JP3124418B2 - Polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester resin composition having excellent impact resistance and pigment coloring properties.

[0002]

2. Description of the Related Art Thermoplastic polyesters, such as polyalkylene terephthalate, have excellent mechanical properties, heat resistance stability, weather resistance, electrical insulation properties, etc., so that electrical and
It is used in a wide range of fields such as electronic parts and automobile parts. However, its use is limited because of its low impact resistance, especially its notched impact strength.

[0003] Many inventions and techniques have been improved to overcome this shortcoming. The most effective method is a method in which a graft copolymer obtained by graft-polymerizing a monomer such as styrene, acrylonitrile, or methyl methacrylate onto a rubber-like elastomer (elastic body) is mixed with a polyester resin, There are many reports on this.

Among them, JP-A-2-150446 discloses a composite rubber comprising a polyorganosiloxane rubber and a poly (meth) acrylic rubber as a vinyl-based single rubber having weather resistance and improved impact resistance. A resin composition of a composite rubber-based graft copolymer obtained by graft polymerization of a monomer and a thermoplastic polyester has been proposed.

[0005]

SUMMARY OF THE INVENTION
When the composite rubber-based graft copolymer disclosed in JP-A-2-150446 is used as the rubber component of the impact-resistant resin, the particle size of the rubber component is larger than 0.08 μm. The coloring property of the plastic polyester resin composition was poor and the industrial value was low. Therefore, there has been a strong demand for the development of an impact-resistant resin having good impact resistance and excellent coloring properties when a pigment is added.

[0006]

The inventors of the present invention have conducted intensive studies on the relationship between the particle size of the graft copolymer and the coloring property when a pigment is added. When a composite rubber having a fine particle diameter of a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component is produced using an organosiloxane component, a resin comprising a graft composite rubber obtained from the composite rubber and a polyester resin is obtained. The present inventors have found that the composition exhibits excellent impact resistance and at the same time exhibit good pigment coloring properties, and arrived at the present invention.

That is, the gist of the present invention is to provide a composite rubber comprising a polyorganosiloxane component and an alkyl (meth) acrylate rubber component, and a number-average particle diameter obtained by graft-polymerizing one or more vinyl monomers. Is 0.01 ~
The resin composition is a mixture of a graft composite rubber (A) having a particle volume of 0.07 μm and a particle size larger than 0.10 μm of 20% or less of the total particle volume and a polyester resin (B). The present invention also includes a resin composition obtained by further mixing a filler (C).

The graft composite rubber (A) of the present invention has a number average particle size in the range of 0.01 to 0.07 μm,
The volume of the particles larger than μm is 20% or less of the volume of all the graft composite rubber particles. Number average particle size is 0.01μm
If it is smaller, the impact resistance of a molded product obtained from the graft composite rubber (A) and the polyester resin (B) or a molded product obtained from the filler (C) is further deteriorated.
On the other hand, when the number average particle diameter is larger than 0.07 μm, the particle size becomes close to the wavelength region of visible light and light scattering by the particles becomes large, so that the pigment coloring property of the molded product is deteriorated. still,
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 on a composite rubber in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component cannot be separated substantially. belongs to. The composite rubber can take various forms, such as a form 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, A form in which the organosiloxane and the polyalkyl (meth) acrylate are layered can be used, and these forms may be appropriately mixed. Examples of the laminar form include a form in which 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 thereon. An embodiment in which a first layer of polyalkyl (meth) acrylate and a second layer of polyorganosiloxane are present thereon.

