JPH06157889A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in impact resistance and pigmentability. CONSTITUTION:This resin composition is prepared by mixing a resin composition comprising a graft copolymer prepared by grafting at least one vinyl monomer onto a composite rubber comprising apolyorganosiloxane component and an alkyl (meth)acrylate rubber component and having a number-mean particle diameter of 0.01-0.07mum and a ratio of the total volume of particles of diameters of 0.10mum or larger to the total particle volume of 20% or below and a polycarbonate resin with optionally a polyester resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin-based resin composition excellent in impact resistance and pigment coloring.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as thermoplastic resins having excellent heat resistance and impact resistance. However, polycarbonate resin has a structure of -20 ° C.
Its use is limited because of its low impact resistance at low temperatures and the large difference in impact resistance depending on the wall thickness of the molded product. Therefore, various methods have been conventionally proposed in order to improve this drawback. For example, a method of blending a polycarbonate resin with an ABS resin is disclosed in JP-B-38-152.
No. 25, Japanese Patent Publication No. 55-27579, Japanese Patent Publication No. 58-46269, Japanese Patent Publication No. 58-149938.

However, the above polycarbonate resin and AB
By the method of blending with S resin, it is possible to balance the impact strength and heat resistance of the obtained resin composition, but the original excellent weather resistance of the polycarbonate resin is deteriorated and the heat stability is inferior. Have a point.

Therefore, Japanese Patent Application Laid-Open No. 64-79257 discloses that a composite rubber composed of a polyorganosiloxane rubber and a poly (meth) acrylic rubber is used as a vinyl-based monomer in order to improve weather resistance and impact resistance. A resin composition of a composite rubber-based graft copolymer obtained by graft-polymerizing a polymer and a polycarbonate resin has been proposed. Further, Japanese Patent Application Laid-Open No. 1-230664 discloses a resin composition of a composite rubber graft copolymer, a polycarbonate resin and a polyester resin.

[0005]

SUMMARY OF THE INVENTION
When the composite rubber-based graft copolymers disclosed in 64-79257 and Japanese Patent Application Laid-Open No. 1-230664 are used as the rubber component of the impact resistant resin, the particle diameter of the rubber component is larger than 0.08 μm. However, the coloring property of the polycarbonate resin composition when the pigment was added was poor and the industrial value was low. Therefore, it has been strongly desired to develop an impact-resistant resin which has good impact resistance and is excellent in colorability when a pigment is added.

[0006]

Means for Solving the Problems The inventors of the present invention have made earnest studies on the relationship between the particle size of the graft copolymer and the coloring property when a pigment is added, and as a result, surprisingly, it was found that a polymer having a small particle size is used. When a composite rubber having a fine particle size of a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber is produced using an organosiloxane, a resin composition composed of a graft composite rubber and a polycarbonate resin obtained from this composite rubber is obtained. The present invention has been accomplished by finding that they exhibit excellent impact resistance and at the same time exhibit good pigment coloring.

That is, the gist of the present invention is that the composite rubber comprising a polyorganosiloxane component and an alkyl (meth) acrylate rubber component is graft-polymerized with one or more vinyl monomers to obtain a number average particle diameter. Is 0.01 ~
A resin composition comprising a graft composite rubber (A) having a volume of particles of 0.07 μm and larger than 0.10 μm of 20% or less of the total particle volume and a polycarbonate resin (B). Further, the present invention further relates to a polyester resin (C)
And a resin composition obtained by mixing.

The graft composite rubber (A) of the present invention has a number average particle diameter in the range of 0.01 to 0.07 μm, and is 0.10.
The volume of particles larger than μm is 20% or less of the volume of all graft composite rubber particles. Number average particle size is 0.01μm
If it is smaller, the impact resistance of the molded product obtained from the graft composite rubber (A) and the polycarbonate resin (B), or the molded product obtained from the polyester resin (C) is deteriorated. If the number average particle size is larger than 0.07 μm, the size of the particles is close to the wavelength range of visible light, and light scattering by the particles becomes large, so that the pigment coloring property of the molded product deteriorates. The volume of particles larger than 0.01 μm is preferably 10% or less.

