JPH04100812A - Composite rubber graft copolymer - Google Patents

Abstract

PURPOSE:To obtain a composite rubber graft copolymer used as an impact modifier which is added to various resins to improve their impact resistance, heat resistance, mechanical strengths, surface appearances, etc., by grafting a vinyl monomer onto composite rubber particles composed of intertwined silicone rubber and acrylic rubber components. CONSTITUTION:A polymer prepared by grafting a vinyl monomer onto a composite rubber comprising 10-90wt.% polyorganosiloxane rubber component (A) and 90-10wt.% polyalkyl (meth)acrylate rubber component (B) polymerized with an alkyl (meth)acrylate, a polyalkyl (meth)acrylate crosslinking agent for rubber and a polyalkyl (meth)acrylate graft-crosslinking agent for rubber, having a structure composed of intertwined components A and B (the total of components A and B is 100wt.%) and having a mean particle diameter of 0.08-0.6mum is used as a composite rubber graft copolymer useful as an impact modifier.

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention relates to a composite rubber-based graft copolymer that is extremely useful as an impact modifier, and more specifically, it can be added to various resins to improve impact resistance, heat resistance, mechanical strength, and surface appearance without causing delamination. The present invention relates to a composite rubber-based graft copolymer that can give molded products with excellent properties and can be used as a resin composition with excellent moldability and fluidity. [0002]

BACKGROUND OF THE INVENTION Impact resistance modifiers are used to impart impact resistance to various resins, and various types have been proposed to date. For example, glass transition temperature (Tg) as an impact modifier.
It is well known that a polybutadiene elastomer with a low carbon content is grafted with a polymerizable monomer. However, such polybutadiene-based elastomers are thermally unstable because unsaturated bonds remain in the elastomer.
A practical product with excellent thermal stability has not been obtained. [0003] Also known is an impact modifier made of a graft copolymer obtained by grafting a polymerizable monomer onto an acrylic rubber having a relatively high Tg, but the effect of improving wall impact resistance is not so remarkable. [0004] Furthermore, a polyorganosiloxane rubber-based graft copolymer in which a polymerizable monomer is grafted onto silicone rubber having a low Tg is disclosed in JP-A-60-252613,
Although it has some effect of improving impact resistance, there is a need for a higher improvement effect, and there is also a problem that resins to which it is added have poor surface gloss. [0005]

[Means to solve the problem]