In the present invention, as a raw material of the polyorganosiloxane, for example, a mixture comprising a diorganosiloxane and a siloxane-based grafting agent or a mixture further containing a siloxane-based crosslinking agent is used. The latex obtained by emulsifying this mixture with an emulsifier and water is atomized using a homomixer that atomizes by shearing force due to high-speed rotation, a homogenizer that atomizes by jetting power from a high-pressure generator, or the like. A polyorganosiloxane can be obtained by dropping into a benzenesulfonic acid aqueous solution at a constant rate for polymerization, and then neutralizing dodecylbenzenesulfonic acid with an alkaline substance. Although the size of the polyorganosiloxane is not particularly limited, the number average particle diameter is 0.003 to 0.06 μm, and 0.10 μm
It is preferred that the volume of the larger particles be no more than 20% of the total particle volume. The polyorganosiloxane having such a small size and a narrow width of the particle diameter 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 more at a very small speed. Can be obtained by:

Examples of the organosiloxane constituting the organosiloxane mixture include various organosiloxane cyclics having three or more member rings, and those having a three to six member ring are preferred. Specifically, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, etc. These may be used alone or in combination of two or more. These are used in an amount of at least 50% by weight, preferably at least 70% by weight in the organosiloxane-based 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.
Particularly, a tetrafunctional crosslinking agent is preferable, and among them, tetraethoxysilane is most preferable. The amount of the crosslinking agent to be used is 0 to 30% by weight, preferably 0.5 to 10% by weight in the organosiloxane-based mixture.

As the siloxane-based graft-linking agent, a compound capable of forming a unit represented by the following formula is used.

[0014]

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

(Meth) which can form a unit of the formula (I-1)
Acryloyloxysiloxane can form an effective graft chain because of its high grafting efficiency, and is advantageous in terms of exhibiting impact resistance. Note that methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the 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.

Examples of the unit capable of forming the unit of the formula (I-2) include vinylsiloxane, and specific examples include tetramethyltetravinylcyclotetrasiloxane. As a unit capable of forming a unit of the formula (I-3),
p-vinylphenylmethyldimethoxysilane, 2- (p
-Vinylphenyl) ethylmethyldimethoxysilane, 3
-(P-vinylbenzoyloxy) propylmethyldimethoxysilane and the like. As a compound capable of forming the unit of the formula (I-4), γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane and the like can be mentioned.

The amount of the grafting agent used in the organosiloxane mixture is not more than 10% by weight, preferably from 0.5 to 5% by weight.

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

These emulsifiers are used in an amount of 0.5 to 30 parts based on 100 parts of the organosiloxane mixture. If the amount is less than 0.5 part, the dispersion state becomes unstable and the emulsified state of a fine particle diameter cannot be maintained. On the other hand, if the amount exceeds 30 parts, the resulting polyorganosiloxane is inconveniently colored due to the emulsifier.

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

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Examples thereof include alkyl acrylates such as ethylhexyl acrylate and the like, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate. The use of butyl acrylate is preferred.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
Examples include 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 in the alkyl (meth) acrylate component.
%, Preferably 0.5 to 10% by weight.

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

The above-mentioned alkyl (meth) acrylate component is added to the neutralized latex of the polyorganosiloxane rubber component, and is polymerized by the action of a usual radical polymerization initiator. As the polymerization initiator, a peroxide, an azo initiator, or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide is particularly preferable.

As the polymerization proceeds, the polyorganosiloxane component and the polyalkyl (meth) acrylate rubber
A latex of a composite rubber of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component which cannot be separated substantially is obtained.

In the composite rubber according to the present invention comprising a polyorganosiloxane and a polyalkyl (meth) acrylate rubber, the polyorganosiloxane component is from 1 to 9
It is about 0% by weight. If the amount is less than 1% by weight, the characteristics of the polyorganosiloxane cannot be exhibited, and the impact resistance decreases.
On the other hand, if it exceeds 90% by weight, the gloss derived from the polyorganosiloxane is reduced, and the pigment coloring property is also reduced.

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

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

Examples of vinyl monomers to be graft-polymerized on the composite rubber include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyl toluene; methacrylic compounds such as methyl methacrylate and 2-ethylhexyl methacrylate. Acid esters; acrylic esters such as methyl acrylate, ethyl acrylate and butyl acrylate;
Various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl compounds containing an epoxy group such as glycidyl methacrylate; vinyl compounds containing a carboxylic acid group such as methacrylic acid; Are used alone or in combination of two or more.

