JPH0830102B2 - Composite rubber-based graft copolymer particles - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite rubber-based graft copolymer particle which is extremely useful as an impact resistance improver. More specifically, it is added to various resins so as not to cause delamination, and to have high impact resistance and heat resistance. TECHNICAL FIELD The present invention relates to a composite rubber-based graft copolymer particle capable of giving a molded article having excellent properties, mechanical strength and surface appearance, and capable of providing a resin composition having excellent moldability and fluidity.

[0002]

2. Description of the Related Art Impact resistance improvers are for imparting impact resistance to various resins, and various kinds have been proposed to date.
For example, a glass transition temperature (Tg) as an impact resistance improver
It is well known that a polybutadiene elastomer having a low viscosity is grafted with a polymerizable monomer. However, such a polybutadiene elastomer is thermally unstable because an unsaturated bond remains in the elastomer,
Practical and excellent thermal stability has not been obtained.

Further, an impact resistance improver comprising a graft copolymer obtained by grafting a polymerizable monomer onto an acrylic rubber having a relatively high Tg is also known, but the effect of improving the impact resistance is not so remarkable.

Furthermore, a polyorganosiloxane rubber-based graft copolymer obtained by grafting a polymerizable monomer on a silicone rubber having a low Tg is disclosed in JP-A-60-252613, and although it has an effect of improving impact resistance to some extent,
There is a problem that a higher improvement effect is required and that the resin to which this is added is inferior in surface gloss.

[0005]

In view of such a situation, the present inventors have added impact resistance superior to conventional ones by adding it to a resin without significantly reducing the surface gloss of the resin. As a result of diligent study on various impact resistance improvers,
A composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer with high efficiency onto a composite rubber in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated The present invention has been accomplished by finding that it can be an impact resistance improver that improves impact resistance without deteriorating the surface appearance.

That is, the gist of the present invention is that the polyorganosiloxane rubber component is 10 to 90% by weight, and the alkyl (meth) is
90% to 10% by weight of a polyalkyl (meth) acrylate rubber component obtained by polymerizing an acrylate, a cross-linking agent for a polyalkyl (meth) acrylate rubber, and a graft crossing agent for a polyalkyl (meth) acrylate rubber are separated from each other. One or more types of composite rubber having an entangled structure and having an average particle diameter of 0.08 to 0.6 μm in which the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component is 100% by weight. The composite rubber-based graft copolymer particles are obtained by graft-polymerizing a vinyl-based monomer.

Instead of the above-mentioned composite rubber, one or more of polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber is used as a rubber source, and one or more vinyl monomers are added to the rubber source. It does not become an excellent impact resistance improver even if it is grafted with, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated, and a composite rubber is obtained. It becomes an excellent impact modifier only when used as a rubber source.

Further, when the polyorganosiloxane rubber component in the composite rubber exceeds 90% by weight, the surface appearance of the molded product from the composition obtained by adding the graft copolymer using the composite rubber to the resin is deteriorated. On the contrary, when the polyalkyl (meth) acrylate rubber component exceeds 90% by weight, the effect of improving the impact resistance of the obtained graft copolymer is lowered.
Therefore, as the composite rubber used in the present invention, the two rubber components constituting the composite rubber are both 10 to 90% by weight.
It is necessary to be in the range of (total amount of both rubber components 100% by weight), and preferably in the range of 20 to 80% by weight.

The average particle size of the composite rubber is 0.08 to
It must be in the range of 0.6 μm. If the average particle size is less than 0.08 μm, the effect of improving the impact resistance of the resulting graft copolymer 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 is obtained. The surface appearance of the molded product obtained from the composition obtained by adding the resin to the resin deteriorates. The emulsion polymerization method is most suitable for producing a composite rubber having an average particle diameter within the above range. First, a latex of polyorganosiloxane rubber is prepared, and a monomer for synthesizing a polyalkyl (meth) acrylate rubber is prepared. In addition to this latex, it is preferable to impregnate the polyorganosiloxane rubber particles in the latex before polymerizing these monomers.