The graft composite rubber of the present invention has a structure in which a vinyl monomer is graft-polymerized onto the composite rubber in a state in which the polyorganosiloxane component and the polyalkyl (meth) acrylate rubber component cannot be substantially separated. belongs to. This composite rubber can take various forms, such as a mixture in which both components are almost uniformly mixed and dispersed, a form in which a polyalkyl (meth) acrylate rubber component is dispersed in a polyorganosiloxane in a salami structure, The organosiloxane and the polyalkyl (meth) acrylate may have a layered form or the like, and these forms may be appropriately mixed. As an example of the layered morphology, a polyalkyl (meth) acrylate is used as a core, and a first layer of polyorganosiloxane and a second layer of polyalkyl (meth) acrylate are present on the core, or a polyorganosiloxane is used as a core. A form in which a first layer of polyalkyl (meth) acrylate and a second layer of polyorganosiloxane are present on the top surface is mentioned.

In the present invention, as the raw material of the polyorganosiloxane, for example, a mixture of diorganosiloxane and a siloxane-based graft crossing agent or a mixture of a siloxane-based crosslinking agent is used. The mixture is emulsified with an emulsifier and water, and the latex is atomized using a homomixer that atomizes by a shearing force by high-speed rotation or a homogenizer that atomizes by a jet output from a high-pressure generator, and then hot dodecyl A polyorganosiloxane can be obtained by dropping the solution into an aqueous solution of benzenesulfonic acid at a constant rate for polymerization and then neutralizing dodecylbenzenesulfonic acid with an alkaline substance. The size of the polyorganosiloxane is not particularly limited, but the number average particle size is 0.003 to 0.06 μm and 0.10 μ
It is preferred that the volume of the larger particles be 20% or less of the total particle volume. Such a polyorganosiloxane having a small size and a narrow particle size distribution is polymerized by dropping a finely divided latex into an aqueous solution of an acid catalyst such as dodecylbenzenesulfonic acid having a low concentration of 50 ° C. or higher at a minute speed. Can be obtained by

Examples of the organosiloxane that constitutes the organosiloxane mixture include various organosiloxane cyclic compounds having three or more membered rings, and those having 3 to 6 membered rings are preferable. Specifically, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, etc. These may be used alone or in admixture of two or more. The amount of these used is 50% by weight or more, preferably 70% by weight or more, in the organosiloxane mixture.

As the siloxane-based crosslinking agent, a trifunctional or tetrafunctional silane-based crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra Butoxysilane or the like is used.
In particular, a tetrafunctional crosslinking agent is preferable, and among these, tetraethoxysilane is most preferable. The amount of the cross-linking agent used is 0 to 30% by weight, preferably 0.5 to 10% by weight in the organosiloxane mixture.

As the siloxane-based graft crossing agent, compounds capable of forming a unit represented by the following formula are used.

[0014]

[Chemical 1]

In the above formula, R ¹ is a methyl group, an ethyl group, a propyl group or a phenyl group, R ² is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is a number from 1 to 6. .

A unit of formula (I-1) may be formed (meta).
Acryloyloxysiloxane has a high grafting efficiency and thus can form an effective graft chain, and is advantageous in that it exhibits impact resistance. Methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of formula (I-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl. Examples thereof include ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and δ-methacryloyloxybutyldiethoxymethylsilane.

Vinyl siloxanes are mentioned as those capable of forming the unit of the formula (I-2), and specific examples thereof include tetramethyltetravinylcyclotetrasiloxane. As those capable of forming the unit of formula (I-3),
p-vinylphenylmethyldimethoxysilane, 2- (p
-Vinylphenyl) ethylmethyldimethoxysilane, 3
Examples thereof include-(p-vinylbenzoyloxy) propylmethyldimethoxysilane. Examples of the unit that can form the unit of formula (I-4) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, and γ-mercaptopropyldiethoxymethylsilane.

The amount of the graft crossing agent used in the organosiloxane mixture is 10% by weight or less, preferably 0.5 to 5% by weight.