The ratio of the composite rubber to the vinyl monomer when 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 a vinyl monomer 90
-5% by weight, preferably about 80-10% by weight.
When the amount of the vinyl monomer is less than 5% by weight, the graft composite rubber component is not sufficiently dispersed in the resin composition mixed with another resin, and when the amount exceeds 90% by weight, the impact strength tends to decrease. Is not preferred.

The graft composite rubber (A) can be obtained by adding a vinyl monomer to a composite rubber latex and polymerizing it in one step or in multiple steps by a radical polymerization technique.

After the completion of the graft polymerization, the latex is poured into hot water in which a metal salt such as calcium chloride or aluminum sulfate is dissolved, salted out and solidified to separate and recover the graft composite rubber. .

The polyester resin (B) used in the present invention includes an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid having 8 to 22 carbon atoms and an alkylene glycol, a cycloalkylene glycol or an aralkylene having 2 to 22 carbon atoms. It is composed of glycols and may optionally contain a subordinate amount of an aliphatic dicarboxylic acid such as adipic acid or sebacic acid. It may also contain a 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.

As the filler (C), for example, fibrous fillers such as glass fiber, carbon fiber, aramid fiber, metal fiber, whisker, glass beads, glass flake, calcium carbonate, talc, mica, aluminum oxide, Examples include fillers in various forms such as magnesium hydroxide and beryllium oxide. These fillers have an effect of reinforcing mechanical properties, particularly rigidity and heat resistance, and are used alone or in combination.

The composition of the graft composite rubber (A), the thermoplastic polyester (B) and the filler (C) in the resin composition of the present invention is not particularly limited, but the components are based on the weight of the whole resin composition. It is preferable that (A) is 1 to 50% by weight, component (B) is 99 to 50% by weight, and component (C) is 0 to 60% by weight. If the component (A) is less than 1% by weight, the effect of improving the impact resistance of the polyester resin composition is insufficient, and if it exceeds 50% by weight, the mechanical strength of the polyester 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) with a usual and known kneading machine and extruding. Such machines include mixing rolls,
Examples include a calender roll, a Banbury mixer, an extruder, an injection molding machine, a blow molding machine, an inflation molding machine, and the like. The resin composition of the present invention may optionally contain a dye, a pigment, a stabilizer, a reinforcing agent, a glass fiber, a filler, a flame retardant, and the like.

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

In the reference examples, the particle size of the polyorganosiloxane in the latex was measured by a dynamic light scattering method.
This measurement is a method utilizing the fact that particles in the latex have Brownian motion. When the particles in the latex are irradiated with a laser beam, the particles show fluctuations in accordance with the particle diameter. By analyzing this fluctuation, the particle diameter can be calculated. The number average particle size and the particle size distribution were determined using a DLS-700 model of Otsuka Electronics Co., Ltd.

The degree of swelling and gel content of the crosslinked polyorganosiloxane were measured by the following method using a 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 absorbed 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 the polyorganosiloxane in toluene at 23 ° C. for 48 hours.

In the examples, the Izod impact strength is
Measured according to ASTM D 258 (1/4 "notched).
The surface hardness was measured according to ASTM D 785 (Rockwell hardness). Gloss was measured according to ASTM D 523-62 (60 ° specular gloss). The pigment coloring property is JIS Z 8729
(Method of displaying object color using L ^* a ^* b ^* color system).

The number average particle diameter of the graft composite rubber and 0.10
The volume fraction of particles having a size of μm or more was determined by observing an ultrathin section sample with a transmission electron microscope. This ultra-thin section sample was melt-mixed in an extruder with 90 parts of polymethyl methacrylate and 10 parts of a graft composite rubber, and pelletized.
The pellet was cut out from a press-formed test piece using a microtome.

