JP3450450B2 - Graft copolymer and thermoplastic resin composition thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact resistant resin excellent in impact resistance and pigment coloring.

[0002]

2. Description of the Related Art Improving the impact resistance of resin materials not only expands the applications of the materials, but also makes it possible to cope with thinner and larger molded products, which is of great industrial utility. The invention is large and has been invented by various methods.

In particular, a resin material in which a rubber component having a low Tg and a low elastic modulus is dispersed in a resin matrix has been industrialized due to its excellent impact resistance.

Further, in order to improve the impact resistance of the resin material in which such a rubber component is dispersed, the use of polyorganosiloxane having a lower Tg and a lower elastic modulus as the rubber component is disclosed in JP-A-60-252613. Proposed in the gazette.

However, in this method, a matte molding appearance defect derived from polyorganosiloxane occurs, and if the particle diameter of the graft rubber is reduced to improve the molding appearance, the impact resistance is deteriorated, resulting in high resistance. Since it is not possible to achieve both impact properties and a good molding appearance, it has low industrial value.

JP-A-63-69859 discloses that a vinyl monomer is graft-polymerized on a composite rubber composed of a polyorganosiloxane rubber and a poly (meth) acrylate rubber in order to improve the surface appearance of a resin molded product. Graft copolymers have been proposed.

Further, Japanese Patent Laid-Open No. 5-279434 discloses a method for improving the pigment coloring of impact-resistant resin.
20% by volume or less of particles having a number average particle size of 0.01 to 0.07 μm and a particle size of more than 0.10 μm obtained by graft-polymerizing a vinyl monomer onto a composite rubber composed of polyorganosiloxane and (meth) acrylate. It has been proposed to use polymers.

Further, JP-A-62-280210 discloses a graft copolymer composed of a core of crosslinked silicone, a first shell of crosslinked acrylate rubber, and a second shell of a vinyl polymer component. Coalescing is proposed.

Further, JP-A-64-6012 discloses a graft copolymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a rubber composed of a core such as a crosslinked acrylate rubber and a shell of polyorganosiloxane. Proposed.

[0010]

However, Japanese Patent Laid-Open No. 63-69859 discloses a method for producing a polyorganosiloxane rubber that constitutes a composite rubber, in which 0 to 10 parts by weight of a graft crossing agent containing a vinyl polymerizable functional group is used. In the examples, 0 to 0.5 parts by weight of γ-methacryloxypropyldimethoxymethylsilane is used, that is, the siloxane units containing γ-methacryloxypropyl groups are based on all siloxane units, although the use of parts by weight is mentioned. 0-0.1
Only the use of 6 mol% of polyorganosiloxane is described, and in the graft copolymer using the polyorganosiloxane having the content of the vinyl polymerizable functional group in such a range, polyorganosiloxane and (meth) siloxane are used. ) The pigment coloring property is low because the compounding with the acrylate rubber is insufficient.

Further, in the specification of JP-A-5-279434, a graft crossing agent is used as a polyorganosiloxane constituting a composite rubber in an amount of 10 parts by weight or less, preferably 0.5.
Although it is disclosed to use ~ 5 parts by weight, the examples use 0.5 parts by weight of γ-methacryloxypropyldimethoxymethylsilane, i.e. the siloxane units containing γ-methacryloxypropyl groups are based on all siloxane units. No. 6,096,086, only the use of 0.16 mol% of polyorganosiloxane is not mentioned, and the effect of the content of vinyl-polymerizable functional groups in the polyorganosiloxane on the molding appearance and impact resistance is not suggested.

Further, in the specification of JP-A-62-280210, as a polyorganosiloxane constituting the core of a crosslinked silicone, a radical unit attackable unit is preferably on all silicon. 2-1 based on substituents
Although disclosed to contain 0 mol%, in the examples, 2.6 mol% of a siloxane unit having a vinyl group.
Containing 42.1% by weight of polyorganosiloxane rubber, 18.1% by weight of acrylate rubber and acrylonitrile-styrene copolymer or methylmethacrylate
Or methyl methacrylate-styrene copolymer 3
Only the use of a graft copolymer containing 9.8% by weight is described, and the resin composition containing the graft copolymer thus obtained has particularly poor pigment colorability.