As the emulsifier, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium laurylsulfonate, sodium sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfate, etc. is used.
Particularly, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

These emulsifiers are used in the range of 0.5 to 30 parts based on 100 parts of the organosiloxane mixture. If it is less than 0.5 part, the dispersed state becomes unstable and the emulsified state of a fine particle size cannot be maintained. On the other hand, if the amount exceeds 30 parts, the coloring of the obtained polyorganosiloxane due to the emulsifier becomes extremely large, which is inconvenient.

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

Alkyl (meth) acrylates include
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Alkyl acrylates such as ethylhexyl acrylate and hexyl methacrylic acid, alkyl methacrylic acid such as 2-ethylhexyl methacrylic acid, n-lauryl methacrylic acid and the like, and particularly n- The use of butyl acrylate is preferred.

Examples of polyfunctional alkyl (meth) acrylates include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,4-butylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate and the like can be mentioned. The amount of the polyfunctional alkyl (meth) acrylate used is 0.1 to 20 in the alkyl (meth) acrylate component.
%, Preferably 0.5 to 10% by weight.

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

The above alkyl (meth) acrylate component is added to the latex of the neutralized polyorganosiloxane rubber component, and the usual radical polymerization initiator is allowed to act to polymerize. As the polymerization initiator, a peroxide, an azo initiator, or a redox 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 in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined is particularly preferable.

As the polymerization proceeds, the polyorganosiloxane component and the polyalkyl (meth) acrylate rubber are
A latex of a composite rubber of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component which are practically inseparable is obtained.

In the composite rubber composed of the polyorganosiloxane and the polyalkyl (meth) acrylate rubber of the present invention, the polyorganosiloxane component is 1 to 9
It is about 0% by weight. If it is less than 1% by weight, the characteristics of polyorganosiloxane cannot be exhibited and the impact resistance is lowered.
On the other hand, when it exceeds 90% by weight, the gloss derived from polyorganosiloxane is lowered and the pigment colorability is also lowered.

In the practice of the present invention, octamethyltetracyclosiloxane is used as the dialkylorganosiloxane, tetraethoxysilane is used as the siloxane crosslinking agent, and γ-methacryloyloxypropyldimethoxymethylsilane is used as the siloxane grafting agent. It is preferable to use a composite rubber obtained by compounding a polyalkyl (meth) acrylate rubber component having a repeating unit of n-butyl acrylate as a main skeleton with the obtained polyorganosiloxane rubber.

The composite rubber thus produced by emulsion polymerization can be graft-copolymerized with a vinyl monomer, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component can be used. Are strongly entangled with each other, and cannot be extracted and separated with a normal organic solvent such as acetone or toluene. The gel content measured by extracting this composite rubber with toluene at 90 ° C. for 12 hours is preferably 80% by weight or more.

As the vinyl-based monomer to be graft-polymerized on the composite rubber, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methacrylates such as methylmethacrylate and 2-ethylhexylmethacrylate. Acid ester; acrylic acid ester such as methyl acrylate, ethyl acrylate, butyl acrylate;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; epoxy group-containing vinyl compounds such as glycidyl methacrylate; various vinyl-based monomers such as carboxylic acid group-containing vinyl compounds such as methacrylic acid. Are used alone or in combination of two or more.

The ratio of the composite rubber and the vinyl-based monomer in obtaining the graft composite rubber of this composite rubber is 10 to 95% by weight of the composite rubber based on the weight of the obtained graft composite.
Preferably 20 to 90% by weight, and vinyl monomer 90
It is about 5 to 5% by weight, preferably about 80 to 10% by weight.
If the vinyl-based monomer is less than 5% by weight, the dispersion of the graft composite rubber component in the resin composition mixed with other resin is not sufficient, and if it exceeds 90% by weight, the impact strength tends to decrease. It is not preferable because it exists.

The graft composite rubber (A) can be obtained by adding a vinyl-based monomer to the latex of the composite rubber and polymerizing it in a single stage or multiple stages by a radical polymerization technique.

After the graft polymerization is completed, the latex can be separated and recovered by introducing the latex into hot water in which a metal salt such as calcium chloride or aluminum sulfate is dissolved, and salting out and coagulating. .