In view of this situation, the present inventors have conducted intensive studies on impact resistance modifiers that can be added to resins to impart better impact resistance than conventional ones without significantly reducing the surface gloss of the resins. As a result, a composite rubber-based graft copolymer is obtained by graft-polymerizing a vinyl monomer with high efficiency to a composite rubber in which a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component are entangled in an inseparable manner. The inventors have discovered that this is an impact resistance modifier that improves the impact resistance of the resin without degrading its surface appearance, and has arrived at the present invention. [0006] That is, the gist of the present invention is that 10 to 90% by weight of a polyorganosiloxane rubber component and an alkyl (meth)acrylate,
90 to 10% by weight of a polyalkyl (meth)acrylate rubber component obtained by polymerizing a crosslinking agent for polyalkyl (meth)acrylate rubber and a graft crosslinking agent for polyalkyl (meth)acrylate rubber are intertwined with each other so that they cannot be separated. structure, and the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component is 100% by weight, with an average particle diameter of 0.08 to 0.
A composite rubber-based graft copolymer is obtained by graft-polymerizing one or more vinyl monomers onto a 6 μm composite rubber. [0007] Instead of the above-mentioned composite rubber, one of polyorganosiloxane rubber and polyalkyl (meth)acrylate rubber, or a simple mixture of both, is used as a rubber source, and one or more vinyl monomers are added thereto. Even if a t-grafted material is used, it does not result in an excellent impact modifier, and the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component are entangled with each other so that they cannot be separated, forming a composite. Only when composite rubber is used as a rubber source does it become an excellent impact modifier. [0008] Furthermore, if the polyorganosiloxane rubber component in the composite rubber exceeds 90% by weight, the surface appearance of a molded product obtained from a composition obtained by adding a graft copolymer using this composite rubber to a resin will deteriorate. On the other hand, if the polyalkyl (meth)acrylate rubber component exceeds 90% by weight, the effect of improving the impact resistance of the resulting graft copolymer decreases. Therefore, in the composite rubber used in the present invention, the two rubber components constituting the composite rubber must both be in the range of 10 to 90% by weight (total amount of both rubber components 100% by weight),
It is preferably in the range of 20 to 80% by weight. [0009] The average particle diameter of the composite rubber needs to be in the range of 0.08 to 0.6 μm. Average particle size is 0.08μm
If it is less than 0.6 μm, the effect of improving the impact resistance of the graft copolymer obtained is reduced, and if it is larger than 0.6 μm, the effect of improving the impact resistance of the graft copolymer is reduced, and the graft copolymer obtained by adding the graft copolymer to the resin decreases. The surface appearance of molded articles made from the composition deteriorates. The emulsion polymerization method is optimal for producing composite rubber with an average particle size within the above range. First, a latex of polyorganosiloxane rubber is prepared,
Preferably, monomers for polyalkyl (meth)acrylate rubber synthesis are added to the latex to impregnate the polyorganosiloxane rubber particles in the latex, and then these monomers are polymerized. [0010] The polyorganosiloxane rubber component constituting the above composite rubber can be prepared by emulsion polymerization using the organosiloxane and crosslinking agent for polyorganosiloxane rubber (hereinafter referred to as crosslinking agent (I)) shown below. Grafting agent for polyorganosiloxane rubber (hereinafter referred to as grafting agent)
I) can also be used in combination. [0011] Examples of the organosiloxane include cyclic organosiloxanes having 3 or more membered rings, and those having 3 to 6 membered rings are preferably used. Specific examples of preferred cyclic organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclo. Examples include tetrasiloxane, which may be used alone or in combination of two or more. The amount of cyclic organosiloxane used is preferably 50% by weight or more, more preferably 70% by weight or more in the polyorganosiloxane rubber component. [0012] As the crosslinking agent (I), a trifunctional or tetrafunctional silane crosslinking agent, that is, a silane compound having three or four alkoxy groups, is used, and specific examples thereof include trimethoxymethylsilane, triethoxysilane, etc. Examples include phenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. As the crosslinking agent (I), a tetrafunctional one is preferable, and among the tetrafunctional crosslinking agents, tetraethoxysilane is particularly preferable. The amount of crosslinking agent (I) used is 0.1 to 30]ii-% in the polyorganosiloxane rubber component. [0013] The graft crossover agent (I) is represented by the following formula (% formula %): an elementary atom or a methyl group, n represents Oll or 2, and p represents an integer of 1 to 6. ) are used. [0014] (Meth)acryloyloxysiloxane that can form the unit of formula (I-1) has a high grafting efficiency, so it is possible to form an effective graft chain, and is advantageous in terms of impact resistance development. . Note that methacryloyloxysiloxane is particularly preferred as a compound capable of forming the unit of formula (I-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyl. Examples include ethoxydiethylsilane, γ-methacryloyloxypropyljethoxymethylsilane, and δ-methacryloyloxybutyljethoxymethylsilane. The amount of the grafting agent (■) used is 0 to 10% by weight in the polyorganosiloxane rubber component. [0015] This polyorganosiloxane rubber manufacturing method is described, for example, in US Pat. No. 2,891,920 and US Pat.
