JP3532994B2 - Thermoplastic resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to impact resistance and pigment coloring.
The present invention relates to an impact-resistant resin composition having excellent resistance. [0002] Improving the impact resistance of resin materials
Is not only expanding the use of materials, but also
Industrial availability, such as the ability to respond to
The invention has been invented by various methods.
Was. In particular, a rubber component having a low Tg or a low elastic modulus is
The resin material dispersed during the trick has excellent impact resistance
This has led to industrialization. Conventionally, such rubber components have been used in resin matrices.
Impact resistance by dispersing in
ABS resin is one of the materials. [0005] ABS resin is acryloyl polybutadiene.
ABS graph obtained by graft polymerization of nitrile and styrene
FT-Polymer as SAN (Styrene-Acrylonitrile)
Dispersed in resin matrix
Various industrial materials utilizing the balance of physical properties and moldability
Has been used as. [0006] The ABS graph constituting the ABS resin
Toppolymer is a polycarbonate resin, polyester resin
Impact resistance by blending with other resins such as fat
It is used as a modifier to be applied. [0007] However, the ABS graft polymer
The effect as an impact modifier is not always sufficient,
In particular, SAN resin, polycarbonate resin and SAN /
Resin using polycarbonate blend as matrix
In the composition, in particular, due to insufficient impact strength of the molded article,
Can not be used for applications used in harsh conditions
No. Furthermore, the impact resistance of the ABS graft polymer
Improves the effect as a property modifier, especially in low-temperature atmosphere
As a method of improving the impact strength of
No. 7, PC and / or copolyester carbon
-A and resin matrix consisting of SAN resin
BS graft polymer and polyorganosiloxane
Polyvinyl acrylate is added to the composite rubber containing polyalkyl acrylate.
From composite rubber-based graft copolymer obtained by graft polymerization of polymer
A method using a resin composition has been proposed. [0009] However, Japanese Patent Application Laid-Open
No. 6-1897 discloses PC and / or copolyester.
Resin polymer consisting of stelka carbonate and SAN resin
ABS graft polymer and polyorgan
Composite resin containing polysiloxane and polyalkyl acrylate
Composite rubber graph with vinyl monomer graft polymerized on rubber
Excellent impact resistance due to resin composition combined with copolymer
Although it is shown that it has
Concrete impact resistance for material with resin matrix alone
The company did not disclose how to improve the impact.
Further, a component constituting the composite rubber-based graft copolymer
The composition and content of are not particularly limited,
Further, the resin compositions shown in the examples have a pigment coloring property.
Colored using pigments such as carbon black
If the color is not deep, it may be the viewpoint of the design of the molded product.
Can not be industrially satisfactory. [0010] Further, the amount of the pigment to be compounded is increased.
Improves the color tone of the resulting resin composition
In this case, the impact resistance inherent to the resin composition
Is not preferred because it is significantly impaired. That is, a conventional SAN resin matrix
High impact resistance and better performance
No method showing good pigment coloring properties has been found.
Development of technology that satisfies two performances at the same time is strongly desired
Was. Means for Solving the Problems The present inventors have developed a SAN tree.
Fat matrix, ABS graft polymer and polio
Compounds containing luganosiloxane and polyalkyl acrylate
Composite rubber-based rubber with vinyl monomer graft polymerized to synthetic rubber
Impact resistance and face of resin composition composed of raft copolymer
Surprisingly, as a result of diligent examination of the coloring property,
Specific organosiloxanes and polyalkyl acrylates
With vinyl monomer graft polymerized on composite rubber containing
The rubber-based graft copolymer is converted to SAN resin and ABS
ABS resin by using with
(SAN resin + ABS graft polymer-)
Good impact resistance without compromising good pigment coloring.
The present invention has been found to achieve the above. That is, the gist of the present invention is as follows.
Each of the following components (A), (B) and (C) is contained as a main component.
The thermoplastic resin composition. (A) An aromatic alkenyl is added to the rubbery polymer.