Reference Example 1 Production of polyorganosiloxane rubber latex SiL-1: 2 parts of tetraethoxysilane, γ
-0.5 part of methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. To this, sodium dodecylbenzenesulfonate was added.
After adding 300 parts of distilled water in which 67 parts were dissolved, the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes, and then passed twice through a homogenizer at a pressure of 300 kg / cm ² to obtain a stable premixed organosiloxane latex. Separately, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a separable flask equipped with a cooling condenser to prepare a 10% by weight aqueous solution of dodecylbenzenesulfonic acid.

While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 2 hours, and after completion of the addition, the temperature was maintained for 3 hours and the system was cooled. The reaction was then held at room temperature for 12 hours before adding sodium hydroxide.
The polymerization was completed by neutralization with an aqueous solution of dimethyl ether to obtain a polyorganosiloxane rubber latex SiL-1.

The latex thus obtained was mixed with 17
When the solid content was determined by drying at 0 ° C. for 30 minutes, 18.
It was 2% by weight. The swelling degree of this latex is 15.
6, the gel content is 87.6%, and the number average particle size is 0.8.
03 μm, volume fraction of particle size larger than 0.10 μm is 6.8%
Met.

Reference Example 2 Production of Graft Composite Rubber Gf-1: 54.9 parts of the latex SiL-1 obtained in Reference Example 1 was collected and placed in a separable flask equipped with a stirrer, and 170 parts of distilled water was added. After that, 58.8 parts of butyl acrylate,
A mixture of 1.2 parts of allyl methacrylate and 0.12 parts of tertiary butyl hydroperoxide was charged, and 30
The mixture was stirred for 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. Liquid temperature is 60
At the time when the temperature reached ° C, an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, and 0.24 part of Rongalite were dissolved in 10 parts of distilled water was added to start 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 30 parts of methyl methacrylate was added to the composite rubber latex.
Then, the mixture was kept at 70 ° C. for 4 hours to complete the graft polymerization onto the composite rubber.

The obtained graft composite rubber latex was gradually dropped into 200 parts of water (25 ° C.) containing 1.5% by weight of calcium chloride to coagulate, and then the temperature was raised to 90 ° C. to solidify. The coagulate is then 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 Graft composite rubber Gf-
2, Gf-3 and grafted silicone rubber Gs-4
Production of (for comparative example): Graft composite rubber Gf- was produced in the same manner as in Reference Example 2 except that the charged composition ratio of latex SiL-1 and butyl acrylate (BA) and allyl methacrylate (AMA) was set to the value shown in Table 1. 2, Gf-3 and grafted silicone rubber Gs-4 were obtained.

Reference Example 6 Production of Graft Composite Rubber Gf-5: 39.2 parts of the latex SiL-1 obtained in Reference Example 1 was collected and placed in a separable flask equipped with a stirrer, and 182 parts of distilled water was added. After addition, butyl acrylate 42.0
Parts, a mixture of 0.86 parts of allyl methacrylate and 0.2 parts of tertiary butyl hydroperoxide,
The mixture was stirred for 30 minutes to impregnate the polyorganosiloxane rubber particles. A nitrogen stream was passed through the separable flask to replace the nitrogen, and the temperature was raised to 60 ° C. Liquid temperature is 6
At 0 ° C., an aqueous solution obtained by dissolving 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, and 0.24 part of Rongalite in 10 parts of distilled water was added to start radical polymerization. Was. 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 mixture of 0.12 parts of tert-butyl hydroperoxide and 50 parts of methyl methacrylate was added dropwise to the composite rubber latex over 25 minutes, and the mixture was kept at 70 ° C. for 4 hours. The graft polymerization to 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 96.3 parts of a dry powder of the graft composite rubber Gf-5. The number average particle diameter of this graft composite rubber is 0.05 μm, and 0.10
The volume fraction of particles larger than μm was 6.1%.

