy Release Rate of Cured Resin
[0088] Each of the epoxy resin compositions was cast between glass
plates, into which a 3 mm thick spacer is interposed, and then
cured with heating in a hot air dryer under the conditions at
130.degree. C. for one hour to obtain a 2 mm thick cured resin
sheet. With respect to this cured resin sheet, test pieces were
made in accordance with ASTM D5045 (SENB method) to obtain an
energy release rate GIc of the cured resin. At this time, the
cutting portion was provided with a notch using a cutter.
(3) Measurement of Tg of Cured Resin
[0089] Each of the epoxy resin compositions was cast between glass
plates, into which a 2 mm thick spacer is interposed, and then
cured with heating in a hot air dryer under the conditions at
130.degree. C. for one hour to obtain a 2 mm thick cured resin
sheet. With respect to this cured resin sheet, a peak temperature
of a loss tangent Tan .delta. as measured by a rheometer
(manufactured by Rheometrix Corp under the trade name of RDA-700)
under the conditions of a temperature rise rate of 10.degree.
C./min and a measuring frequency of 10 radians per second was taken
as a glass transition temperature Tg of the cured resin.
TABLE-US-00003 TABLE 3 Comparative Examples Examples 6 7 8 9 10 11
3 Epoxy EP828 30 30 30 30 30 30 30 resin EP1002 40 40 40 40 40 40
40 AER4152 30 30 30 30 30 30 30 DICY 5 5 5 5 5 5 5 DCMU 4 4 4 4 4 4
4 Modifier IM-1 -- -- -- -- -- -- -- IM-2 5 10 20 -- -- -- -- IM-3
-- -- -- 5 10 20 -- IM-4 -- -- -- -- -- -- -- Physical GIc
[J/m.sup.2] 720 832 968 696 1003 1357 365 properties Glass 142 142
142 142 143 143 145 of cured transition resin temperature [.degree.
C.]
Examples 12 to 13 and Comparative Example 4
Preparation of Clear Coating Material for Evaluation of sag
[0090] In a 500 mL stainless steel vessel, 90 parts of a modifier
for resin and 210 parts of xylene were charged and stirred at 2000
rpm for 10 minutes using a disper stirrer to obtain a xylene
dispersion having a resin solid content of 30% of a modifier for
resin.
[0091] In a 500 mL four-necked flask equipped with a thermometer, a
stirrer and a condenser, 180 parts of xylene was added and 120
parts of a solid acrylic resin (BR-73, manufactured by Mitsubishi
Rayon Co., Ltd.) was slowly added. After heating to 50.degree. C.
in a hot water bath and stirring for one hour, a xylene solution
having a resin solid content of 40% of an acrylic resin was
obtained.
[0092] In a 500 mL stainless steel vessel, 250 parts of the 40%
xylene solution of the acrylic resin prepared in the above
preparation example was charged and the xylene dispersion was added
so as to add the modifier for resin in the amount described in
Table 5 (for example, 55 parts of a 30% xylene dispersion of a
modifier for resin is added in case of 16.5 parts of the modifier
for resin), followed by stirring. The resulting mixture was diluted
with xylene so as to adjust the viscosity within a range from 16 to
17 seconds with Zahn cup No. 4 to obtain a clear coating material
for evaluation of sag. The resulting coating material was evaluated
by the following procedure. The results are shown in Table 4.
(1) Evaluation of Sag
[0093] On a glass plate (thickness: 2 mm) measuring 120
mm.times.120 mm, the clear coating material prepared in the above
preparation example was coated using a sag tester. Immediately, the
test piece was vertically stood and was allowed to stand for 30
minutes. The maximum film thickness at which the coating material
does not flow was recorded and then evaluated by the following
criteria. As the sag tester, a sag tester manufactured by TAIYU
KIZAI CO., LTD. (9 mm, 25 to 250 .mu.m, space: 2 mm) was used
TABLE-US-00004 25 to 50 .mu.m: D 75 to 100 .mu.m: C 125 to 175
.mu.m: B 200 to 250 .mu.m: A
[0094] TABLE-US-00005 TABLE 4 Comparative Examples Examples 12 13 4
Acrylic resin BR-73 100 100 100 Modifier IM-1 -- -- -- IM-2 16.5
33.0 -- IM-3 -- -- -- IM-4 -- -- -- Sag B (125 .mu.m) B (150 .mu.m)
D (50 .mu.m)
Examples 14 to 15 and Comparative Example 5
Preparation of White Coating Material for Evaluation of Impact
Resistance
[0095] In a 300 mL glass bottle with a lid, 250 parts of the 40%
xylene solution of the acrylic resin prepared in the above
preparation example was charged and 83.5 parts of titanium oxide
(CR-90, manufactured by Ishihara Sangyo Kaisya, Ltd.) and 25 parts
of dioctyl phthalate was added, followed by mixing. After
dispersing in a planet ball mill for one hour, the 30% xylene
solution of the modifier was added so as to add the modifier for
resin in the amount described in Table 5 (for example, 83.5 parts
of a 30% xylene dispersion of a modifier is added in case of 25
parts of the modifier for resin). The resulting mixture was diluted
with xylene so as to adjust the viscosity within a range from 12 to
13 seconds with Ford cup No. 4 to obtain a white coating material.
The resulting coating material was evaluated by the following
procedure. The results are shown in Table 5.
(1) Evaluation of Impact Resistance
[0096] The white coating material prepared in the above preparation
example was spray coated on a test base material (a base material
measuring 0.8.times.70.times.150 mm obtained by subjecting a
phosphated steel sheet to electrodeposition coating, intermediate
coating and water polishing treatment (Dull Steel Sheet D-7,
manufactured by Nippon Route Service Co.), followed by standing at
room temperature for 20 minutes and further drying at 60.degree. C.
for one hours to obtain a test piece having a dry thickness of 50
.mu.m. In the evaluation of impact resistance, a DuPont type impact
deformation tester was used and a 1/2 inch weight of 500 g was
used. The impact resistance was evaluated (JIS K5400) by the height
of the weight, at which cracking or peeling of the coating film is
not observed, according to the following criteria. TABLE-US-00006
25 cm or less: D 30 to 35 cm: C 40 to 45 cm: B 50 cm or more: A
[0097] TABLE-US-00007 TABLE 5 Comparative Examples Examples 14 15 5
Acrylic resin BR-73 100 100 100 Titanium oxide 83.5 83.5 83.5
Dioctyl phthalate 25.0 25.0 25.0 Modifier IM-1 -- -- -- IM-2 12.5
25.0 -- IM-3 -- -- -- IM-4 -- -- -- DuPont type impact A (>50
cm) A (>50 cm) D (25 cm) deformation test
INDUSTRIAL APPLICABILITY
[0098] The modifier for resin of the present invention can be well
dispersed by adding to various thermoplastic resins and curable
resins thereby to impart high impact resistance.
* * * * *