The polyorganosiloxane rubber component constituting the composite rubber is a cross-linking agent for organosiloxane and polyorganosiloxane rubber (hereinafter referred to as cross-linking agent (I)).
It can also be prepared by emulsion polymerization using a polyorganosiloxane rubber graft crossing agent (hereinafter referred to as graft crossing agent (I)).

Examples of the organosiloxane include cyclic organosiloxanes having 3 or more membered rings, and those having 3 to 6 membered rings are preferably used. Hexamethylcyclotrisiloxane as a specific example of a preferred cyclic organosiloxane,
Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane,
Tetramethyltetraphenylcyclotetrasiloxane,
Examples include octaphenylcyclotetrasiloxane,
These may be used alone or in admixture of two or more.
The amount of the cyclic organosiloxane used is preferably 50% by weight or more in the polyorganosiloxane rubber component,
It is more preferably 70% by weight or more.

As the cross-linking agent (I), a trifunctional or tetrafunctional silane cross-linking agent, that is, a silane compound having three or four alkoxy groups is used, and specific examples thereof include trimethoxymethylsilane and triethoxy. Examples include phenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. As the crosslinking agent (I), a tetrafunctional one is preferable, and tetraethoxysilane is particularly preferable among the tetrafunctional crosslinking agents. The amount of the crosslinking agent (I) used is 0.1 to 30% by weight in the polyorganosiloxane rubber component.

As the graft crossing agent (I), the following formula CH ₂ = CR ² -COO- (CH ₂ ) _p -SiR ¹ _n O _{(3-n) / 2} (I-1) CH ₂ = CH-SiR ¹ _n O _{(3-n) 2} (I-2) or HS- (CH ₂ ) _p -SiR ¹ _n O _{(3-n) / 2} (I-3) (wherein R ¹ is a methyl group, ethyl Group, propyl group or phenyl group, R ² is a hydrogen atom or a methyl group, n is 0, 1
Alternatively, 2 and p represent an integer of 1 to 6. The compound etc. which can form the unit represented by these are used.

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. The amount of the graft crossing agent (I) used is 0 to 10% by weight in the polyorganosiloxane rubber component.

As the method for producing the polyorganosiloxane rubber, for example, the methods described in US Pat. No. 2891920, US Pat. No. 3,294,725 and the like can be used. In the practice of the present invention, for example, a mixture of an organosiloxane and a crosslinking agent (I) and, if desired, a graft-linking agent (I) is mixed in the presence of a sulfonic acid-based emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. It is preferable to produce by a method of shear mixing with water using a homogenizer or the like. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid and the like in combination because it is effective in maintaining the polymer stably during the graft polymerization.

Next, the polyalkyl (meth) acrylate rubber component constituting the above polyorganosiloxane rubber is a cross-linking agent for alkyl (meth) acrylate and polyalkyl (meth) acrylate rubber (hereinafter referred to as cross-linking agent (I
I)) and a graft crossing agent for polyalkyl (meth) acrylate rubber (hereinafter referred to as graft crossing agent (II)).

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 hexyl methacrylate, 2-ethylhexyl methacrylate, alkyl methacrylates such as n-lauryl methacrylate, and n-butyl acrylate is preferably used.

Examples of the cross-linking agent (II) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

Examples of the graft crossing agent (II) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent (II). Crosslinking agent (II) and graft crossing agent (II)
Are used alone or in combination of two or more. The total amount of the crosslinking agent (II) and the graft crossing agent (II) used is 0.1 to 20 in the polyalkyl (meth) acrylate rubber component.
% By weight.

The polymerization of the polyalkyl (meth) acrylate rubber component is carried out by adding the above alkyl (meth) acrylate to the latex of the polyorganosiloxane rubber component neutralized by the addition of an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. ) An acrylate, a cross-linking agent (II) and a graft crossing agent (II) are added and impregnated into the polyorganosiloxane rubber particles, and then a normal radical polymerization initiator is allowed to act. As the polymerization progresses, a crosslinked network of polyalkyl (meth) acrylate rubbers entwined with each other in the crosslinked network of polyorganosiloxane rubber is formed, and a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component which are practically inseparable A composite rubber latex of is obtained. In implementing the present invention,
As the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate rubber component is n.
-A composite rubber having a repeating unit of butyl acrylate is preferably used.