Further, in JP-A-64-6012, there is no particular description about the amount of vinyl-polymerizable functional groups in the all-silicon substituents of the polyorganosiloxane used for the first shell, and in the examples, vinyl-polymerizable functional groups. 3 polyorganosiloxanes containing 2.1 mol% of siloxane units having groups
Only the graft copolymer containing 0% by weight is disclosed, and the resin composition containing the graft copolymer thus obtained is inferior in pigment coloring property.

That is, conventionally, polyorganosiloxanes, poly (meth) acrylates and graft polymers have been used.
In the graft copolymer consisting of, no attention has been paid to the amount of siloxane units containing a vinyl-polymerizable functional group in the polyorganosiloxane, the amount of polyorganosiloxane in the composite rubber, and the amount of graft polymer. There has been a strong demand for the development of a graft copolymer that satisfies the impact resistance and pigment colorability of a resin composition containing the graft copolymer at the same time.

[0015]

SUMMARY OF THE INVENTION The inventors of the present invention have made a polymer of polyorganosiloxane constituting a graft copolymer.
As a result of diligent studies on the structure and the polymer composition of the graft copolymer, and the impact resistance and pigment coloring of the resin composition containing the same, surprisingly, the siloxane containing a vinyl polymerizable functional group in the polyorganosiloxane. The resin composition containing the graft copolymer is produced by limiting the amount of units and the crosslinking density, the amount of polyorganosiloxane in the graft copolymer, the amount of alkyl (meth) acrylate rubber and the amount of graft polymer. The present invention has been accomplished by finding that the product exhibits excellent impact resistance and pigment coloring property which have never been obtained.

That is, the gist of the present invention is that
(A) Vinyl polymerizable functional group-containing siloxane unit 0.2 to
3 mol% and dimethylsiloxane units 97-99.8
Polydimethylsiloxane, characterized by comprising 1 mol% or less of silicon atoms having 3 or more siloxane bonds, based on the total silicon atoms in the polydimethylsiloxane, and (B) alkyl (meth). Graft copolymerization in which one or more monomers selected from (C) aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds are graft-polymerized to a composite rubber composed of an acrylate rubber. 1 to 20 of the polysiloxane (A) in the composite rubber
8% by weight of alkyl (meth) acrylate rubber (B)
A graft copolymer containing 0 to 99% by weight and 50 to 80% by weight of the graft component (C) with respect to the total graft copolymer; and the graft copolymer and an acrylonitrile-styrene copolymer. It is in a thermoplastic resin composition with a polymer.

The polyorganosiloxane constituting the graft copolymer according to the present invention comprises 0.2 to 3 mol% of a vinyl-polymerizable functional group-containing siloxane unit and 97 to 99.8 mol% of a dimethylsiloxane unit, and further 3 The number of silicon atoms having at least one siloxane bond is 1 mol% or less based on all silicon atoms in the polydimethylsiloxane.

When the content of the siloxane unit containing a vinyl-polymerizable functional group in the polyorganosiloxane is less than 0.2 mol%, the compounding with the alkyl (meth) acrylate rubber becomes insufficient and the resin composition containing the graft copolymer is obtained. Poor appearance due to bleed-out of polyorganosiloxane on the surface of the molded product occurs.

Further, the vinyl-polymerizable functional group-containing siloxane unit in the polyorganosiloxane exceeds 3 mol%,
Alternatively, when the silicon atom having three or more siloxane bonds exceeds 1 mol% with respect to the total silicon atoms in the polyorganosiloxane, the impact resistance of the resin composition containing the graft copolymer is low, which is not preferable.

Further, considering both the impact resistance and the appearance of molding of the resin composition containing the graft copolymer, 0.3 to 2 mol% of the vinyl polymerizable functional group-containing siloxane unit in the polyorganosiloxane is more preferable. It is 0.3 to 1 mol%.

The amount of polyorganosiloxane in the composite rubber according to the present invention is 1 to 20% by weight. If it is less than 1% by weight, the impact resistance becomes low because the amount of polyorganosiloxane is small, and if it exceeds 20% by weight. The pigment coloring property of the resin composition molded article containing the graft copolymer is poor and its industrial value is low. In consideration of both impact resistance and pigment colorability of the resin composition containing the graft copolymer, the amount of polyorganosiloxane in the composite rubber is preferably 6 to 20% by weight,
More preferably, it is 10 to 20% by weight.