The method described in the specification etc. of No. 1 can be used. In the practice of the present invention, for example, a mixture of an organosiloxane, a crosslinking agent (I), and optionally a grafting agent (I) is mixed in the presence of a sulfonic acid emulsifier such as an alkylbenzenesulfonic acid or an alkylsulfonic acid. It is preferable to manufacture by a method of shear mixing with water using a homogenizer or the like. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use an alkylbenzenesulfonic acid metal salt, an alkylsulfonic acid metal salt, or the like in combination, since this is effective in maintaining the polymer stably during graft polymerization. [0016] Next, the polyalkyl (meth)acrylate rubber component constituting the polyorganosiloxane rubber is the alkyl (meth)acrylate shown below, a crosslinking agent for polyalkyl (meth)acrylate rubber (hereinafter referred to as crosslinking agent (II)). )
and a graft cross-agent for polyalkyl (meth)acrylate rubber (hereinafter referred to as graft cross-agent (II)). [0017] Examples of alkyl (meth)acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate,
Examples include alkyl methacrylates such as n-lauryl methacrylate, and n-butyl acrylate is preferably used. [0018] Examples of the crosslinking agent (II) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate.
Examples include 4-butylene glycol dimethacrylate. [0019] Examples of the graft cross-agent (II) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like. Allyl methacrylate can also be used as a crosslinking agent (■■). These crosslinking agents (II) and grafting agents (II) may be used alone or in combination of two or more. The total amount of crosslinking agent (II) and grafting agent (II) used is the polyalkyl (
It is 0.1 to 20% by weight in the meth)acrylate rubber component. [0020] The polymerization of the polyalkyl (meth)acrylate rubber component is
The above alkyl (
After adding the meth)acrylate crosslinking agent (II) and the graft crosslinking agent (II) and impregnating them into the polyorganosiloxane rubber particles, a conventional radical polymerization initiator is applied. As the polymerization progresses, a crosslinked network of polyalkyl (meth)acrylate rubber is formed that is intertwined with the crosslinked network of polyorganosiloxane rubber, and the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are virtually inseparable. Composite rubber latex is obtained. In carrying out the present invention, the main skeleton of the polyorganosiloxane rubber component has repeating units of dimethylsiloxane, and the main skeleton of the polyalkyl (meth)acrylate rubber component has repeating units of n-butyl acrylate as the composite rubber. Composite rubber having the following properties is preferably used. [0021] The composite rubber thus prepared by emulsion polymerization is
It can be graft copolymerized with vinyl monomers, and since the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are tightly intertwined, they cannot be extracted and separated using ordinary organic solvents such as acetone and toluene. do not have. This composite rubber has a gel content of 80% by weight or more as measured by extraction with toluene at 90°C for 12 hours. It is often used. [0022] Vinyl monomers to be graft-polymerized to this composite rubber include aromatic alkenyl compounds such as styrene, α-tacylstyrene, and vinyltoluene; methyl methacrylate;
Various vinyl monomers such as methacrylic acid esters such as 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; are used alone or in combination of two or more. Among these vinyl monomers, aromatic alkenyl compounds are preferred, and styrene is particularly preferred. [0023] The ratio of the composite rubber to the vinyl monomer in the composite rubber graft copolymer is such that the polyorganosiloxane rubber is 30 to 30% based on the weight of the graft copolymer.
95% by weight, preferably 5 to 70% by weight of vinyl monomer, and 40 to 70% by weight of polyorganosiloxane rubber.
It is more preferable that the vinyl monomer content is 90% by weight and 10 to 60% by weight. If the vinyl monomer content is less than 5% by weight, the graft copolymer will not be sufficiently dispersed in the resin, and if it exceeds 70% by weight, the effect of imparting impact resistance will be reduced, which is not preferable. [0024] The composite rubber-based graft copolymer is obtained by adding the above-mentioned vinyl monomer to a composite rubber latex, and polymerizing the composite rubber-based graft copolymer latex in one step or in multiple stages using radical polymerization technology, by chlorinating the composite rubber-based graft copolymer latex. It can be separated and recovered by pouring it into hot water in which a metal salt such as calcium or magnesium sulfate has been dissolved, followed by salting out and coagulation. [0025] The composite rubber-based graft copolymer obtained in the present invention can be used as an impact-resistant resin by itself, but when mixed with various thermoplastic resins, it imparts high impact resistance to these resins. Moreover, it is useful as an impact modifier because it does not deteriorate the surface appearance of the resin. [0026] The thermoplastic resin whose impact resistance can be improved by adding this composite rubber-based graft copolymer is a mixture of a polyphenylene ether resin and a polystyrene resin, a polycarbonate resin and/or a polyester resin, and an aromatic resin. 70 to 100% by weight of at least one vinyl monomer selected from the group consisting of vinyl cyanide compounds and (meth)acrylic acid esters, and 0% of other vinyl monomers copolymerizable with these alkenyl compounds. Homopolymers or copolymers obtained by polymerizing up to 30% by weight can be mentioned. [0027] Examples of the method of adding the graft copolymer of the present invention to the resin include a method of mechanically mixing it using a known device such as a Banbury mixer roll mill or a twin-screw extruder and shaping it into pellets. can. The extruded pellets can be molded in a wide temperature range, and a normal injection molding machine is used for molding. [0028] Further, stabilizers, plasticizers, lubricants, flame retardants, pigments, fillers, etc. may be added to this resin composition as necessary. Specifically, stabilizers such as triphenyl phosphite; lubricants such as polyethylene wax and polypropylene wax; phosphate flame retardants such as triphenyl phosphate and tricresyl phosphate; brominated retardants such as decabromo biphenyl and decabromo biphenyl ether; Examples include flame retardants such as flame retardants and antimony trioxide; pigments such as titanium oxide, zinc sulfide, and zinc oxide; fillers such as glass fiber, asbestos wolastonite, mica, and talc. [0029]