In the present invention, the polycarbonate resin (B) used is one produced by a known method. That is, a transesterification reaction between a diester of carbonic acid obtained from a monofunctional aromatic or aliphatic hydroxy compound and a dihydroxy compound, an ester of a dihydroxy compound with itself or with a bisalkyl of another dihydroxy compound, or a bisallylcarbonate. An exchange reaction, a reaction of a dihydroxy compound and phosgene in the presence of an oxygen binder, and a production method by a reaction of a dihydroxy compound and a bischlorocarbonic acid ester of a dihydroxy compound in the presence of an oxygen binder can be mentioned. Typically, there is a production method in which bisphenol A is reacted with carbonyl chloride in the presence of an oxygen binder and a solvent.

The polyester resin (C) used in the present invention includes aromatic dicarboxylic acids or aliphatic dicarboxylic acids having 8 to 22 carbon atoms and alkylene glycols, cycloalkylene glycols or aralkylenes having 2 to 22 carbon atoms. It is composed of glycol, and may optionally contain a subordinate amount of an aliphatic dicarboxylic acid such as adipic acid or sebacic acid. It may also contain polyalkylene glycol such as polyethylene glycol and polytetramethylene glycol. The thermoplastic polyesters may be used alone or in combination of two or more. Particularly preferred polyesters include polyethylene terephthalate and polytetramethylene terephthalate. By using the thermoplastic polyester (C), the chemical resistance of the resin composition can be greatly improved.

The composition of the graft composite rubber (A), the polycarbonate resin (B) and the thermoplastic polyester resin (C) in the resin composition of the present invention is not particularly limited, but based on the weight of the entire resin composition. Ingredient (A) is 1
It is preferable that the component (B) is 99 to 50% by weight and the component (C) is 0 to 60% by weight. When the content of the component (A) is less than 1% by weight, the impact resistance improving effect of the polycarbonate resin composition is insufficient, and when it exceeds 50% by weight, the mechanical strength of the polycarbonate resin composition decreases.

The resin composition of the present invention can be obtained by kneading the component (A) and the component (B) or further the component (C) by an ordinary known kneading machine and extrusion molding. For such machines, mixing rolls,
Examples include calender rolls, Banbury mixers, extruders, injection molding machines, blow molding machines, and inflation molding machines. Dyes, pigments, stabilizers, reinforcing agents, glass fibers, fillers, flame retardants and the like can be added to the resin composition of the present invention as required.

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

In the Reference Example, the particle size of the polyorganosiloxane in the latex was measured by the dynamic light scattering method.
This measurement is a method that utilizes the Brownian motion of particles in latex. When the particles in the latex are irradiated with laser light, they show fluctuations according to the particle diameters, so the particle diameters can be calculated by analyzing these fluctuations. The number average particle size and the particle size distribution were determined using a DLS-700 type manufactured by Otsuka Electronics Co., Ltd.

The swelling degree and gel content of the crosslinked polyorganosiloxane were measured by the following method using polyorganosiloxane obtained by dropping latex into isopropanol, coagulating and drying. That is, the degree of swelling was determined as a value obtained by dividing the weight of toluene occluded by the polyorganosiloxane when the polyorganosiloxane was immersed in toluene at 23 ° C. for 48 hours by the weight of the polyorganosiloxane before immersion. The gel content was determined by extracting polyorganosiloxane in toluene at 23 ° C. for 48 hours.

In the examples, the Izod impact strength is
Measured according to ASTM D 258 (with 1/4 "notch).
The surface hardness was measured by ASTM D785 (Rockwell hardness). Gloss was measured according to ASTM D 523-62 (60 ° specular gloss). Pigment colorability is JIS Z 8729
(L ^* a ^* b ^* object color display method by color system).

The number average particle size of the graft composite rubber and 0.10
The volume fraction of particles of μm or more was determined by observing an ultrathin section sample with a transmission electron microscope. This ultrathin section sample was melt-mixed in an extruder with 90 parts of polymethylmethacrylate and 10 parts of graft composite rubber to form pellets,
The pellets were cut from a press-molded test piece using a microtome.