The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are firmly entangled. Therefore, it cannot be extracted and separated with ordinary organic solvents such as acetone and toluene. Toluene is 9 for this composite rubber
80% by weight of gel content measured by extraction at 0 ° C for 12 hours
That is all. Used well.

As the vinyl-based monomer to be graft-polymerized on the composite rubber, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; methyl acrylate, Acrylic esters such as ethyl acrylate and butyl acrylate;
Various vinyl-based monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile may be used, and these may be used alone or in combination of two or more. Of these vinyl monomers, aromatic alkenyl compounds are preferable, and styrene is particularly preferable.

The ratio of the composite rubber to the vinyl monomer in the composite rubber-based graft copolymer is 30 to 95% by weight of the polyorganosiloxane-based rubber and the vinyl-based based on the weight of the graft copolymer. The amount of the monomer is preferably 5 to 70% by weight, and the polyorganosiloxane rubber is
More preferably, it is 40 to 90% by weight and the vinyl monomer is 10 to 60% by weight. If the vinyl-based monomer is less than 5% by weight, the dispersion of the graft copolymer in the resin is insufficient, and
If it exceeds 70% by weight, the effect of imparting impact resistance decreases, which is not preferable.

The composite rubber-based graft copolymer is obtained by adding the above vinyl-based monomer to the composite rubber latex and polymerizing the composite rubber-based graft copolymer latex obtained by radical polymerization technique in one step or in multiple steps. It can be separated and recovered by pouring it into hot water in which a metal salt such as calcium or magnesium sulfate is dissolved, and salting out and coagulating.

The composite rubber-based graft copolymer obtained in the present invention can be used as an impact resistant resin by itself, but when it is used in a mixture with various thermoplastic resins, it imparts a high impact resistance to these resins. It is useful as an impact resistance improver since it does not deteriorate the surface appearance of the resin.

The thermoplastic resin which can be added with the composite rubber-based graft copolymer to improve the impact resistance is a mixture of polyphenylene ether resin and polystyrene resin, polycarbonate resin and / or polyester resin, and aromatic resin. 70 to 100% by weight of at least one vinyl monomer selected from the group consisting of alkenyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters
And a homopolymer or a copolymer obtained by polymerizing 0 to 30% by weight of another vinyl-based monomer copolymerizable therewith.

Examples of the method for adding the graft copolymer of the present invention to a resin include a method of mechanically mixing and shaping into pellets using a known apparatus such as a Banbury mixer, a roll mill, a twin-screw extruder. You can Extruded pellets can be molded in a wide temperature range,
A normal injection molding machine is used for molding.

Further, if necessary, stabilizers, plasticizers, lubricants, flame retardants, pigments, fillers and the like may be added to the resin composition. 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 flame retardants such as decabromobiphenyl and decabromobiphenyl ether. Flame retardants, flame retardants such as antimony trioxide; pigments such as titanium oxide, zinc sulfide and zinc oxide; fillers such as glass fiber, asbestos, wollastonite, mica and talc.

[0029]

The present invention will be specifically described with reference to the following examples.

In the following description, all "parts" mean parts by weight.

The methods for measuring various physical properties in the respective examples and comparative examples are as follows. Tensile Modulus-By the method of ASTM D-638. Gloss-By the method of ASTM D-523-62T (600 specular gloss). Bending strength-according to the method of ASTM D-790. Izod impact strength-By the method of ASTM D-256. (With 1/4 "notch) Vicat softening temperature-By the method of ISO R306.

[0032]

Example 1 Production of composite rubber-based graft copolymer (S-1): 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane are mixed. Then, 100 parts of a siloxane mixture was obtained. The mixed siloxane 10 was added to 200 parts of distilled water in which 1 part each of dodecylbenzene sulfonic acid and sodium dodecylbenzene sulfonate was dissolved.
After adding 0 part and preliminarily stirring at 10,000 rpm with a homomixer, the mixture was emulsified and dispersed with a homogenizer at a pressure of 300 kg / cm ² to obtain an organosiloxane latex.
This mixture was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C for 5 hours while stirring and mixing, and then allowed to stand at 20 ° C, and 48 hours later, the pH of the latex was adjusted to 6.9 with an aqueous sodium hydroxide solution. Polyorganosiloxane rubber latex (hereinafter referred to as polyorganosiloxane rubber latex-1)
I got The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the average particle size of the polyorganosiloxane rubber was 0.16 μm.