【Example】

The present invention will be specifically explained by the following examples. [0030] In the following description, all "parts" mean parts by weight. [0031] The physical properties in each Example and Comparative Example were measured by the following methods. Tensile Modulus According to the method of ASTM D-638. Gloss ASTM D-523-62T (6
00 specular gloss) method. Bending strength According to the method of ASTM D-790. Izod Impact Strength According to the method of ASTM D-256. (With 1/4” notch) Vicat softening temperature According to the method of ISOR306. [0032]

[Example 1] Production of composite rubber-based graft copolymer (S-1): Mixing 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of octamethylcyclotetrasiloxane. 100 parts of a siloxane mixture was obtained. 100 parts of the above mixed siloxane was added to 200 parts of distilled water in which 1 part each of dodecylbenzenesulfonic acid and sodium dodecylbenzenesulfonate had been dissolved, and after preliminary stirring at 10.000 rpm with a homogenizer, the mixture was mixed with 300 kg/cm using a homogenizer.
The mixture was emulsified and dispersed at a pressure of 2 to obtain an organosiloxane latex. Transfer this mixed solution to a separable flask equipped with a condenser and stirring blades, and while stirring and mixing,
After heating at 0°C for 5 hours, the latex was left at 20°C, and after 48 hours, the pH of the latex was adjusted to 6.
9 and terminated the polymerization to obtain polyorganosiloxane rubber latex (hereinafter referred to as polyorganosiloxane rubber latex-1). The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the average particle diameter of the polyorganosiloxane rubber was 0.16 μm. [0033] The above polyorganosiloxane rubber latex-1 was added to 11
Collect 7 parts, put it in a separable flask equipped with a stirrer, add 57.5 parts of distilled water, and add 57.5 parts of distilled water for 50' while purging with nitrogen.
C., a mixed solution of 33.95 parts of n-butyl acrylate, 1.05 parts of allyl methacrylate and 0.26 parts of ter-butyl hydroperoxide was added, stirred for 30 minutes, and this mixed solution was added to polyorganosiloxane rubber particles. infiltrated into. Next, a mixture of 0.002 parts of ferrous sulfate, 0.006 parts of thorium acetate of ethylenediaminetetraacetic acid, 0.26 parts of Rongalite, and 5 parts of distilled water was added to start radical polymerization, and then kept at an internal temperature of 70°C for 2 hours. A composite rubber latex was obtained. A portion of this latex was sampled and the average particle size of the composite rubber was measured to be 0.19 μm.
Met. In addition, this latex is dried to obtain a solid substance,
After extraction with toluene at 90°C for 12 hours, the gel content was measured and found to be 97.3% by weight. This composite rubber latex contains 0.12% of tert-butyl hydroperoxide.
and 30 parts of styrene was added dropwise over 15 minutes, and then maintained at 70°C for 4 hours to perform graft polymerization to the composite rubber. The polymerization rate of styrene was 91.5%. The obtained graft copolymer latex was dropped into 200 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and then dried at 75°C for 16 hours to form a composite rubber-based graft copolymer (hereinafter referred to as , 97.8 parts of dry powder (referred to as S-1) was obtained. [0034] This composite rubber-based graft copolymer S-1 was extruded and shaped at a cylinder temperature of 230°C, and the resulting pellets were
Injection molding machine (Promatsu) 165/75 type: Sumitomo Heavy Industries (
Co., Ltd.) A 1-go dumbbell was molded at 230°C and its tensile modulus and gloss were measured, and the tensile modulus was 2600 kg/
cm2 gloss was 89%. [0035]

[Example 2] Production of composite rubber-based graft copolymer (S-2): [00
36] 2 parts of tetraethoxysilane and 98 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of mixed siloxane. Add 100 parts of the above mixed siloxane to 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid have been dissolved,
As in the production of S-1, preliminary dispersion using a homomixer and emulsification and dispersion using a homogenizer were performed, followed by heating at 80°C for 5 hours, and then left at 20°C for 48 hours, and the pH of the latex was adjusted to 6 with an aqueous sodium hydroxide solution. The mixture was neutralized to a temperature of 9°C to obtain a polyorganosiloxane rubber latex (hereinafter referred to as polyorganosiloxane rubber latex-2). The polymerization rate of the obtained polyorganosiloxane rubber was 88.9.
%, and the average particle diameter was 0.16 μm. [0037] The above polyorganosiloxane rubber latex-2 was added to 11
After collecting 7 parts and adding 57.5 parts of distilled water, 33.95 parts of n-butyl acrylate, 1.05 parts of allyl methacrylate and 0.26 parts of ter-butyl hydroperoxide were added in the same manner as in the production of S-1. Prepare the mixed solution and use S- for the rest.
Polymerization to form a composite rubber was carried out under the same conditions and method as in the production of Example 1. The average particle size of this composite rubber is 0.20 μm,
The gel content measured by the toluene extraction method in the same manner as in Example 1 was 92.4% by weight. 0.12% of tert-butyl hydroperoxide was added to the obtained composite rubber latex.
A mixed solution of 30 parts of styrene and 30 parts of styrene was added thereto, and graft polymerization was carried out under the same conditions and method as in S-1. The graft copolymer latex thus obtained was coagulated in the same manner as in Example 1.
The mixture was separated and dried to obtain 97.6 parts of dry powder of a composite rubber-based graft copolymer (hereinafter referred to as S-2). [0038] This composite rubber-based graft copolymer S-2 was extruded and shaped at a cylinder temperature of 230°C, and the resulting pellets were
Injection molding machine (Promatsu) 165/75 type: Sumitomo Heavy Industries (
) A No. 1 dumbbell was molded at 230°C and its tensile modulus and gloss were measured, and the tensile modulus was 2900 kg.
/cm2 The gloss was 82%. [0039]