Reference Example 1 Production of polyorganosiloxane rubber latex SiL-1: 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxyxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed,
100 parts of siloxane mixture are obtained. 300 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added to this, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes, and then homogenized at a pressure of 300 kg / cm ² for 2 minutes.
It was passed around to obtain a stable premixed organosiloxane latex. On the other hand, 10 parts of dodecylbenzenesulfonic acid and 9 parts of distilled water were placed in a separable flask equipped with a cooling condenser.
0 parts was injected to prepare a 10 wt% dodecylbenzenesulfonic acid aqueous solution.

With the aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 2 hours, and after the completion of the addition, the temperature was maintained for 3 hours and cooled. The reaction was then kept at room temperature for 12 hours before caustic soaking.
The polymerization was completed by neutralizing with a da water solution to obtain polyorganosiloxane rubber latex SiL-1.

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 degree of swelling of this latex is 15.
6, the gel content was 87.6%, and the number average particle size was 0.
Volume fraction of particles larger than 03μm and 0.10μm is 6.8%
Met.

Reference Example 2 Production of Grafted Composite Rubber Gf-1: 54.9 parts of the latex SiL-1 obtained in Reference Example 1 was collected,
Place in a separable flask equipped with a stirrer and add distilled water 17
After adding 0 part, a mixed solution of 58.8 parts of butyl acrylate, 1.2 parts of allyl methacrylate and 0.12 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes to impregnate the polyorganosiloxane rubber particles. .
Nitrogen was replaced by passing a nitrogen stream through the separable flask, and the temperature was raised to 60 ° C. When the temperature of the solution reached 60 ° C, 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalit were dissolved in 10 parts of distilled water to add radical polymerization. Started. The liquid temperature rose to 82 ° C. due to the polymerization of the butyl acrylate mixed liquid. This state was maintained for 1 hour to complete the polymerization of butyl acrylate to obtain a composite rubber latex. After the liquid temperature dropped to 75 ° C, a mixed liquid of 0.12 parts of tert-butylhydroperoxide and 30 parts of methyl methacrylate was added dropwise to this composite rubber latex over 15 minutes, and then the mixture was kept at 70 ° C for 4 hours to obtain a composite rubber. The graft polymerization to was completed.

The obtained graft composite rubber latex was gradually dropped into 200 parts of water (25 ° C.) containing 1.5% by weight of calcium chloride for coagulation, and then heated to 90 ° C. to be solidified. Then, the coagulated product is separated from the liquid, and after washing,
After drying at 75 ° C. for 16 hours, 96.8 parts of a dry powder of the graft composite rubber Gf-1 was obtained. The number average particle diameter of this graft composite rubber was 0.05 μm, and the volume fraction of particles larger than 0.10 μm was 5.6%.

Reference Examples 3 to 5 Grafted composite rubber Gf-
2, Gf-3 and grafted silicone rubber Gs-4
Production of (for Comparative Example): The graft composite rubber Gf was prepared in the same manner as in Reference Example 2 except that the composition ratio of the latex SiL-1 to butyl acrylate (BA) and allyl methacrylate (AMA) was changed to the values shown in Table 1.
-2, Gf-3, and graft silicone rubber Gs-4
Got

Reference Example 6 Production of Grafted Composite Rubber Gf-5: 39.2 parts of the latex SiL-1 obtained in Reference Example 1 was sampled and placed in a separable flask equipped with a stirrer, and 182 parts of distilled water was added. After addition, 42.0 parts of butyl acrylate,
Charge a mixed solution of 0.86 part of allyl methacrylate and 0.2 part of tert-butyl hydroperoxide,
The polyorganosiloxane rubber particles were impregnated with stirring for a minute. Nitrogen was passed through the separable flask to replace the nitrogen, and the temperature was raised to 60 ° C. Liquid temperature is 60 ℃
When 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of distilled water, an aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 82 ° C. due to the polymerization of the butyl acrylate mixed liquid. This state was maintained for 1 hour to complete the polymerization of butyl acrylate to obtain a composite rubber latex. After the liquid temperature dropped to 75 ° C., a mixed liquid of 0.12 parts of tert-butyl hydroperoxide and 50 parts of methyl methacrylate was added to this composite rubber latex 25 times.
The mixture was added dropwise over a period of minutes and then kept at 70 ° C. for 4 hours to complete the graft polymerization on the composite rubber.