Monomer, vinyl cyanide monomer and copolymerizable with them
Grafting a monomer mixture consisting of functional vinyl monomers
Graft copolymer. (B) (b-1) Contains a vinyl polymerizable functional group
0.2 to 3 mol% of siloxane units and dimethylsiloxy
The sun unit consists of 97 to 99.8 mol%, and 3 or more
The above silicon atom having a siloxane bond is polydimethyl
Not more than 1 mol% based on all silicon atoms in the siloxane
And (b-
2) Composite composed of alkyl (meth) acrylate rubber
(B-3) aromatic alkenyl monomer, methacrylic
Acrylate, acrylate or vinyl cyanide
One or two or more monomers selected from
Raft polymerized graft copolymer. (C) an aromatic alkenyl monomer component,
Vinyl monomer components and vinyl copolymerizable with them
A copolymer comprising a monomer component as a component of the copolymer. The graft copolymer (A) according to the present invention comprises
Examples of the rubbery polymer to be formed include polybutadiene and polybutadiene.
Soprene, styrene-butadiene random copolymer and
And block copolymer, hydrogenation of the block copolymer
Product, acrylonitrile-butadiene copolymer, butadiene
Diene rubbers such as ethylene-isoprene copolymer, ethylene
-Random copolymer and block copolymer of propylene
, Ethylene-butene random copolymer and block
Copolymer, a copolymer of ethylene and an α-olefin,
Acrylics such as butyl acrylate-butadiene copolymer
Acid ester-butadiene copolymer, crosslinked acrylate, etc.
Acrylic elastomer, ethylene-vinyl acetate copolymer,
Ethylene-propylene-ethylidene norbornene copolymer
, Ethylene-propylene-hexadiene copolymer, etc.
Ethylene-propylene non-conjugated dienter polymers,
Tylene-isoprene copolymer, chlorinated polyethylene, etc.
These can be used alone or in combination of two or more.
Can be. Impact resistance and molding of the obtained resin composition
Considering workability, a preferable rubber-like elastic body is
Tylene-propylene rubber, butyl acrylate-butadi
Ene copolymer, acrylic elastomer, diene rubber, ethylene
A len-propylene non-conjugated dienter polymer,
More preferably, polybutadiene, butyl acrylate
Butadiene copolymer, styrene-butadiene copolymer
is there. The graft copolymer (A) according to the present invention comprises:
An aromatic alkenyl monomer, cyan
Vinyl monomers and vinyl monomers copolymerizable with them
Graft copolymerization of a monomer mixture consisting of
It is a polymer. As the aromatic alkenyl monomer used,
Is, for example, styrene, α-methylstyrene, vinyl
Ene, etc., and as a vinyl cyanide compound
Acrylonitrile, methacrylonitrile, etc.
As a copolymerizable vinyl monomer, methyl methacrylate
Rate, ethyl methacrylate, 2-ethylhexylmethyl
Methacrylic acid esters such as tacrylate, methyl acrylate
Rate, ethyl acrylate, butyl acrylate, etc.
Acrylic acid esters, maleimide compounds, etc.
Used in consideration of the impact resistance of the resin composition used
Styrene and acrylonitrile are preferred
It is used well. The copolymer (C) according to the present invention comprises an aromatic alcohol.
Lucenyl monomer component, vinyl cyanide monomer component and
A vinyl monomer component copolymerizable therewith is used to form a copolymer.
It is a copolymer as a component. Examples of the aromatic alkenyl monomer include, for example,
Styrene, α-methylstyrene, vinyl toluene, mono
Chlorostyrene, dichlorostyrene, monobromostyrene
, Dibromostyrene, p-tert-butylstyrene
, Ethyl styrene, vinyl naphthalene, etc.
Or styrene or α-methylstyrene. Also Shea
Examples of vinyl chloride compounds include acrylonitrile,
Tacrylonitrile and the like, preferably acrylonitrile.
Tril. Also as a copolymerizable vinyl monomer
Are methyl methacrylate, ethyl methacrylate, 2
-Ethylhexyl methacrylate, glycidyl methacrylate
Methacrylic acid esters such as latex, methyl acrylate
Acrylate, ethyl acrylate, butyl acrylate, etc.