[Examples 3 and 4, Comparative Examples 1 and 2] Production of composite rubber-based graft copolymers S-3 to S-6: [
[0040] A composite was prepared in the same manner as in Example 1, except that the polyorganosiloxane rubber latex-1 prepared during the production of composite comb-based graft copolymer S-1 was used, and the components shown in Table 1 were used in predetermined amounts. Rubber latexes 3 to 6 were obtained. [0041] Styrene 30 is added to each composite rubber latex thus obtained.
and 0.12 parts of tert-butyl hydroperoxide, and a graft polymerization reaction to the composite rubber was carried out in the same manner as in Example 1. After the reaction, each latex obtained was added to the mixture of 0.12 parts of tert-butyl hydroperoxide. Coagulate, separate, and dry in the same manner as above to obtain composite rubber-based graft copolymers (hereinafter referred to as S-3 to S-3, respectively).
5-6) Dry powder was obtained. [0042]

[Table 1] [0043] The composite rubber graft copolymers S-3 to 6 were extruded and shaped at a cylinder temperature of 230°C, and the resulting pellets were molded using an injection molding machine (Promatsu) 165/75 model: Sumitomo Heavy Industries. Co., Ltd.) No. 1 dumbbells were molded at 230°C, and the tensile modulus and gloss were measured, and the results shown in Table 1 were obtained. [0044] From Table 1, it can be seen that when the polyorganosiloxane content in the composite rubber is less than 10%, the tensile modulus does not decrease, and when the polyorganosiloxane content in the composite rubber exceeds 90%, the composite rubber graft copolymer is It can be seen that the luster of the coalescence is lowered, which is not preferable. [0045]

[Example 5] Production of composite rubber-based graft copolymers S-7 to S-8: [
[0046] Using polyorganosiloxane rubber latex-1 prepared during the production of composite rubber-based graft copolymer S-1,
Two types of composite rubber-based graft copolymers with different amounts of styrene monomer used in graft polymerization were produced. [0047] That is, 117 parts of the above siloxane rubber latex-1 were collected, put into a separable flask equipped with a stirrer together with 200 parts of distilled water, and after purging with nitrogen, the temperature was raised to 50°C.
- A mixed solution of 33.95 parts of butyl acrylate, 1.05 parts of allyl methacrylate and 0.26 parts of ter-butyl hydroperoxide was charged and stirred for 30 minutes, followed by 0.002 parts of ferrous sulfate and disodium ethylenediaminetetraacetic acid salt. A mixed solution of 0.006 parts of Rongalit, 0.26 parts of Rongalit, and 5 parts of distilled water was charged and polymerization was started to produce a composite rubber latex. The average particle size of this composite rubber is 0
．． The gel content was 97.3% by weight as measured by the toluene extraction method in the same manner as in Example 1. A mixed solution of 0.20 parts of tert-butyl hydroperoxide and 50 parts of styrene was added to this composite rubber latex at 70°C.
The mixture was added dropwise for 15 minutes, and then maintained at 70°C for 4 hours to complete graft polymerization to the composite rubber. Then Example 1
A dry powder of a composite rubber-based graft copolymer (hereinafter referred to as S-7) was obtained by coagulating and drying in the same manner as above. In addition, graft polymerization was carried out in the same manner as in S-7 except that a mixed solution of 10 parts of styrene and 0.04 parts of tert-butyl hydroperoxide was added to the composite rubber latex, and coagulation, separation, and drying were carried out in the same manner as in Example 1. A dry powder of a composite rubber-based graft copolymer (hereinafter referred to as S-8) was obtained by processing. [0048] The composite rubber-based graft copolymers S-7 to 8 were extruded at a cylinder temperature of 230°C, and the resulting pellets were molded using an injection molding machine (Promatsu) Model 165/75: Sumitomo Heavy Industries, Ltd. ) When a bait dumbbell was molded at 230°C and the tensile modulus and gloss were measured, the tensile modulus of S-7 was 3200 kg/cm2 and the gloss was 87%, and S-8
The tensile modulus is 2100 kg/cm2, and the gloss is 81%.
Met. [0049]