Graft copolymerization in which one or more monomers selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds in the graft copolymer according to the present invention are graft polymerized. The amount of the coalescence is 50 to 80% by weight. If it is less than 50% by weight, the pigment coloring property of the resin composition molded article containing the graft copolymer is poor, and if it exceeds 80% by weight, the rubber amount becomes low. It is not preferable because the impact resistance becomes low. Further, in consideration of both impact resistance and pigment colorability of the resin composition containing the graft copolymer, it is selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds in the graft copolymer. The amount of the graft copolymer obtained by graft-polymerizing one or more monomers is preferably 50 to 70% by weight, more preferably 50 to 60% by weight.

The vinyl-polymerizable functional group present in the polyorganosiloxane constituting the graft copolymer according to the present invention is not particularly limited as long as it is capable of cross-linking with an alkyl (meth) acrylate rubber. However, considering the reactivity with the acrylate rubber, a methacryl group, a vinyl group, an aromatic alkenyl group, a mercapto group, an azo group and the like are preferable, and a methacryl group is more preferable.

The method for producing the polyorganosiloxane according to the present invention is as follows. A latex prepared by emulsifying a mixture of dimethylsiloxane and a vinyl-polymerizable functional group-containing siloxane or a mixture containing a siloxane-based crosslinking agent with an emulsifier and water is rotated at high speed. After homogenizing using a homomixer that atomizes by shearing force due to, or a homogenizer that atomizes by jetting output from a high-pressure generator, polymerize at high temperature using an acid catalyst, and then acid with an alkaline substance. It neutralizes.

As a method of adding an acid catalyst used for polymerization,
There are a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping a latex in which the siloxane mixture is made into fine particles into a hot acid aqueous solution at a constant rate.
Considering the ease of controlling the particle size of the polyorganosiloxane, a method is preferred in which a latex in which the siloxane mixture is made into fine particles is dropped into the high temperature aqueous acid solution at a constant rate.

The size of the polyorganosiloxane is not particularly limited, but considering the pigment colorability of the resin composition containing the graft copolymer, the weight average particle diameter is preferably 0.2 μm or less, more preferably 0.1 μm. It is the following.

As the dimethylsiloxane used for producing the polyorganosiloxane, a dimethylsiloxane cyclic compound having a 3-membered ring or more is mentioned, and a 3-membered 6-membered ring is preferable. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc. These may be used alone or in combination of two or more.

The vinyl-polymerizable functional group-containing siloxane is not particularly limited as long as it has a vinyl-polymerizable functional group and can be bonded to dimethylsiloxane through a siloxane bond, but the reactivity with dimethylsiloxane is not limited. Considering the above, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable. Specifically, β-methacryloxyethyldimethoxymethylsilane, γ-methacryloxypropyldimethoxymethylsilane, γ-methacryloxypropylmethoxydimethylsilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylethoxydiethylsilane, Methacryloxysiloxanes such as γ-methacryloxypropyldiethoxymethylsilane and δ-methacryloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane and γ-mercaptopropyldimethoxy. Examples thereof include mercaptosiloxanes such as methylsilane and γ-mercaptopropyltrimethoxysilane.

These vinyl-polymerizable functional group-containing siloxanes may be used either individually or as a mixture of two or more thereof, but the amount used is based on the siloxane units of the resulting polyorganosiloxane and contains vinyl-polymerizable functional group-containing siloxane units. The siloxane unit is in the range of 0.2 to 3 mol%,
Preferably 0.3 to 2 mol%, more preferably 0.3
~ 1 mol%. When a vinyl-polymerizable functional group-containing siloxane capable of forming three siloxane bonds is used, the silicon atom of the vinyl-polymerizable functional group-containing siloxane must be 1 mol% or less based on the total silicon atoms in the polyorganosiloxane. However, 3 in the range exceeding 1 mol%
The use of a vinyl-polymerizable functional group-containing siloxane capable of forming two siloxane bonds is not preferable because the impact resistance of the resin composition containing the graft copolymer is impaired.

As the siloxane-based cross-linking agent, trifunctional or tetrafunctional silane-based cross-linking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane are used. The amount of silicon atom in the siloxane-based cross-linking agent must be 1 mol% or less with respect to all the silicon atoms in the polyorganosiloxane, and when used in a range exceeding 1 mol%, the graft copolymer is used. The impact resistance of the resin composition containing is impaired, which is not preferable.