Lylic acid ester, N-phenylmaleimide, N-methyl
Maleimide compounds such as maleimide, maleic anhydride, etc.
No. Preferred examples of the copolymer (C) include
Tylene-acrylonitrile copolymer (SAN resin) and
And styrene-acrylonitrile-N-phenylmaleimi
Copolymers. As a method for producing the copolymer (C), bulk
Usually known polymerization, such as solution polymerization, suspension polymerization, emulsion polymerization
A method is used. Further, the copolymer (C) is a graft copolymer.
Polymer (A) or composite rubber-based graft copolymer (B)
The ungrafted copolymer produced during the production of
Including. The composite rubber-based graft copolymer according to the present invention
(B) is (b-1) a vinyl polymerizable functional group-containing siloxae.
0.2 to 3 mol% and dimethylsiloxane unit
97 to 99.8 mol%, and 3 or more white
Polydimethylsiloxa having a silicon atom having a xanth bond
Is less than 1 mol% based on all silicon atoms in the
(B-2) alkyl
(Meth) acrylate rubber and composite rubber
(B-3) Aromatic alkenyl monomer, methacrylic acid S
Ter, acrylate or vinyl cyanide monomer
One or two or more monomers selected from
The graft copolymer was combined. The biorganic compound in the polyorganosiloxane (b-1)
Not more than 0.2 mol% of siloxane units containing phenyl polymerizable functional groups
In full, alkyl (meth) acrylate rubber (b-2)
Is insufficiently complexed with the resin containing the graft copolymer.
Polyorganosiloxane on the Surface of Fat Composition Molded Article
Appearance failure resulting from the bleed-out occurs. Further, polyorganosiloxane (b-1)
3 mol% of siloxane units containing vinyl polymerizable functional groups
More than or has three or more siloxane bonds
Silicon atoms are all silicon atoms in polyorganosiloxane
If it exceeds 1 mol%, the resulting resin composition
The impact resistance is slightly reduced. Further, a resin composition containing a graft copolymer
Considering both impact resistance and molded appearance of polyorgan
Vinyl-polymerizable functional group-containing siloxane in siloxane
The position is preferably 0.5 to 2 mol%, more preferably 0.1 to 2 mol%.
5 to 1 mol%. The above polyorganosiloxane (b-1)
The vinyl polymerizable functional group present in the
Cross-linkable with (meth) acrylate rubber (b-2)
Which is an anti-alkyl (meth) acrylate rubber
Considering the reactivity, methacryl group, vinyl group, aromatic alcohol
Lucenyl group, mercapto group and azo group are preferred,
More preferably, it is a methacryl group. The copolymer constituting the copolymer (B) according to the present invention
Although the composition ratio of the synthetic rubber is not particularly limited, it is preferable.
Or the amount of the polyorganosiloxane (b-1) therein is 1
~ 20% by weight, alkyl (meth) acrylic rubber is 99 ~
80% by weight ((b-1) + (b-2) = 100% by weight)
If less than 1% by weight, the amount of polyorganosiloxane is
Due to the small amount, the impact resistance slightly decreases, and exceeds 20% by weight.
Pigmentation of Resin Composition Molded Article Containing Graft Copolymer
The properties are slightly poor. In addition, a tree containing a graft copolymer
Considering both the impact resistance and pigment coloring of the fat composition,
The amount of polyorganosiloxane in the composite rubber is more preferred
6-20% by weight, alkyl (meth) acrylic rubber
99-80% by weight ((b-1) + (b-2) = 100 weights
%), And more preferably polyorganosiloxa.
10-20% by weight, alkyl (meth) acrylic rubber
Is 90 to 80% by weight ((b-1) + (b-2) = 100
% By weight). As a method for producing the above polyorganosiloxane,
Is dimethylsiloxane and vinyl polymerizable functional group containing silo
Mixture of xane or further siloxane-based crosslinker
Which emulsifies a mixture containing water with an emulsifier and water
Homogenizer that makes particles fine by the shearing force of high-speed rotation
-And homogenizers that are atomized by the injection power of a high-pressure generator
After the particles are made into fine particles using an
Polymerization under temperature, then neutralize acid with alkaline substance
Is what you do. As a method for adding the acid catalyst used in the polymerization,
Mixing with siloxane mixture, emulsifier and water
Method and a latex with a siloxane mixture
There is a method of dropping at a constant rate into a hot acid aqueous solution,
Considering easy control of particle size of polyorganosiloxane
Considering the latex in which the siloxane mixture is finely divided,
A method of dropping at a constant rate into a hot acid aqueous solution is preferred.