117 parts of the above polyorganosiloxane rubber latex-1 was collected, placed in a separable flask equipped with a stirrer, 57.5 parts of distilled water was added, and the atmosphere was replaced with nitrogen.
The temperature was raised to 50 ° C., a mixed solution of 33.95 parts of n-butyl acrylate, 1.05 part of allyl methacrylate and 0.26 part of ter-butyl hydroperoxide was charged and stirred for 30 minutes, and this mixed solution was permeated into the polyorganosiloxane rubber particles. Then, a mixed solution of 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongalit and 5 parts of distilled water was charged to start radical polymerization, and then the internal temperature was changed.
It was kept at 70 ° C. for 2 hours to obtain a composite rubber latex. A part of this latex was sampled and the average particle size of the composite rubber was measured to be 0.19 μm. The latex was dried to obtain a solid, which was extracted with toluene at 90 ° C for 12 hours, and the gel content was measured and found to be 97.3% by weight. To this composite rubber latex, tert-butyl hydroperoxide 0.1
A mixed solution of 2 parts and 30 parts of styrene was added dropwise over 15 minutes, and then held at 70 ° C. for 4 hours to carry out graft polymerization on the composite rubber. The polymerization rate of styrene was 91.5%.
The obtained graft copolymer latex was added to calcium chloride.
Dropped in 200 parts of 1.5% by weight of hot water, coagulated, separated, washed, and dried at 75 ° C. for 16 hours to obtain 97.8 parts of a dry powder of a composite rubber graft copolymer (hereinafter referred to as S-1). It was

This composite rubber-based graft copolymer S-1 was extruded at a cylinder temperature of 230 ° C. and shaped, and the obtained pellets were injected into an injection molding machine (Promat 165/75 type:
Sumitomo Heavy Industries Ltd. Molded No. I dumbbell at 230 ° C and measured tensile elastic modulus and gloss, the tensile elastic modulus was 260.
It was 0 kg / cm ² and the gloss was 89%.

[0035]

Example 2 Production of composite rubber-based graft copolymer (S-2):

2 parts of tetraethoxysilane and 98 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of mixed siloxane. The mixed siloxane 10 described above was added to 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were dissolved.
0 parts was added, and pre-dispersion with a homomixer and emulsification and dispersion with a homogenizer were performed in the same manner as in the production of S-1.
After heating at 80 ℃ for 5 hours, leave it at 20 ℃ for 48 hours, neutralize the PH of the latex to 6.9 with sodium hydroxide aqueous solution to obtain polyorganosiloxane rubber latex (hereinafter referred to as polyorganosiloxane rubber latex-2). Obtained. The polymerization rate of the obtained polyorganosiloxane rubber is 8
It was 8.9% and the average particle diameter was 0.16 μm.

117 parts of the above polyorganosiloxane rubber latex-2 was collected, 57.5 parts of distilled water was added, and then S-
33.95 parts of n-butyl acrylate as in the production of 1,
A mixed solution of 1.05 parts of allyl methacrylate and 0.26 parts of ter-butyl hydroperoxide was charged, and the polymerization of the composite rubber was carried out under the same conditions and method as in the production of S-1. The average particle size of this composite rubber was 0.20 μm, and the gel content measured by the toluene extraction method in the same manner as in Example 1 was 92.4% by weight.
Met. 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 carried out under the same conditions and method as for 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 a composite rubber-based graft copolymer (hereinafter referred to as S-2).
I got 7.6 copies.