As the emulsifier used in the production of the polyorganosiloxane according to the present invention, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylenenonylphenyl ether sulfate, etc. Is used.
Particularly, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

These emulsifiers are based on the siloxane mixture 10
It is used in the range of about 0.05 to 5 parts by weight with respect to 0 parts by weight. When the amount used is small, the dispersion state becomes unstable, and it becomes impossible to maintain the emulsified state with a fine particle size. Further, if the amount used is large, the coloring of the resin composition molded product due to the emulsifier becomes extremely large, which is inconvenient.

The method of mixing the siloxane mixture, the emulsifier, water and / or the acid catalyst includes mixing by high speed stirring, mixing by a high pressure emulsifying device such as a homogenizer, and the method using a homogenizer is a polyorganosiloxane. This is a preferable method because the particle size distribution of the latex becomes small.

Examples of the acid catalyst used for the polymerization of 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 may be used alone or in combination of two or more. Among these, aliphatic-substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable, because it is also excellent in stabilizing the polyorganosiloxane latex. Also, n-
The combined use of dodecylbenzene sulfonic acid and a mineral acid such as sulfuric acid can reduce the coloring of the resin composition due to the emulsifier component of the polyorganosiloxane latex.

The polymerization temperature of polyorganosiloxane is 5
The temperature is preferably 0 ° C or higher, more preferably 80 ° C or higher.

The polymerization time of the polyorganosiloxane is 2 hours or more, and more preferably 5 hours or more when the acid catalyst is mixed with the siloxane mixture, the emulsifier and water to be finely divided and polymerized. In the method of reducing the latex in which the siloxane mixture is made into fine particles, it is preferable to hold the latex for about 1 hour after the completion of the dropping of the latex.

The termination of the polymerization can be carried out by cooling the reaction solution and further neutralizing the latex with an alkaline substance such as caustic soda, potassium hydroxide and sodium carbonate.

The polyorganosiloxane latex thus produced was impregnated with an alkyl (meth) acrylate component composed of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate. A composite rubber can be obtained by polymerizing.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Alkyl acrylates such as ethylhexyl acrylate and hexyl methacrylates, 2-ethylhexyl methacrylate, alkyl methacrylates such as n-lauryl methacrylate, and the like, particularly n-butyl acrylate. It is preferable to use

Examples of polyfunctional alkyl (meth) acrylates include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate.
And 1,4-butylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate and the like. The amount of the polyfunctional alkyl (meth) acrylate used is 0.1 to 20% by weight, preferably 0.2 to 5% by weight in the alkyl (meth) acrylate component.
More preferably, it is 0.2 to 1% by weight.

The alkyl (meth) acrylate and polyfunctional alkyl (meth) acrylate may be used alone or in combination of two or more kinds.

The composite rubber comprising the polyorganosiloxane and the alkyl (meth) acrylate rubber according to the present invention is
It can be prepared by adding the above-mentioned alkyl (meth) acrylate component to the latex of the polyorganosiloxane component and polymerizing it by allowing a usual radical polymerization initiator to act. As a method of adding the alkyl (meth) acrylate, there are a method of mixing with the latex of the polyorganosiloxane component at once and a method of dropping it into the latex of the polyorganosiloxane component at a constant rate. Considering the impact resistance of the resulting resin composition containing the graft copolymer, a method of mixing the latex of the polyorganosiloxane component at once is preferable. As the radical polymerization initiator used for polymerization, a peroxide, an azo-based initiator, or a redox-based initiator in which an oxidizing agent and a reducing agent are combined is used. Among these, a redox type initiator is preferable, and a sulfoxylate type initiator obtained by combining ferrous sulfate / ethylenediaminetetraacetic acid with a sodium salt / longalide / hydroperoxide is particularly preferable.

In the composite rubber comprising the polyorganosiloxane and the alkyl (meth) acrylate rubber according to the present invention, the amount of polyorganosiloxane is 1 to 20% by weight and the amount of alkyl (meth) acrylate rubber is 80 to 9%.
When the amount of the polyorganosiloxane is less than 1% by weight, the impact resistance becomes low because the amount of polyorganosiloxane is small, and when the amount exceeds 20% by weight, the pigment of the resin composition molded article containing the graft copolymer is obtained. Poor coloring and low industrial value. In consideration of both impact resistance and pigment coloring of the resin composition containing the graft copolymer, the amount of polyorganosiloxane in the composite rubber is preferably 6 to 20% by weight, and the alkyl (meth) acrylate rubber is preferably The amount of
94% by weight, more preferably 10 to 20% by weight of polyorganosiloxane, and 80 to 90% by weight of the amount of alkyl (meth) acrylate rubber.