Reference Example 7 Production of Graft Composite Rubber Gf-6: 70.6 parts of the latex SiL-1 obtained in Reference Example 1 was collected and placed in a separable flask equipped with a stirrer, and 121 parts of distilled water was added. After addition, 75.6 butyl acrylate
Parts, a mixed solution of 1.54 parts of allyl methacrylate and 0.2 part of tertiary butyl hydroperoxide,
The mixture was 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 liquid temperature reaches 60 ° C., an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, and 0.24 part of Rongalite are dissolved in 10 parts of distilled water is added, and radical polymerization is performed. Was started. 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 drops to 75 ° C,
To this composite rubber latex, a mixture of 0.12 parts of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was added dropwise over 25 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 95.5 parts of dry powder of the graft composite rubber Gf-6. The number average particle diameter of this graft composite rubber is 0.03 μm, and 0.10
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. (No siloxane crosslinking agent used). 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, the premixed latex was added dropwise to a high-temperature aqueous solution of dodecylbenzenesulfonic acid for polymerization. In this reference example, after maintaining the high temperature for 3 hours after the completion of dropping of the premixed latex, the mixture was cooled to room temperature and immediately neutralized with an aqueous solution of sodium hydroxide to obtain a polyorganosiloxane latex SiL-2.

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

Reference Example 9 Production of Graft Composite Rubber Gf-7: The procedure of Reference Example 2 was repeated, except that the latex SiL-2 obtained in Reference Example 8 was used.
1 part). The number average particle size of this graft composite rubber is
The particle volume was 0.05 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 comparison): 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane And the siloxane mixture 1
00 parts were obtained. To 200 parts of distilled water in which 4 parts of dodecylbenzenesulfonic acid and 2 parts of sodium dodecylbenzenesulfonate are dissolved, 100 parts of the mixed siloxane is added, and the resulting mixture is preliminarily dispersed by a homomixer and emulsified and dispersed by a homogenizer. After heating, cool, 20 ℃
For 48 hours, and then with aqueous sodium hydroxide solution to pH
Was neutralized to 7.0 to complete the polymerization to obtain a polyorganosiloxane latex SiL-3. The polymerization rate of this polyorganosiloxane rubber is 89.6%, the average particle size is 0.05 μm,
The volume fraction of the particle diameter larger than 0.1 μm was 67.3%.

Reference Example 11 Production of Graft Composite Rubber Gf-8 (for Comparative Example): Latex SiL-3 obtained in Reference Example 10
In the same manner as in Reference Example 2, except that was used, a graft composite rubber Gf-8 (97.1 parts) was obtained. The number average particle diameter of this graft composite rubber was 0.07 μm, and the volume fraction of particles larger than 0.10 μm was 27.2%.

Reference Example 12 Production of Graft Composite Rubber Gf-9 (for Comparative Example): Sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid were each added to 0.1 g each.
A polyorganosiloxane rubber latex SiL-4 was obtained in the same manner as in Reference Example 9 except that the amount was changed to 67 parts. The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the number average particle diameter was 0.16 μm.

33.4 parts of this latex SiL-4 was collected, put into a separable flask equipped with a stirrer, 191.6 parts of distilled water was added, the atmosphere was replaced with nitrogen, and 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 tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixed solution was impregnated into polyorganosiloxane rubber particles. Then, ferrous sulfate 0.002 part, ethylenediaminetetraacetic acid disodium salt 0.006 part, Rongalit 0.
An aqueous solution obtained by dissolving 26 parts in 10 parts of distilled water was added to start radical polymerization. Thereafter, the internal temperature was kept at 82 ° C. for 1 hour to complete the polymerization to obtain a composite rubber latex. Liquid temperature is 75
C., a mixture of 0.12 parts of tert-butyl hydroperoxide and 30 parts of methyl methacrylate was added dropwise to the composite rubber latex over 25 minutes.
It was kept at 70 ° C. for 4 hours to complete the graft polymerization to the composite rubber.