The obtained latex of the graft composite rubber was coagulated, separated, washed and dried in the same manner as in Reference Example 2 to obtain 96.3 parts of a dry powder of the graft composite rubber Gf-5. The number average particle size of this graft composite rubber is 0.05 μm,
The volume fraction of particles larger than μm was 6.1%.

Reference Example 7 Production of Grafted Composite Rubber Gf-6: 70.6 parts of the latex SiL-1 obtained in Reference Example 1 was sampled and put in a separable flask equipped with a stirrer, and 121 parts of distilled water was added. After addition, 75.6 parts of butyl acrylate,
Charge a mixed solution of 1.54 parts of allyl methacrylate and 0.2 parts of tertiary butyl hydroperoxide, and add 30 parts.
The polyorganosiloxane rubber particles were impregnated with stirring for a minute. Nitrogen was replaced by passing a nitrogen stream through the separable flask, and the temperature was raised to 60 ° C. Liquid temperature is 60
When the temperature reached ℃, 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, and 0.24 part of Rongalit were dissolved in 10 parts of distilled water, and an aqueous solution was added to initiate radical polymerization. . The liquid temperature rose to 84 ° C. due to the polymerization of the butyl acrylate mixed liquid. This state was maintained for 1 hour to complete the polymerization of butyl acrylate to obtain a composite rubber latex. After the liquid temperature dropped to 75 ° C, a mixed liquid of 0.12 parts of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was added to the composite rubber latex.
Drop over 25 minutes, then hold at 70 ° C for 4 hours,
The graft polymerization on the composite rubber was completed.

The obtained graft composite rubber latex was coagulated, separated, washed and dried in the same manner as in Reference Example 2 to obtain 95.5 parts of a dry powder of the graft composite rubber Gf-6. The number average particle diameter of this graft composite rubber is 0.03 μm,
The volume fraction of particles larger than μm was 2.1%.

Reference Example 8 Production of polyorganosiloxane rubber latex SiL-2: 2.0 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 98.0 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. (A system using no siloxane-based crosslinking agent). To this, 300 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added and treated with a homomixer and a homogenizer in the same manner as in Reference Example 1 to obtain a stable premixed organosiloxane latex. In the same manner as in Reference Example 1 below, the premixed latex was dropped into a high temperature aqueous solution of dodecylbenzenesulfonic acid to polymerize. In this reference example, after the premixed latex was dropped, the temperature was kept high for 3 hours, then cooled to room temperature and immediately neutralized with a caustic soda aqueous solution to obtain polyorganosiloxane latex SiL-2.

The latex thus obtained had a solid content of 18.0% by weight, and the polyorganosiloxane rubber had a number average particle size of 0.03 μm and a volume fraction of particles larger than 0.1 μm was 7.1%. there were.

Reference Example 9 Production of Grafted Composite Rubber Gf-7: The grafted composite rubber Gf-7 (99.1) was prepared in the same manner as in Reference Example 2 except that the latex SiL-2 obtained in Reference Example 8 was used.
Part). The number average particle size of this graft composite rubber is 0.
The particle size was 05 μm, and the volume fraction of particles larger than 0.10 μm was 6.3%.

Reference Example 10 Production of polyorganosiloxane rubber latex SiL-3 (for comparative example): 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane. Were mixed to obtain 100 parts of a siloxane mixture. Dodecylbenzene sulfonic acid 4 parts and dodecyl benzene sulfonic acid sodium 2
10 parts of the above-mentioned mixed siloxane in 200 parts of distilled water
Add 0 parts of the mixture, carry out preliminary dispersion with a homomixer and emulsification / dispersion with a homogenizer, heat at 80 ° C for 5 hours, then cool, let stand at 20 ° C for 48 hours, then adjust the pH to 7.0 with an aqueous sodium hydroxide solution. After the completion of the polymerization, the polymerization was completed to obtain polyorganosiloxane latex SiL-3. The polymerization rate of this polyorganosiloxane rubber was 89.6%, the average particle size was 0.05 μm, and the volume fraction of particles larger than 0.1 μm was 6%.
It was 7.3%.