This composite rubber-based graft copolymer S-2 was extruded at a cylinder temperature of 230 ° C. and shaped, and then the obtained pellets were injected into an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries Ltd.) 230. When a No. I dumbbell was molded at ℃ and the tensile modulus and gloss were measured, the tensile modulus was 2900 kg / cm ² and 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:

In the same manner as in Example 1 except that the polyorganosiloxane rubber latex-1 prepared at the time of producing the composite rubber-based graft copolymer S-1 was used and the components shown in Table 1 were used in predetermined amounts. Composite rubber latexes 3 to 6 were obtained.

A mixed liquid of 30 parts of styrene and 0.12 part of tet-butyl hydroperoxide was added to each composite rubber latex thus obtained, and a graft polymerization reaction was carried out on the composite rubber in the same manner as in Example 1 above, and the reaction was completed. Then, each latex obtained was coagulated, separated and dried in the same manner as in Example 1 above to obtain a composite rubber-based graft copolymer (hereinafter, S-3 to
A dry powder of S-6) was obtained.

[0042]

[Table 1]

This composite rubber-based graft copolymer S-3 to
6 was extruded at a cylinder temperature of 230 ° C. and shaped, and the obtained pellets were molded into a No. I dumbbell at 230 ° C. with an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries, Ltd.) to obtain a tensile modulus of elasticity. The gloss was measured and the results in Table 1 were obtained.

From Table 1, 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-based graft copolymer It can be seen that the gloss of the united body is lowered and it is not preferable.

[0045]

Example 5 Composite rubber-based graft copolymer S-7 to S-
Production of 8:

Polyorganosilosan rubber latex-1 prepared during the production of the composite rubber-based graft copolymer S-1
Was used to prepare two kinds of composite rubber-based graft copolymers having different amounts of styrene monomer used for graft polymerization.

That is, the siloxane rubber latex-1
Of 117 parts of distilled water and 200 parts of distilled water were put into a separable flask equipped with a stirrer, and after nitrogen substitution, the temperature was raised to 50 ° C., and 33.95 parts of n-butyl acrylate, 1.05 part of allyl methacrylate and ter-butyl were added. A mixed solution of 0.26 parts of hydroperoxide was charged and stirred for 30 minutes, and then ferrous sulfate 0.003 was added.
2 parts, ethylenediaminetetraacetic acid disodium salt 0.006 parts,
A mixed solution of 0.26 parts of Rongalit and 5 parts of distilled water was charged and polymerization was initiated to produce a composite rubber latex. The average particle size of this composite rubber was 0.19 μm, and the gel content measured by the toluene extraction method in the same manner as in Example 1 was 97.3% by weight. A mixed solution of 0.20 parts of tert-butyl hydroperoxide and 50 parts of styrene was added to this composite rubber latex.
Drop at 70 ° C for 15 minutes, then hold at 70 ° C for 4 hours,
The graft polymerization on the composite rubber was completed. After that, coagulation and drying treatment were performed in the same manner as in Example 1 to obtain a dry powder of a composite rubber-based graft copolymer (hereinafter referred to as S-7). Also, S-7 except that a mixed solution of 10 parts of styrene and 0.04 part of tert-butyl hydroperoxide was added to the above composite rubber latex.
Graft polymerization is performed in the same manner as in Example 1 and coagulation is performed in the same manner as in Example 1.
It was separated and dried to obtain a dry powder of a composite rubber graft copolymer (hereinafter referred to as S-8).

This composite rubber-based graft copolymer S-7 to
8 was extruded at a cylinder temperature of 230 ° C. and shaped, and the obtained pellets were molded into a No. I dumbbell at 230 ° C. with an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries, Ltd.) to obtain a tensile elastic modulus. When the gloss was measured, the tensile elastic modulus of S-7 was 3200.
kg / cm ² , gloss is 87%, S-8 tensile modulus is 2100
kg / cm ² , gloss was 81%.