The obtained graft composite rubber latex 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, and 0.10
The volume fraction of particles larger than μm was 93.4%.

Reference Example 13 Grafted acrylic rubber Ga-
Production of Comparative Example 10 (for Comparative Example): A separable flask equipped with a stirrer was charged with 215 parts of distilled water and 1.0 part of sodium dodecylbenzenesulfonate, and then charged with butyl acrylate 6
A mixed liquid of 8.6 parts, 1.4 parts of allyl methacrylate, and 0.2 part of tertiary butyl hydroperoxide was charged, and nitrogen was replaced by passing a nitrogen stream through this separable flask, and the temperature was raised to 60 ° C. . Liquid temperature is 60
At the time when the temperature reached ° C, an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, and 0.24 part of Rongalite were dissolved in 10 parts of distilled water was added to start 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 an acrylic rubber latex. After the liquid temperature drops to 75 ° C,
To this latex, a mixed solution of 0.12 parts of tert-butyl hydroperoxide and 30 parts of methyl methacrylate was dropped over 25 minutes, and then kept at 70 ° C. for 4 hours to complete the graft polymerization onto 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 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 A tufpet PBT: N-1000 manufactured by Mitsubishi Rayon Co., Ltd. was used as a polyester resin.
Graft rubbers Gf-1 to Gf- obtained in 11 to 13
9, Gs-4, and Ga-10 were mixed at the ratios shown in Table 2, and further mixed with carbon black (MCF8 manufactured by Mitsubishi Kasei Corporation).
8) 0.5 parts were mixed. This was supplied to a 30 m / m φ twin screw extruder (model ZSK-30 manufactured by Werner Faudler), melt-kneaded at a cylinder temperature of 240 ° C., and shaped into pellets. After the obtained pellets were dried, they were supplied to an injection molding machine (Promat 165/75, manufactured by Sumitomo Heavy Industries, Ltd.) and injection molded at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. to obtain various evaluation test pieces. . Table 2 shows the results of evaluation using this test piece.

When the colorimetric L ^* value 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 more than 18, it will not be practical.

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

From the results of Examples 6 and 7, it was found that even when the amount of the vinyl monomer to be graft-polymerized to the composite rubber was changed, good impact resistance and mechanical strength were exhibited. Example 8
From the results of Nos. 10 to 10, it was found that the resin composition obtained by mixing the graft composite rubber without using the siloxane-based crosslinking agent and the polyester-based resin also exhibited good impact resistance and pigment coloring.

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

Examples 11 and 12 As polyester-based resins, polyester-based thermoplastic elastomer obtained by block copolymerizing 70% by weight of polytetramethylene terephthalate and 30% by weight of polytetramethylene ether glycol having an average molecular weight of 1,000, and Mitsubishi Rayon Co., Ltd. ) Toughpet PBT: N-1000 was used in combination. These resins and the graft composite rubber Gf-1 obtained in Reference Example 2 were mixed at the ratio shown in Table 3. Evaluation test pieces were produced in the same manner as in Example 1 except for the amount of carbon black added and the pellet shaping conditions, and the results shown in Table 3 were obtained.

As is clear from the results 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 polyester resins.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-198358 (JP, A) JP-A-3-231907 (JP, A) JP-A-5-86255 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 67/00-67/04

Claims (3)

(57) [Claims] 1. A composite rubber comprising a polyorganosiloxane component and an alkyl (meth) acrylate rubber component,
The number average particle diameter obtained by graft polymerization of one or more vinyl monomers is 0.01 to 0.07 μm and 0.10 μm.
graft composite rubber (A) and polyester resin (B) in which the volume of particles larger than m is 20% or less of the total particle volume
A resin composition comprising: 2. The resin composition according to claim 1, wherein the amount of the graft composite rubber (A) is 1 to 50% by weight and the amount of the polyester resin (B) is 99 to 50% by weight. 3. The resin composition according to claim 1, further comprising a filler (C).