Reference Example 11 Production of Grafted Composite Rubber Gf-8 (for Comparative Example): Grafted composite rubber Gf-8 (97) was used in the same manner as in Reference Example 2 except that the latex SiL-3 obtained in Reference Example 10 was used. .1
Part). The number average particle size of this graft composite rubber is 0.
07 μm, and the volume fraction of particles larger than 0.10 μm is 2
It was 7.2%.

Reference Example 12 Production of Grafted Composite Rubber Gf-9 (for Comparative Example) Polyorgano was prepared in the same manner as in Reference Example 9 except that sodium dodecylbenzene sulfonate and dodecylbenzene sulfonic acid were changed to 0.67 parts. Siloxane rubber latex SiL-4 was obtained. The obtained polyorganosiloxane rubber had a polymerization rate of 89.7% and a number average particle diameter of 0.16μ.
It was m.

33.4 parts of this latex SiL-4 was sampled, placed in a separable flask equipped with a stirrer, 191.6 parts of distilled water was added, and after nitrogen substitution, the temperature was raised to 60 ° C. A mixed solution of 58.8 parts of acrylate, 1.2 parts of allyl methacrylate, and 0.3 part of tertiary butyl hydroperoxide was charged and stirred for 30 minutes, and the mixed solution was impregnated into polyorganosiloxane rubber particles. Next, 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, Rongalit.
An aqueous solution prepared by dissolving 26 parts in 10 parts of distilled water was added to initiate radical polymerization, and then the internal temperature was maintained at 82 ° C. for 1 hour to complete the polymerization to obtain a composite rubber latex. Liquid temperature is 75
After the temperature was lowered to 0 ° C, a mixed solution of 0.12 parts of tert-butyl hydroperoxide and 30 parts of methyl methacrylate was added dropwise to this composite rubber latex over 25 minutes.
The temperature was maintained at 70 ° C for 4 hours to complete the graft polymerization on the composite rubber.

The obtained latex of the graft composite rubber was coagulated, separated, washed and dried in the same manner as in Reference Example 2 to obtain 95.4 parts of a dry powder of the graft composite rubber Gf-9. The number average particle diameter of this graft composite rubber is 0.25 μm,
The volume fraction of particles larger than μm was 93.4%.

Reference Example 13 Grafted acrylic rubber Ga-
Production of 10 (for Comparative Example): In a separable flask equipped with a stirrer, distilled water 215 was added.
Parts, 1.0 part of sodium dodecylbenzene sulfonate and then a mixed solution of 68.6 parts of butyl acrylate, 1.4 parts of allyl methacrylate, and 0.2 parts of tertiary butyl hydroperoxide were charged, and the separable flask was charged. Perform nitrogen replacement by passing a nitrogen stream through the
The temperature was raised to 0 ° C. When the liquid temperature reached 60 ° C, 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, and 0.24 part of Rongalit were added to 1 part of distilled water.
An aqueous solution dissolved in 0 part was added to initiate radical polymerization. Liquid temperature is 8 due to polymerization of butyl acrylate mixture.
It rose to 4 ° C. This state was maintained for 1 hour to complete the polymerization of butyl acrylate to obtain an acrylic rubber latex. After the liquid temperature dropped to 75 ° C, te was added to this latex.
A mixed solution of 0.12 parts of rt-butylhydroperoxide and 30 parts of methyl methacrylate was added dropwise over 25 minutes, and then the mixture was kept at 70 ° C for 4 hours to complete the graft polymerization on the acrylic rubber.

The obtained graft acrylic rubber latex was coagulated, separated, washed and dried in the same manner as in Reference Example 2 to obtain 96.5 parts of a dry powder of the graft acrylic rubber Ga-10. The number average particle diameter of this graft rubber was 0.31 μm, and the volume fraction of particles larger than 0.10 μm was 92.6%.