No. The size of the polyorganosiloxane is particularly limited.
Although not specified, the face of the resin composition containing the graft copolymer
In consideration of coloring properties, the weight average particle size should be 0.2 μm or less.
Is preferable, and more preferably 0.1 μm or less.
You. Further, it is used for the production of polyorganosiloxane.
Some dimethylsiloxanes have three or more ring
And a 3- to 6-membered ring
preferable. Specifically, hexamethylcyclotrisiloxa
Octamethylcyclotetrasiloxane, decamethyl
Cyclopentasiloxane, dodecamethylcyclohexacyclo
Roxane and the like, which may be used alone or in combination of two or more.
These are used as a mixture. Also, a siloxane containing a vinyl polymerizable functional group
Is a dimethylsiloxane containing a vinyl polymerizable functional group and
Which can be bonded to siloxane through a siloxane bond
Considering its reactivity with dimethylsiloxane, vinyl
Various alkoxysilane compounds containing polymerizable functional groups
preferable. Specifically, β-methacryloxyethyldimethyl
Toximethylsilane, γ-methacryloxypropyldim
Toximethylsilane, γ-methacryloxypropyl meth
Xidimethylsilane, γ-methacryloxypropyl tri
Methoxysilane, γ-methacryloxypropyl ethoxy
Diethylsilane, γ-methacryloxypropyldiethoxy
Simethylsilane and δ-methacryloxybutyldiet
Methacryloxysiloxane such as xylmethylsilane, tet
Vinyls such as lamethyltetravinylcyclotetrasiloxane
Siloxane, p-vinylphenyldimethoxymethyl
Run and γ-mercaptopropyldimethoxymethyl
Orchid, γ-mercaptopropyltrimethoxysilane, etc.
And mercaptosiloxane. As the siloxane-based cross-linking agent, trifunctional or
Or a tetrafunctional silane crosslinking agent such as trimethoxymeth
Tylsilane, triethoxyphenylsilane, tetrameth
Xysilane, tetraethoxysilane, tetrabutoxy
Runs are used, but the amount used is
Silicon atom in the polyorganosiloxane
1 mol% or less, preferably more than 1 mol%, based on elemental atoms
When used in the range described above, the resin group containing the graft copolymer
The impact resistance of the product is slightly reduced. Further, the polyorganosiloxa according to the present invention
Anionic emulsifiers are used as emulsifiers in the production of
Preferably, sodium alkylbenzene sulfonate,
Lioxyethylene nonylphenyl ether sulfate
An emulsifier selected from sodium and the like is used.
In particular, sodium alkylbenzenesulfonate, lauryl
Sulfonic acid-based emulsifiers such as sodium sulfonate are preferred.
Good. These emulsifiers are used in the siloxane mixture 10
Used in the range of 0.05 to 5 parts by weight with respect to 0 parts by weight
Is done. If the amount used is small, the dispersion state will be unstable and very small
It becomes impossible to maintain an emulsified state having a large particle diameter. In addition, high usage
The coloring of the resin composition molded article caused by the cousin emulsifier is severe.
It is inconvenient. The siloxane mixture, emulsifier, water and / or
Alternatively, the method of mixing the acid catalyst may be mixing by high-speed stirring,
Mixing with a high-pressure emulsifying device such as a modifier
However, the method using a homogenizer is a polyorganosynthesis.
Loxane latex has a small particle size distribution.
It is a better way. Acid used for polymerization of polyorganosiloxane
As the catalyst, aliphatic sulfonic acid, aliphatic substituted benzene
Sulfonic acid, aliphatic substituted naphthalene sulfonic acid, etc.
Examples include sulfonic acids and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid.
Can be These acid catalysts may be used alone or in combination of two or more.