The graft copolymer according to the present invention is one or two selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds in the composite rubber produced by emulsion polymerization as described above. It can be produced by graft polymerization of the above monomers. Among the monomers used in the graft polymerization, the aromatic alkenyl compound is, for example, styrene, α-methylstyrene, vinyltoluene, etc., and the methacrylic acid ester is, for example, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl. Methacrylate and the like, acrylic ester such as methyl acrylate, ethyl acrylate, butyl acrylate, and the like, and vinyl cyanide compound such as acrylonitrile and methacrylonitrile.

In the graft polymerization, one or more monomers selected from an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester or a vinyl cyanide compound are added to a latex of a composite rubber, and one step is carried out by a radical polymerization technique. Although it can be carried out in multiple steps or in multiple steps, it is preferable to carry out the polymerization in two or more steps in consideration of impact resistance and pigment coloring of the resulting resin composition containing the graft copolymer.

The amount of one or more monomers selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds used in the graft polymerization depends on the weight of the resulting graft copolymer. It is 50 to 80% by weight based on the standard. If it is less than 50% by weight, the pigment coloring property of the resin composition molded article containing the graft copolymer is poor, and if it exceeds 80% by weight, the rubber amount becomes low and the impact resistance becomes low. It is not preferable because it is less effective. Further, in consideration of both impact resistance and pigment colorability of the resin composition containing the graft copolymer, it is selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds in the graft copolymer. The amount of one or more kinds of monomers is preferably 50 to 70% by weight, more preferably 50 to 60% by weight.

Further, various chain transfer agents for adjusting the molecular weight and graft ratio of the graft polymer can be added to the monomers used in the graft polymerization.

The particle size of the graft copolymer prepared as described above is not particularly limited, but both the impact resistance and the pigment coloring property of the resin composition containing the obtained graft copolymer are obtained. Considering that, the weight average particle size is 0.0
The thickness is preferably 7 to 0.2 μm, more preferably 0.10 to 0.15 μm.

After the graft polymerization is completed, the latex may be poured into hot water in which a metal salt such as calcium chloride or aluminum sulfate is dissolved, salted out and coagulated to separate and recover the graft copolymer. it can.

This graft copolymer can be extruded alone or together with a thermoplastic resin by an ordinary known kneading machine. Examples of such a molding machine include an extruder, an injection molding machine, a blow molding machine, a calendar molding machine and an inflation molding machine.

Further, the resin composition containing the graft copolymer may be blended with dyes, pigments, stabilizers, reinforcing agents, fillers, flame retardants, etc., if necessary.

The present invention will be described below with reference to examples. still,
In the Reference Examples, Examples and Comparative Examples, "parts" and "%" are "parts by weight" and "% by weight" unless otherwise specified.
Means

The weight average particle diameter of the polyorganosiloxane in the latex in the reference example and the weight average particle diameter of the graft copolymer in the latex in the examples were measured by using DLS-700 manufactured by Otsuka Electronics Co., Ltd. It was determined by the dynamic light scattering method.

The Izod impact strength in the examples and comparative examples was measured by the method according to ASTM D258.

The surface hardness (Rockwell hardness) in the examples and comparative examples was measured by the method according to ASTM D785.

In addition, the evaluation of the molding appearance of the resin compositions in Examples and Comparative Examples was carried out by using an injection molding machine IS-100EN manufactured by Toshiba Machine Co., Ltd. to mold 110 mm × 110.
By visually observing the surface of the mm x 3 mm plate, the pigment coloring property is J
Each was evaluated by a hue measurement according to IS Z8729.

[0057]

【Example】

Reference Example 1 Production of Polyorganosiloxane Latex L-1 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture. To this, 300 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added, and 10,000 parts were added using a homomixer.
After stirring for 2 minutes at rotation / minute, add 300 to the homogenizer.
It was passed once at a pressure of kg / cm ² to obtain a stable premixed organosiloxane latex.

On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device, and 1
A 0% by weight aqueous dodecylbenzenesulfonic acid solution was prepared.

With this aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the addition was completed, the temperature was maintained for 1 hour and cooled. The reaction was then neutralized with aqueous caustic soda.

The latex thus obtained was mixed with 17
When the solid content was determined by drying at 0 ° C. for 30 minutes, 17.
It was 7% by weight. The weight average particle diameter of the polyorganosiloxane in the latex was 0.05 μm.