[0049]

Comparative Example 3 Production of Composite Rubber-based Graft Copolymer S-9:

Polyorganosiloxane rubber latex-
117 parts of 1 was taken and put in a separable flask equipped with a stirrer together with 57.5 parts of distilled water, and after nitrogen replacement, the temperature was raised to 50 ° C., and a mixed solution of 33.95 parts of n-butyl acrylate and 0.26 part of tert-butyl hydroperoxide. Was charged and stirred for 30 minutes. Then, a mixed solution of the same amount of the redox initiator used in Example 1 was charged and emulsion polymerization was performed to obtain a rubber latex. Here, unlike Example 1, allyl methacrylate was not added. The average particle size of this rubber latex and the gel content measured by the toluene extraction method were 0.22 μm and 63% by weight, respectively. To this rubber latex, a mixed solution of 0.12 parts of tert-butyl hydroperoxide and 30 parts of styrene was added dropwise at 70 ° C for 15 minutes, and then held at 70 ° C for 4 hours to carry out graft polymerization. Example 1
Coagulation, separation and drying were carried out in the same manner as in 1. to obtain a dry powder of a graft copolymer (hereinafter referred to as S-9).

This composite rubber-based graft copolymer S-9 was extruded at a cylinder temperature of 230 ° C. and shaped, and the obtained pellets were injected into an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries Ltd.) 230 A No. I dumbbell was molded at ℃ and the tensile elastic modulus and gloss were measured and the results were 4300 kg / cm ² and 61%, respectively. The value of the tensile elastic modulus could not be lowered and the surface gloss of the impact resistant resin was poor by simply graft-polymerizing the vinyl monomer to the polyorganosiloxane rubber in two steps.

[0052]

Comparative Example 4 Production of Composite Rubber-based Graft Copolymer S-10:

Polyorganosiloxane rubber latex-
117 parts of 1 was taken and put in a separable flask equipped with a stirrer together with 57.5 parts of distilled water, and after nitrogen substitution, a mixed solution of 35 parts of n-butyl acrylate, 30 parts of styrene and 0.26 part of tert-butyl hydroperoxide was prepared in Example 1. Polymerization was carried out by adding dropwise the same amount of the redox-type initiator mixture used in Step 30 at 70 ° C. for 30 minutes. After that, the mixture was kept at 70 ° C. for 4 hours to complete the polymerization, and then coagulated, separated and dried in the same manner as in Example 1 above to obtain a dry powder of a graft copolymer (hereinafter referred to as S-10).

This composite rubber-based graft copolymer S-10
Was extruded at a cylinder temperature of 230 ° C and shaped, and the resulting pellets were molded into a No. I dumbbell with an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries, Ltd.) 230 ° C to obtain tensile elasticity and gloss. Was measured, and a result of 5100 kg / cm ² , 53% was obtained. The value of the tensile elastic modulus could not be lowered and the surface gloss of the impact resistant resin was poor by simply mixing the vinyl monomer in the polyorganosiloxane rubber and graft-polymerizing it.

[0055]

Comparative Example 5 Production of Composite Rubber-based Graft Copolymer S-12:

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. To 200 parts of distilled water in which 4 parts of dodecylbenzenesulfonic acid and 2 parts of sodium dodecylbenzenesulfonate were dissolved, 100 parts of the above-mentioned mixed siloxane was added, and pre-dispersion with a homomixer and emulsification with a homogenizer were carried out in the same manner as in the production of S-1. After heating at 80 ℃ for 5 hours, cool it at 20 ℃ for 48 hours.
Let stand for an hour, then add PH with sodium hydroxide solution to 7.
Neutralized to 0, polyorganosiloxane rubber latex-
3 was obtained. The polymerization rate of this polyorganosiloxane rubber is
89.6% and the average particle diameter was 0.05 μm.

117 parts of the above polyorganosiloxane rubber latex-3 was sampled, 57.5 parts of distilled water was added, and S was added.
N-butyl acrylate 33.95 as in the production of -1
Part, allyl methacrylate 1.05 parts and tert-butyl hydroperoxide 0.26 parts except that a mixed solution was charged, S-1
The composite rubber was polymerized in the same manner as in the production of. 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.
Met.

A mixed solution of 0.12 parts of tert-butyl hydrobell oxide and 30 parts of styrene was added to the obtained composite rubber latex, and graft polymerization was carried out 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 S-12).