Used together. Also, among these, Polyol
Excellent stabilizing effect of ganosiloxane latex
Aliphatic substituted benzenesulfonic acid is preferable in terms of
Decylbenzenesulfonic acid is particularly preferred. Also, n-
Dodecylbenzenesulfonic acid combined with mineral acids such as sulfuric acid
Then, the emulsifier component of the polyorganosiloxane latex
Can reduce the coloring of the resin composition due to the
You. The polymerization temperature of the polyorganosiloxane is 5
0 ° C or higher is preferable, and more preferably 80 ° C or higher.
You. The polymerization time of the polyorganosiloxane depends on the acid
Mix catalyst with siloxane mixture, emulsifier and water
In the case where the polymerization is carried out by making the particles fine, two hours or more,
It is preferably 5 hours or more, and the white
Method of lowering particulated latex with xan mixture
Then, hold for about one hour after the end of the latex dripping
Is preferred. To stop the polymerization, cool the reaction solution,
Of caustic soda, caustic potash, sodium carbonate, etc.
Can be done by neutralizing with an alkaline substance
You. The graft copolymer (B) according to the present invention is
Alkyl (meth) acrylate rubber to be formed (b-2)
Are alkyl (meth) acrylates and polyfunctional alkyls
It is a polymer with (meth) acrylate.
Liorganosiloxane (b-1) latex with alkyl
(Meth) acrylate and polyfunctional alkyl (meth)
Alkyl (meth) acrylate composed of acrylate
Manufactured by impregnating and then polymerizing
Can be. Examples of alkyl (meth) acrylate include
For example, methyl acrylate, ethyl acrylate, n-propyl
Propyl acrylate, n-butyl acrylate, 2-e
Alkyl acrylates such as tylhexyl acrylate
And hexyl methacrylate, 2-ethylhexyl methacrylate
Alkyl such as acrylate and n-lauryl methacrylate
And methacrylate. Particularly, n-butyl acrylate
The use of a metal is preferred. Multifunctional alkyl (meth) acryl
As the rate, for example, allyl methacrylate, ethyl
Glycol dimethacrylate, propylene glycol
Dimethacrylate, 1,3-butylene glycol dimeth
Acrylate, 1,4-butyleneglycol dimethacrylate
-Triallyl cyanurate, triallyl isocyanurate
And the like. In addition, polyfunctional alkyl (meth)
(T) The amount of acrylate used is alkyl (meth) acrylate.
0.1 to 20% by weight, preferably 0.2 to 20% by weight in the late component
The content is 5% by weight, more preferably 0.2 to 1% by weight.
Alkyl (meth) acrylate and polyfunctional alkyl (meth)
T) Acrylate may be used alone or in combination of two or more.
Can be The polyorganosiloxane according to the present invention and
The composite rubber consisting of the rubber (meth) acrylate rubber is
Into the latex of the polyorganosiloxane component
Add the kill (meth) acrylate component and add
It is prepared by polymerizing with the action of a polymerization initiator.
Wear. A method of adding an alkyl (meth) acrylate;
Of the polyorganosiloxane component latex
Method of mixing and latte of polyorganosiloxane component
There is a method of dropping at a constant speed in a box. In addition, obtained
Consideration of impact resistance of resin composition containing graft copolymer
Then the latex of the polyorganosiloxane component is batched.
Is preferred. In addition, the radio
As polymerization initiators, peroxides, azo initiators, and
Is a redox initiator that combines an oxidizing agent and a reducing agent.
Used. Of these, redox initiators are preferred.
Especially for ferrous sulfate and ethylenediaminetetraacetic acid
Combination of um salt, Rongalid and hydroperoxide
Preferred are sulfoxylate initiators. The graft copolymer (B) according to the present invention comprises
The polyorganosiloxane (b-
1) and alkyl (meth) acrylate rubber (b-2)
(B-3) aromatic alkenyl monomer
Body, methacrylate, acrylate or
One or more selected from vinyl cyanide monomers
Is a graft copolymer obtained by graft polymerization of a monomer of
Among the monomers used for graft polymerization, aromatic alkenyl
Examples of the monomer include styrene, α-methylstyrene,
And methacrylic acid esters.