Reference Example 2 Production of Polyorganosiloxane Latex L-2 99 parts of octamethylcyclotetrasiloxane and 1 part of γ-methacryloxypropyltrimethoxysilane were mixed to obtain 100 parts of a siloxane-based mixture. To this, 300 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added and stirred with a homomixer at 10,000 rpm for 2 minutes, and then 300 kg was added to a homogenizer.
It was passed once at a pressure of / cm ² to obtain a stable premixed organosiloxane latex.

On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device, and 1
A 0% by weight aqueous dodecylbenzenesulfonic acid solution was prepared.

With the aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour and cooled. The reaction was then neutralized with aqueous caustic soda.

The latex thus obtained was
When the solid content was determined by drying at 0 ° C. for 30 minutes, 18.
It was 2% by weight. The weight average particle diameter of the polyorganosiloxane in the latex was 0.05 μm.

Reference Example 3 Production of Polyorganosiloxane Latex L-3 In Reference Example 1, the amount of octamethylcyclotetrasiloxane used was 99.5 parts, and the amount of γ-methacryloxypropyldimethoxymethylsilane was 0.5 parts. A latex was prepared in the same manner as in Reference Example 1 except that it was changed. The solid content of the obtained latex was 18.0% by weight, and the weight average particle size of the polyorganosiloxane in the latex was 0.0.
It was 5 μm.

Reference Example 4 Production of Polyorganosiloxane Latex L-4 In Reference Example 1, the amount of octamethylcyclotetrasiloxane used was changed to 90 parts and the amount of γ-methacryloxypropyldimethoxymethylsilane was changed to 10 parts. A latex was prepared in the same manner as in Reference Example 1. The obtained latex had a solid content of 17.8% by weight, and the weight average particle diameter of the polyorganosiloxane in the latex was 0.05 μm.
Met.

Reference Example 5 Production of Polyorganosiloxane Latex L-5 In Reference Example 2, the amount of octamethylcyclotetrasiloxane used was changed to 95 parts, and the amount of γ-methacryloxypropyltrimethoxysilane was changed to 5 parts. Reference example 2
A latex was prepared in the same manner as in. The solid content of the obtained latex was 18.6% by weight, and the weight average particle diameter of the polyorganosiloxane in the latex was 0.05 μm.

Table 1 shows the preparation conditions and results of the polyorganosiloxane of the above reference example.

[0069]

[Table 1]

Example 1 Production of Graft Copolymer S-1 A polyorganosiloxane latex (L- was prepared in Example 1) was placed in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer. 1) 53.3 parts and 0.3 part of N-lauroylsarcosine sodium were collected, and 258.5 parts of distilled water was added and mixed, and then butyl acrylate 5 was added.
A mixture of 7 parts, 0.3 part of allyl methacrylate, 0.1 part of 1,3-butylene glycol dimethacrylate and 0.14 part of cumene hydroperoxide was added.

By passing a nitrogen stream through this reactor, the atmosphere was replaced with nitrogen, and the temperature was raised to 60.degree. When the temperature of the internal liquid reached 60 ° C, 0.001 of ferrous sulfate was added.
01 parts, ethylenediaminetetraacetic acid disodium salt 0.0
An aqueous solution prepared by dissolving 003 parts and 0.24 parts of Rongalid in 10 parts of distilled water was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a latex of a composite rubber of polyorganosiloxane and butyl acrylate rubber.

After the liquid temperature inside the reactor dropped to 60 ° C.,
An aqueous solution prepared by dissolving 0.4 parts of rongalid in 10 parts of distilled water was added, and then 12.9 parts of acrylonitrile, 38.8 parts of styrene and 0.1 part of cumene hydroperoxide.
23 parts of the mixed solution was added dropwise over 2 hours for polymerization. After the dropping, the temperature of 60 ° C was maintained for 1 hour, and then 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.23 parts of rongalid were dissolved in 10 parts of distilled water. An aqueous solution was added, and then a mixed solution of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.13 part of cumene hydroperoxide was added dropwise over 2 hours for polymerization. After dropping, the temperature is 60 ℃
After maintaining the state of 1 hour for 1 hour, it is cooled to form a composite rubber composed of polyoctanosiloxane and butyl acrylate rubber,
A latex of a graft copolymer obtained by graft-polymerizing an acrylonitrile-styrene copolymer was obtained. The weight average particle diameter of the graft copolymer in the latex determined by the dynamic light scattering method was 0.13 μm.