[Comparative Example 3] Production of composite rubber-based graft copolymer S-9: [0050
] 117 parts of polyorganosiloxane rubber latex-1 were collected, put into a separable flask with a stirrer together with 57.5 parts of distilled water, and after purging with nitrogen, the temperature was raised to 50 ° C.
- Charge a mixed solution of 33.95 parts of butyl acrylate and 0.26 parts of tert-butyl hydroperoxide,
Stirred for 0 minutes. Thereafter, the same amount of the redox initiator mixture used in Example 1 was charged and emulsion polymerized to obtain a rubber latex. Here, unlike in Example 1, realyl methacrylate was not added. The average particle diameter and gel content of this rubber latex measured by toluene extraction method were 0.
．． It was 22 μm and 63% by weight. A mixed solution of 0.12 parts of tert-butyl hydroperoxide and 30 parts of styrene was added dropwise to this rubber latex at 70°C for 15 minutes, and then held at 70°C for 4 hours to carry out graft polymerization. Coagulation, separation, as in Example 1 above,
A dry powder of the graft copolymer (hereinafter referred to as S-9) was obtained by drying. [0051] This composite rubber-based graft copolymer S-9 was extruded and shaped at a cylinder temperature of 230°C, and the resulting pellets were
Injection molding machine (Promatsu) 165/75 type: Sumitomo Heavy Industries (
) A No. 1 dumbbell was molded at 230°C, and its tensile modulus and gloss were measured, each being 4300 kg/cm2.61'
A result of 4 was obtained. Simply graft-polymerizing a vinyl monomer onto a polyorganosiloxane rubber in two stages failed to lower the tensile modulus, and the surface gloss of the impact-resistant resin was poor. [0052]

[Comparative Example 4] Production of composite rubber-based graft copolymer 5-10: [005
3] 117 parts of polyorganosiloxane rubber latex-1 were collected, put into a separable flask with a stirrer together with 57.5 parts of distilled water, and after purging with nitrogen, 35 parts of n-butyl acrylate, 30 parts of styrene, and tert-butylhydrocarbon were added. A mixture of 0.26 parts of peroxide was heated at 70°C for 30 minutes in the presence of the same amount of the redox initiator mixture used in Example 1.
It was added dropwise over a period of minutes to polymerize. After that, it was held at 70°C for 4 hours to complete the polymerization, and then solidified in the same manner as in Example 1 above.
After separation and drying treatment, a graft copolymer (hereinafter referred to as 5-10
A dry powder was obtained. [0054] This composite rubber-based graft copolymer 5-10 was extruded at a cylinder temperature of 230°C, and the resulting pellets were molded using an injection molding machine (Promatsu) 165/75 model: Sumitomo Heavy Industries, Ltd.) 230 A No. 1 dumbbell was molded at ℃, the tensile modulus and gloss were measured, and each was 5100 kg/cm2.53.
I got the result of Z. Simply mixing a vinyl monomer with a polyorganosiloxane rubber and subjecting it to graft polymerization failed to lower the tensile modulus and the surface gloss of the impact-resistant resin was poor. [0055]

[Comparative Example 5] Production of composite rubber-based graft copolymer 5-12: [005
6] 2 parts of tetraethoxysilane, 0.5 part of χ-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. 4 parts of dodecylbenzenesulfonic acid and 2 parts of sodium dodecylbenzenesulfonate
10 parts of the above mixed siloxane was dissolved in 200 parts of distilled water.
0 parts, pre-dispersion with a homomixer and emulsification with a homogenizer were carried out in the same manner as in the production of S-1, and 80 parts
'C After heating for 15 hours, it was left to stand at 20℃ for 48 hours after cooling, and then the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution.
Neutralized to polyorganosiloxane rubber latex-3
I got it. The polymerization rate of this polyorganosiloxane rubber is 8
9.6%, and the average particle diameter was 0.05 μm. [0057] The above polyorganosiloxane rubber latex-3 was added to 11
After collecting 7 parts and adding 57.5 parts of distilled water, 33.95 parts of n-butyl acrylate, as in the production of S-1,
A composite rubber was polymerized in the same manner as in the production of S-1, except that a mixed solution of 1.05 parts of allyl methacrylate and 0.26 parts of ert-butyl hydroperoxide was charged. The average particle diameter of this composite rubber was 0.07 μm, and the gel content measured by the toluene extraction method in the same manner as in Example 1 was 95.8% by weight. [0058] A mixed solution of 0.12 parts of tert-butyl hydroperoxide and 30 parts of styrene was added to the obtained composite rubber latex, and graft polymerization was performed under the same conditions as in the production of S-1. The graft copolymer latex thus obtained was coagulated, separated, and dried in the same manner as in Example 1 to obtain a dry powder of the graft copolymer (hereinafter referred to as 5-12) [0
[059] This composite rubber-based graft copolymer 5-12 was extruded and shaped at a cylinder temperature of 230°C, and the resulting pellets were molded using an injection molding machine (Promatsu) 165/75 type: Sumitomo Heavy Industries, Ltd. at 230°C. When a No. 1 dumbbell was molded and the tensile modulus and gloss were measured, the tensile modulus was 4800 kg/
cm2, and the gloss was 85Z. When the particle size of the composite rubber was less than 0.08 μm, the value of tensile modulus could not be lowered. [0060]