For example, methyl methacrylate, ethyl methacrylate,
2-ethylhexyl methacrylate, etc., and acrylic
Examples of the acid ester include methyl acrylate, ethyl
Acrylate, butyl acrylate, etc.
Examples of vinyl compounds include acrylonitrile,
Rilonitrile and the like. The graft polymerization is performed on the latex of the composite rubber.
Aromatic alkenyl compounds, methacrylic acid esters,
Selected from lylic esters or vinyl cyanide compounds
One or two or more monomers
Depending on the technique, it can be performed in one step or in multiple steps.
Impact resistance of the resin composition containing the graft copolymer
Polymerization in two or more stages, taking into account pigment coloring properties
Is preferred. Aromatic alkenylation used for graft polymerization
Compound, methacrylate, acrylate or
Is one or more selected from vinyl cyanide compounds
The amount of the above monomer depends on the weight of the obtained graft copolymer.
It is preferably 50 to 80% by weight, and not more than 50% by weight.
In the case of the pigment of the resin composition molded article containing the graft copolymer
If the coloring property is slightly lowered, and if it exceeds 80% by weight, molding
The gloss of the product tends to decrease. Also, graft copolymerization
Consider both impact resistance and pigment coloring of resin compositions containing
Considering aromatic alkenyl compounds in graft copolymers
Substance, methacrylate, acrylate or
One or more selected from vinyl cyanide compounds
Is more preferably the total amount of the graft copolymer 10
50 to 70% by weight, more preferably 5% to 0% by weight.
0 to 60% by weight. Further, monomers used in the graft polymerization
In some cases, the molecular weight and graft ratio of the graft polymer are adjusted.
Various chain transfer agents can be added. Further, the graft copolymer prepared as described above
The particle size of the polymer (B) is not particularly limited.
Is the impact resistance of the resulting resin composition containing the graft copolymer.
Considering both the impact resistance and pigment coloring, the weight average particle size
Is preferably from 0.07 to 0.2 μm,
Preferably it is 0.10 to 0.15 μm. After the completion of the graft polymerization, the latex
Dissolve metal salts such as calcium chloride or aluminum sulfate
It is poured into hot water that has been
The ft copolymer can be separated and recovered. The graft copolymer (A) according to the present invention,
The compounding amounts of the raft copolymer (B) and the copolymer (C)
Although not particularly limited, preferably each
0.5 to 99.5% by weight, 0.5 to 99.5% by weight and
And 0.5 to 99.5% by weight. The thermoplastic resin composition according to the present invention comprises
Graft copolymer (A) prepared by the method of
The polymer (B) and the copolymer (C) are usually kneaded with a known kneader.
It can be extruded by a machine. like this
Molding machines include extruders, injection molding machines, blow molding machines,
Examples include render molding machines and inflation molding machines.
It is. Further, a resin composition containing a graft copolymer
If necessary, dyes, pigments, stabilizers, reinforcing agents,
Fillers, flame retardants and various thermoplastic resins
Can be. Hereinafter, the present invention will be described with reference to examples. still,
In Reference Examples, Examples and Comparative Examples,
"%" Means "parts by weight" and "% by weight" unless otherwise specified
Means Polyolga in latex in Reference Example
Weight average particle size of
The weight average particle size of the graft copolymer in TEX is large.
Dynamic Light Scattering Using Model DLS-700 manufactured by Tsuka Electronics Co., Ltd.
It was determined by the method. Izod impact in Examples and Comparative Examples
The impact strength is measured by a method based on ASTM D258.
Went better. The surface hardness (b) in Examples and Comparative Examples
(Cockwell hardness) according to ASTM D785
The method was performed as follows. Further, the resin sets in Examples and Comparative Examples
The appearance of the molded product was evaluated using an injection molding machine manufactured by Toshiba Machine Co., Ltd.