Next, 150 parts of an aqueous solution containing 7.5% by weight of aluminum sulfate was heated to 60 ° C. and stirred. 100 parts of the latex of the graft copolymer was gradually dropped into this and coagulated. Then, the precipitate was separated, washed and dried to obtain a graft copolymer.

53 parts of this graft copolymer and 47 parts of an acrylonitrile-styrene copolymer prepared by the suspension polymerization method were mixed using a Henschel mixer, and this mixture was placed in a degassing extruder heated to 230 ° C. It was supplied and kneaded to obtain pellets. The obtained pellets were molded into a test piece by an injection molding machine in which the cylinder temperature was 230 ° C and the mold temperature was 60 ° C. With this test piece, Izod impact strength and Rockwell hardness were measured.

The Izod impact value of 1/4 "thickness is 43
kgcm / cm, Rockwell hardness (R scale
Le) was 94.8.

Next, 53 parts of the graft copolymer, 47 parts of acrylonitrile-styrene copolymer prepared by the suspension polymerization method, and carbon black (Mitsubishi Kasei Co., Ltd.).
0.8 parts of CB-960 manufactured by the company) was mixed using a Henschel mixer, and this mixture was supplied to a degassing extruder heated to 230 ° C. and kneaded to obtain pellets. The obtained pellets were dimensioned by an injection molding machine in which the cylinder temperature was 230 ° C and the mold temperature was 60 ° C.
A mm plate was formed. The appearance of the obtained molded plate was very good with high gloss. Further, when the hue of the molded plate was measured, L ^* was 9.4 and the brightness was low, and the deep blackness was high, showing good pigment colorability.

Table 2 shows the results of the above evaluations.

[0078]

[Table 2]

Example 2 Production of Graft Copolymer S-2 Using the polyorganosiloxane latex (L-2) obtained in Reference Example 2, the same composite rubber reaction and graft copolymer as in Example 1 were carried out. Was prepared. The weight average particle size of the graft copolymer in the obtained latex is
It was 0.13 μm.

Then, the obtained graft copolymer and a mixture of acrylonitrile-styrene copolymer prepared by the suspension polymerization method were extruded and molded to obtain a test piece. The Izod impact strength was 43.7 kgcm / cm, and the Rockwell hardness (R scale) was 94.0.

Further, as in Example 1, carbon black was added and extrusion / molding was carried out to obtain a molded plate for appearance evaluation. The appearance of the obtained molded plate was very good with high gloss. Further, when the hue of the molded plate was measured, it was found that L ^*
Had a low brightness of 9.5 and a high deep blackness, and exhibited good pigment colorability.

Table 2 shows the above evaluation results.

Comparative Examples 1 to 3 Graft Copolymer T-1 to
Using the polyorganosiloxane latexes (L-3 to 5) obtained in Production Reference Examples 3 to 5 of Example 3, the same composite rubber reaction as in Example 1 and the preparation of the graft copolymer were carried out. The obtained graft copolymer and the mixture of acrylonitrile-styrene copolymer prepared by the suspension polymerization method were extruded and molded to obtain a test piece.

Further, as in Example 1, carbon black was added and extrusion / molding was carried out to obtain a molded plate for appearance evaluation. Table 2 shows the Izod impact strength, Rockwell hardness, molding appearance of the black colored molded product, and pigment coloring property evaluation results of the mixture of each graft copolymer and acrylonitrile-styrene copolymer.

Comparative Example 4 Preparation of Graft Copolymer T-4 In Example 1, the amount of polyorganosiloxane latex (L-1) charged into the reactor was 105 parts, the amount of distilled water was 216 parts, and butyl acrylate. Except that the allyl methacrylate was changed to 47.9 parts, the allyl methacrylate was changed to 0.2 part, the 1,3-butylene glycol dimethacrylate was changed to 0.1 part, and the cumene hydroperoxide was changed to 0.12 part. A graft copolymer was produced in the same manner as in Example 1. Extruding the obtained graft copolymer and a mixture of acrylonitrile-styrene copolymer prepared by the suspension polymerization method
Molding was performed to obtain a test piece.

Further, as in Example 1, carbon black was added and extrusion and molding were carried out to obtain a molded plate for appearance evaluation.