[Comparative Example 6] Production of composite rubber-based graft copolymer 5-13: [006
1] Prepare 100 parts of the same mixed siloxane as in the production of polyorganosiloxane rubber latex-3, and add distilled water 2 in which only 0.2 part of dodecylbenzenesulfonic acid is dissolved.
After adding 00 parts and pre-stirring at 10.000 rpm with a homomixer, 140Kg/c with a homogenizer.
The latex was emulsified at a pressure of 5.0 m'' to obtain an organosiloxane rubber latex. This latex was heated at 80°C for 5 hours, left at 5°C for 1 month, and then neutralized to pH 7.0 with an aqueous sodium hydroxide solution. The polymerization was completed to obtain polyorganosiloxane rubber latex-4. The polymerization rate of this polyorganosiloxane rubber was 88.4%, and the average particle size was 0.48 μm. [0062] The above polyorganosiloxane Rubber latex-4 to 11
After collecting 7 parts and adding 57.5 parts of distilled water, 5-12
Polymerization to form a composite rubber was carried out under the same conditions and method as in the production of. The average particle diameter of this composite rubber was 0.7 μm, and the gel content measured by the toluene extraction method in the same manner as in Example 1 was 94.3% by weight. This composite rubber latex
A mixed solution of 0.12 parts of ert-butyl hydroperoxide and 30 parts of styrene was added, and graft polymerization was carried out under the same conditions and method as in S-1. The graft copolymer latex thus obtained was coagulated, separated, and dried in the same manner as in Example 1 to obtain a dry powder of the graft copolymer (hereinafter referred to as 5-13). [0063] This composite rubber-based graft copolymer 5-13 was extruded at a cylinder temperature of 230°C, and the resulting pellets were molded using an injection molding machine (Promatsu Model 165/75: Sumitomo Heavy Industries, Ltd.) 230 A No. 1 dumbbell was molded at .degree. C. and its tensile modulus and gloss were measured, and the former was 5400 kg/cm2 and the latter was 47Z. This result shows that when the particle size of the composite rubber exceeds 0.6 μm, the value of tensile modulus cannot be lowered and the gloss deteriorates. [0064]

[Comparative Example 7] Production of mixed rubber graft copolymer 5-14: [006
5] 97 parts of n-butyl acrylate, 3 parts of allyl methacrylate, and 0.2 parts of tert-butyl hydroperoxide
A mixed solution consisting of 4 parts was emulsified in 195 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate had been dissolved in a separable flask equipped with a stirrer, and the mixture was purged with nitrogen. After that, the temperature was raised to 60°C, and a mixture of 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongarits), and 5 parts of distilled water was charged to start polymerization. Thereafter, polymerization was carried out at 70° C. for 2 hours to obtain poly n-butyl acrylate rubber latex. [0066] Next, 106 parts (solid content 35 parts) of the poly n-butyl acrylate rubber latex obtained by the above method and the polyorganosiloxane rubber latex Noxu 1 obtained in Example 1 were mixed into 1
17 parts of the mixed latex was placed in a separable flask equipped with a stirrer and heated to 70°C, and 0.001 parts of ferrous sulfate was added.
3 parts, ethylenediaminetetraacetic acid disodium salt 0.00
Part 4. A mixed solution of 0.17 parts of Rongarit) and 5 parts of distilled water was charged. After that, a mixture of 30 parts of styrene and 0.12 parts of tert-butyl hydroperoxide was heated at 70°C for 15 minutes.
The mixture was added dropwise over a period of minutes, and then maintained at 70° C. for 4 hours to perform graft polymerization onto the mixed rubber of polyorganosiloxane rubber and poly-n-butyl acrylate rubber. The polymerization rate of styrene was 92.6%. The obtained graft copolymer latex was dropped into 300 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and heated to 75°C.
and dried for 16 hours to form a mixed rubber-based graft copolymer (hereinafter referred to as
98 parts of dry powder (referred to as 5-14) was obtained. [0067] This composite rubber-based graft copolymer 5-14 was extruded at a cylinder temperature of 230° C., and the resulting pellets were molded using an injection molding machine (Promatsu Model 165/75: Sumitomo Heavy Industries, Ltd.) 230 A No. 1 dumbbell was molded at ℃, the tensile modulus and gloss were measured, and each was 5300 kg/cm2.45.
I got a result of '4. This result shows that unless the polyorganosiloxane rubber and poly n-butyl acrylate rubber are combined, the tensile modulus cannot be lowered and the gloss of the impact-resistant resin also deteriorates. [0068]