100mmx100 molded using IS-100EN
By visual observation of the surface of the mm × 3 mm plate, the pigment
Each by hue measurement according to IS Z8729
evaluated. Examples (Reference Example 1) Polyorganosiloxane latex L-
Preparation of 1 98 parts of octamethylcyclotetrasiloxane, γ-meta
Mix 2 parts of acryloxypropyldimethoxymethylsilane
As a result, 100 parts of a siloxane-based mixture was obtained. To this
0.67 parts of sodium rubenzenesulfonate was dissolved
300 parts of distilled water was added, and 10,000
After stirring for 2 minutes at a rotation / minute, the mixture was added to a homogenizer for 300 minutes.
kg / cm ^Two Once at a pressure of
A siloxane latex was obtained. On the other hand, a reagent injection container, a cooling pipe, a jacket
Dodecylbenzene is placed in a reactor equipped with a heater and a stirrer.
10 parts of benzene sulphonic acid and 90 parts of distilled water
A 0% by weight aqueous solution of dodecylbenzenesulfonic acid was prepared.
Was. The solution was heated to 85 ° C.
Preparing mixed organosiloxane latex for 4 hours
After the dropwise addition, the temperature was maintained for 1 hour after the completion of the dropwise addition, followed by cooling. Next
The reaction was then neutralized with aqueous sodium hydroxide solution. The latex thus obtained was mixed with 17
When the solid content was determined by drying at 0 ° C. for 30 minutes, 17.
7% by weight. In addition, polyorgano in latex
The number average particle size of the siloxane was 0.05 μm. Reference Example 2 Composite Rubber Graft Copolymerization
Reagent injection container, cooling tube, jacket heater and stirring device for production of body S-1
In the reactor equipped with the device, the polyorgano obtained in Reference Example 1 was placed.
56 parts of siloxane latex (L-1), N-lauroy
0.3 part of luzarcosin sodium was collected and distilled water 25
After adding and mixing 0 parts, butyl acrylate 63.7 was added.
Part, allyl methacrylate 0.4 part, 1,3-butylene
0.1 part of glycol dimethacrylate and cumench
A mixture of 0.15 parts of dropper-oxide was added. By passing a stream of nitrogen through the reactor,
Then, the atmosphere was replaced with nitrogen, and the temperature was raised to 60 ° C. Inside
When the temperature of the solution reaches 60 ° C., ferrous sulfate 0.00
01 parts, ethylenediaminetetraacetic acid disodium salt 0.0
003 parts and Rongalid 0.24 parts are distilled water 10 parts
Add the aqueous solution dissolved in
I did. Due to polymerization of the acrylate component, the liquid temperature reaches 78 ° C.
Rose. This condition is maintained for one hour,
To complete the polymerization of the polyorganosiloxane
A latex of a composite rubber with acrylate rubber was obtained. After the liquid temperature inside the reactor has dropped to 60 ° C.,
An aqueous solution in which 0.4 part of Rongalid is dissolved in 10 parts of distilled water
And then 11 parts of acrylonitrile, 3 parts of styrene
3 parts and 0.23 part of cumene hydroperoxide
The mixture was added dropwise over 2 hours to carry out polymerization. Drip end
Then, after maintaining the state of the temperature of 60 ° C. for 1 hour, ferrous sulfate
0.0002 parts, disodium ethylenediaminetetraacetate
Distill 0.0006 parts of salt and 0.23 parts of Rongalid
An aqueous solution dissolved in 10 parts of water is added.
7.4 parts of nitrile, 22.2 parts of styrene and cumene
A mixture of 0.13 parts of hydroperoxide was added for 2 hours.
It was dropped and polymerized. After dropping, at a temperature of 60 ° C
Is held for 1 hour and then cooled, and the polyorganosiloxane and
Acrylate is added to a composite rubber consisting of butyl acrylate rubber.
Graft polymerized lonitrile-styrene copolymer
A latex of a raft copolymer was obtained. From dynamic light scattering method
Weight average particle of graft copolymer in latex obtained
The diameter was 0.13 μm. Next, 7.5% by weight of aluminum sulfate was added.
Heat and stir 150 parts of the aqueous solution
Was. 100 parts of the latex of the graft copolymer is put into this.