Examples 1 to 10 and Comparative Examples 1 to 4 Novarex 7022A (Mitsubishi Kasei Co., Ltd.) as a polycarbonate resin and the graft rubbers Gf-1 obtained in Reference Examples 2 to 7, 9 and 11 to 13. ~ Gf-9, Gs-4, Ga-
10 and 10 were mixed at a ratio shown in Table 2, and 0.5 part of carbon black (MCF88 manufactured by Mitsubishi Kasei Co., Ltd.) was further mixed.
This was supplied to a 30 m / mφ twin-screw extruder (ZSK-30 type manufactured by Werner Faudler), melt-kneaded at a cylinder temperature of 260 ° C., and shaped into pellets. The obtained pellets are dried and then injection molding machine (Sumitomo Heavy Industries Ltd. Promat
165/75 type) cylinder temperature 250 ℃, mold temperature 60
Various evaluation test pieces were obtained by injection molding at ℃. The results of evaluation using this test piece are shown in Table 2.

When the L ^* value for colorimetry in the table is about 10, the pigment coloring property is judged to be good, and about 10 to 15 is a range having practical coloring performance. If the L ^* value is more than this, the coloring property will be poor, and if it is 18 or more, it will be unpractical.

As is clear from the results of Examples 1 to 3, the graft composite rubber produced in Reference Example 2 exhibits high impact strength when mixed with a polycarbonate resin, and when colored with carbon black. It showed a good pigment colorability. Also, even if the ratio of the polyorganosiloxane rubber and the polybutyl acrylate rubber in the graft composite rubber is changed over a wide range as shown in Examples 4 to 5 (Gf-2, Gf-3), good performance is obtained. Was confirmed. However, the grafted silicone rubber Gs- of Comparative Example 1
4 and the graft acrylic rubber Ga-10 of Comparative Example 4
In the case of, the impact resistance and pigment color development were poor.

From the results of Examples 6 to 7, it was found that good impact resistance and mechanical strength were exhibited even if the amount of the vinyl-based monomer graft-polymerized on the composite rubber was changed. Example 8
From the results of Nos. 10 to 10, it was found that the resin composition obtained by mixing the graft composite rubber not using the siloxane-based cross-linking agent and the polycarbonate resin also exhibits good impact resistance and pigment coloring property.

However, in the case of the graft composite rubber Gf-9 having a particle size larger than 0.08 μm (Comparative Example 3), 0.1 μm
In the case of the graft composite rubber Gf-8 (Comparative Example 2) in which the volume of larger particles exceeds 20%, it was found that the impact resistance is relatively good but the pigment colorability is poor.

Example 11 Novarex 7022A (Mitsubishi Kasei Co., Ltd.) as a polycarbonate resin and Toughpet PB as a polyester resin
Using T: N-1000 (Mitsubishi Rayon Co., Ltd.), these resins and the graft composite rubber Gf-1 obtained in Reference Example 2 were mixed at the ratio shown in Table 3, and carbon black (Mitsubishi Chemical ( 0.5 parts of MCF88) manufactured by K.K. 30 this
m / m φ twin-screw extruder (Werner Faudler ZS
K-30 type) and melt-kneaded at a cylinder temperature of 260 ° C. to form pellets. After drying the obtained pellets, an injection molding machine (Promatt 165/75 manufactured by Sumitomo Heavy Industries Ltd.)
Mold) and injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. to obtain various evaluation test pieces. The results of evaluation using this test piece are shown in Table 3.

As is clear from the results shown in Table 3, the resin composition of the present invention has excellent impact resistance at room temperature and low temperature.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

Industrial Applicability The resin composition of the present invention has extremely high impact resistance and excellent pigment coloring while maintaining the excellent properties inherent in the polycarbonate resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoki Yamamoto 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Otake Office

Claims (3)

[Claims] 1. A composite rubber comprising a polyorganosiloxane component and an alkyl (meth) acrylate rubber component,
The number average particle size of the graft-polymerized one or more vinyl monomers is 0.01-0.07μm and is 0.10μ
A resin composition comprising a graft composite rubber (A) and a polycarbonate resin (B), wherein the volume of particles larger than m is 20% or less of the total particle volume. 2. The resin composition according to claim 1, wherein the graft composite rubber (A) is 1 to 50% by weight and the polycarbonate resin (B) is 99 to 50% by weight. 3. The resin composition according to claim 1 or 2, further comprising a polyester resin (C) mixed therein.