Each graft copolymer and acrylonitrile-
Table 2 shows the Izod impact strength, the Rockwell hardness of the mixture of styrene copolymers, the molding appearance of the black colored molded product, and the pigment coloring property evaluation results.

Comparative Example 5 Preparation of Graft Copolymer T-5 In Example 1, the amount of polyorganosiloxane latex (L-1) charged into the reactor was 70 parts, the amount of distilled water was 245 parts, and butyl acrylate. Content of 76.2 parts, allyl methacrylate of 0.3 parts, 1,3-butylene glycol dimethacrylate of 0.2 parts and cumene hydroperoxide of 0.19 parts. The amount of acrylonitrile used in the second step was changed to 7.4 parts, the amount of styrene was changed to 22.2 parts, and the amount of cumene hydroperoxide was changed to 0.13 parts. Was manufactured.

A mixture of the obtained graft copolymer and the acrylonitrile-styrene copolymer prepared by the suspension polymerization method was extruded and molded to obtain a test piece. Further, as in Example 1, carbon black was added and extrusion / molding was carried out to obtain a molded plate for appearance evaluation. Table 2 shows the Izod impact strength, Rockwell hardness, molding appearance of the black colored molded product, and pigment coloring property evaluation results of the mixture of each graft copolymer and acrylonitrile-styrene copolymer.

From the examples and comparative examples, the following facts have become clear.

1) The resin compositions containing the graft copolymers of Examples 1 and 2 show high Izod impact strength and surface hardness, and at the same time show excellent molding appearance and pigment colorability by injection molding.

2) Since the resin composition containing the graft copolymer of Comparative Example 1 contains a large amount of polyorganosiloxane which is not complexed with butyl acrylate rubber, it is molded by bleeding out on the surface of the injection molded product. It is not preferable because it deteriorates the design of the product.

3) The resin composition containing the graft copolymer of Comparative Example 2 or Comparative Example 3 is not preferable because it has a low Izod impact strength and cannot be used as an industrial material.

4) The resin composition containing the graft copolymer of Comparative Example 4 or Comparative Example 5 had an L ^* value of 1 for a black colored molded article.
Since it exceeds 0.0, it cannot be used in applications requiring high pigment coloring such as automobile exteriors and household appliances housings, which is not preferable.

[0095]

As described above, the present invention has the following particularly remarkable effects and its industrial utility value is extremely large.

1) The resin composition containing the graft copolymer according to the present invention has an excellent balance of impact resistance, surface hardness and molding appearance, and pigment colorability.

2) Especially, the Izod impact strength shows a very high value which cannot be obtained by the resin material using the conventionally known acrylate rubber as a rubber source, and its utility value as various industrial materials is extremely high.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-5-279434 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 291 / 02,283 / 12 C08L 25/12 C08L 51/00

Claims (2)

(57) [Claims] 1. A composition comprising (A) 0.2 to 3 mol% of a siloxane unit containing a vinyl-polymerizable functional group and 97 to 99.8 mol% of a dimethylsiloxane unit, wherein the silicon atom having 3 or more siloxane bonds is poly. A composite rubber comprising polydimethylsiloxane, which is 1 mol% or less based on all silicon atoms in dimethylsiloxane, and (B) an alkyl (meth) acrylate rubber,
(C) A graft copolymer in which one or more monomers selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds are graft-polymerized, wherein 1 to 20% by weight of siloxane (A), 80 to 99% by weight of alkyl (meth) acrylate rubber (B), and 50 to 8 of graft component (C) based on all graft copolymers.
A graft copolymer containing 0% by weight. 2. A composition comprising (A) 0.2 to 3 mol% of a vinyl-polymerizable functional group-containing siloxane unit and 97 to 99.8 mol% of a dimethylsiloxane unit, wherein the silicon atom having 3 or more siloxane bonds is poly. A composite rubber comprising (B) an alkyl (meth) acrylate rubber and polydimethylsiloxane, which is 1 mol% or less based on all silicon atoms in dimethylsiloxane, and
(C) A graft copolymer obtained by graft-polymerizing one or more monomers selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters, or vinyl cyanide compounds, wherein 1 to 20% by weight of siloxane (A), 80 to 99% by weight of alkyl (meth) acrylate rubber (B), and 50 to 8 of graft component (C) based on all graft copolymers.
A thermoplastic resin composition comprising 0% by weight of a graft copolymer and an acrylonitrile-styrene copolymer.