It was dropped slowly and solidified. The precipitate is then separated, washed
After drying, a graft copolymer was obtained. (Examples 1 to 10 and Comparative Examples 1 and 2)
The following components were used in the examples and comparative examples. Component (A) (ABS graft polymer): polybutadier
50 parts of acrylonitrile (15 parts) and styrene (3 parts)
ABS graft obtained by emulsion graft polymerization of the mixture of (5 parts)
Polymer (average particle size 0.3 μm, acetone insoluble matter
Component (B) (composite rubber-based graft copolymer): Reference Example 2
Composite rubber-based copolymer component (C) (SAN resin) prepared in
Polymerization of a mixture of 30 parts of rilonitrile by suspension polymerization
Reduced viscosity measured in dimethylformamide solution
(Η _SP / C) SAN resin with 0.60 Each component of (A), (B) and (C) is shown in Table 1.
Mix (weight ratio) and add ADEKA as a heat stabilizer.
0.3 parts of Stable C (manufactured by Asahi Denka Co., Ltd.)
0.4 parts of barium stearate as a mold agent
0.4 parts of EBS as a coloring agent, and
Bon Black (CB-960: manufactured by Mitsubishi Chemical Corporation)
0.8 parts each added and mixed, cylinder temperature 230 ° C
The mixture was shaped by a single-screw extruder set to produce pellets.
Next, the pellets were heated at a cylinder-set temperature of 230 ° C.
Injection molding at a mold temperature of 60 ° C, evaluation of physical properties and pigment coloring
Valuable test pieces were obtained. From each of the obtained test pieces, Izod
Obtained from impact strength, Rockwell hardness and hue measurements
L ^* The values are shown in Table 1. [Table 1] The following is clear from the examples and comparative examples.
It was clear. 1) The resin compositions of Examples 1 to 5 are comparative examples
1. Composite rubber-based graft copolymer having the same rubber content as shown in 1
Impact strength and Izod impact strength compared to ABS resin containing no
And high values of Rockwell hardness. 2) The resin compositions of Examples 6 to 10
Composite rubber-based graft copolymer with the same rubber content as shown in Example 2
Izod impact strength and strength compared to ABS resin without body
It shows high values for both Rockwell hardness. 3) The resin compositions shown in the examples have good compositions.
The shape and appearance are shown. 4) The brightness (L) of the black colored product ^* ) Is a comparative example
Equivalent to or less than ABS resin
Same as ABS resin used for various purposes as a material
Excellent, such as being able to obtain a deep black molded appearance
Pigment coloring property. The present invention has been described above.
It has a particularly remarkable effect like that of its industrial value.
The values are very large. 1) The resin composition according to the present invention has an impact resistance
Excellent balance of properties, surface hardness, molded appearance, and pigment coloring
You. 2) In particular, Izod impact strength and surface hardness
Balance cannot be obtained with the conventionally known ABS resin.
This is a very high level and is useful as various industrial materials.
The utility value is extremely high. 3) The resin composition according to the present invention is
Same or better than ABS resin used as industrial material
High designability is required due to excellent pigment coloring
It can be used for required applications, and as an industrial material
The utility value is extremely high.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-116471 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 51/04 C08L 25/12

Claims (1)

(57) [Claims 1] A thermoplastic resin composition containing the following components (A), (B) and (C) as main components. (A) A graft copolymer obtained by grafting a monomer mixture of an aromatic alkenyl monomer, a vinyl cyanide monomer, and a vinyl monomer copolymerizable therewith on a rubbery polymer. (B) (b-1) 0.2 to 3 mol% of a siloxane unit containing a vinyl polymerizable functional group and 97 dimethylsiloxane units
A polydimethylsiloxane comprising at least 1 mol% and at most 1 mol% of all silicon atoms in the polydimethylsiloxane; and (b- 2) A composite rubber composed of an alkyl (meth) acrylate rubber and (b)
-3) A graft copolymer obtained by graft-polymerizing one or two or more monomers selected from aromatic alkenyl monomers, methacrylates, acrylates and vinyl cyanide monomers. (C) A copolymer comprising an aromatic alkenyl monomer component, a vinyl cyanide monomer component, and a vinyl monomer component copolymerizable therewith with the copolymer.