[Comparative Example 8] Production of acrylic rubber-based graft copolymer 5-15: [0
[069] A mixed solution consisting of 58.8 parts of n-butyl acrylate, 1.8 parts of allyl methacrylate, and 0.1 part of tert-butyl hydroperoxide was emulsified in 120 parts of distilled water in which 2 parts of dodecylbenzenesulfonic acid was dissolved. After purging with nitrogen, the temperature was raised to 60°C, and a redox radical initiator was added to initiate polymerization. After the polymerization of butyl acrylate was completed, a mixed solution consisting of 40 parts of styrene and 0.1 part of tert-butyl peroxide was added dropwise to carry out graft copolymerization. After the graft polymerization was completed, coagulation, washing, and drying were performed to obtain a graft copolymer (S-15). [0070] This composite rubber-based graft copolymer 5-15 was extruded at a cylinder temperature of 230°C, and the resulting pellets were molded using an injection molding machine (Promatsu Model 165/75: Sumitomo Heavy Industries, Ltd.) 230 The tensile modulus and gloss measured by molding a No. 1 dumbbell at ℃ were 7300 kg/cm2 and 81X. From these results, it can be seen that the rubber graft polymer made only of n-butyl acrylate has a high tensile modulus and does not exhibit good impact resistance (XJ). [0071]

[Example 6] An example will be shown in which the impact resistant resins produced in Examples 1 to 5 and Comparative Examples 1 to 8 were used as impact resistance modifiers of modified PPE resins. [0072] Each of the graft copolymers S-1 to S-1O8-12 to 5-15 prepared in Examples 1 to 5 and Comparative Examples 1 to 8 was 9.0
Weight % and reduced viscosity (ηsp) measured in chloroform
/ C) is 0.59 dl/g poly(2,6-dimethyl-1,4-phenylene) ether 43.7% by weight and the melt index at 200°C is 30 g/g at a load of 5 kg.
A resin composition was prepared by blending 47.3% by weight of 10% polystyrene. Each of these resin compositions was supplied to a twin-screw extruder (manufactured by Unirna-Faudler Co., Ltd., model ZSK-30), melted and kneaded at a cylinder temperature of 280°C, and after drying each pellet, an injection molding machine (manufactured by Awa-sama Seisakusho, 5J- 35 type) and injection molded at a cylinder temperature of 280°C and a mold temperature of 60°C to obtain various test pieces. Table 2 shows the results of evaluating various physical properties using these various specimens. [0073]

Table 21 [0074] In Experiment Nos. 1 to 6, the tensile modulus of the graft copolymer was 3500 kg/cm2 or less, and when it was made into a modified PPE resin composition, it exhibited excellent impact resistance. However, when the polyorganosiloxane and polybutyl acrylate in Experiment Nos. 7 to 14 were not made into a composite rubber, the tensile modulus of the graft copolymer was high, and the impact resistance of the resin composition deteriorated. Or, it can be seen that the gloss has decreased and the product is defective. [0075] [Effects of the Invention] As detailed above, the composite rubber-based graft copolymer of the present invention can be added to various resins without causing delamination.
Its industrial value is extremely great because it can provide molded products with excellent impact resistance, heat resistance, mechanical strength, and surface appearance, and can also be used as a resin composition with excellent moldability and fluidity.

Claims (1)

[Claims] Claim 1: 1) 10 to 90% by weight of polyorganosiloxane rubber component
and 90 to 10% by weight of a polyalkyl (meth)acrylate rubber component obtained by polymerizing an alkyl (meth)acrylate, a crosslinking agent for polyalkyl (meth)acrylate rubber, and a grafting agent for polyalkyl (meth)acrylate rubber. A composite having an average particle diameter of 0.08 to 0.6 μm, which has a structure in which they are intertwined with each other so that they cannot be separated, and the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component is 100% by weight. 1. A composite rubber-based graft copolymer comprising rubber and one or more vinyl monomers graft-polymerized.