This composite rubber-based graft copolymer S-12
Was extruded at a cylinder temperature of 230 ° C and shaped, and the resulting pellets were molded into a No. I dumbbell with an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries, Ltd.) 230 ° C to obtain tensile elasticity and gloss. Was measured to obtain a tensile elastic modulus of 4800 kg / cm ² and a gloss of 85%. 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 S-13:

Polyorganosiloxane rubber latex
Prepare 100 parts of the same mixed siloxane as in the production of 3 and add 200 parts of distilled water in which only 0.2 parts of dodecylbenzenesulfonic acid was dissolved, pre-stir with a homomixer at 10,000 rpm, and then with a homogenizer to 140 kg / It was emulsified at a pressure of cm ² to obtain an organosiloxane rubber latex. After heating this latex at 80 ° C for 5 hours, 5
After leaving it at ℃ for 1 month, PH with sodium hydroxide aqueous solution
The mixture was neutralized to 7.0 and 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.

117 parts of the above polyorganosiloxane rubber latex-4 was sampled, 57.5 parts of distilled water was added, and S was added.
Polymerization of composite rubber was carried out under the same conditions and method as those used in the production of -12. The average particle size of this composite rubber is 0.7 μm,
The gel content measured by the toluene extraction method in the same manner as in Example 1 was 94.3% by weight. In this composite rubber latex,
A mixed solution of 0.12 parts of tert-butyl hydroperoxide and 30 parts of styrene was added, and graft polymerization was carried out under the same conditions and method as for 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 S-13).

This composite rubber-based graft copolymer S-13
Was extruded at a cylinder temperature of 230 ° C and shaped, and the resulting pellets were molded into a No. I dumbbell with an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries, Ltd.) 230 ° C to obtain tensile elasticity and gloss. The result was 5400 kg / cm ² for the former and 47% for the latter. From this result, it is understood that when the particle diameter of the composite rubber exceeds 0.6 μm, the value of the tensile elastic modulus cannot be reduced and the gloss also deteriorates.

[0064]

[Comparative Example 7] Production of mixed rubber-based graft copolymer S-14:

97 parts of n-butyl acrylate, 3 parts of allyl methacrylate and tert-butyl hydroperoxide
A 0.24 part mixture was emulsified in 195 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate was dissolved in a separable flask equipped with a stirrer, and the atmosphere was replaced with nitrogen. Then, the temperature was raised to 60 ° C., 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongalit and 5 parts of distilled water were charged to initiate polymerization, and then at 70 ° C. for 2 minutes. Polymerization was carried out for a time to obtain a poly-n-butyl acrylate rubber latex.

Then, 106 parts of poly-n-butyl acrylate rubber latex (solid content: 35 parts) obtained by the above method and the polyorganosiloxane rubber latex obtained in Example 1-
1 117 parts of latex was placed in a separable flask equipped with a stirrer and heated to 70 ° C., and ferrous sulfate 0.0013 was added.
Parts, ethylenediaminetetraacetic acid disodium salt 0.004 parts,
A mixed solution of 0.17 part of Rongalit and 5 parts of distilled water was charged. Then, a mixed solution of 30 parts of styrene and 0.12 part of tert-butyl hydroperoxide was added dropwise at 70 ° C. for 15 minutes and then kept at 70 ° C. for 4 hours to obtain a polyorganosiloxane rubber and a poly n-butyl acrylate rubber. Graft polymerization on the mixed rubber was performed. Polymerization rate of styrene is 92.6%
Met. 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 then dried at 75 ° C. for 16 hours, and mixed rubber-based graft copolymer (hereinafter, 98 parts of dry powder of S-14) was obtained.

This composite rubber-based graft copolymer S-14
Was extruded at a cylinder temperature of 230 ° C and shaped, and the resulting pellets were molded into a No. I dumbbell with an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries, Ltd.) 230 ° C to obtain tensile elasticity and gloss. Was measured, and a result of 5300 kg / cm ² , 45% was obtained. From this result, it is understood that the tensile elastic modulus cannot be lowered unless the polyorganosiloxane rubber and the poly-n-butyl acrylate rubber are compounded, and the gloss of the impact resistant resin also deteriorates.

[0068]

[Comparative Example 8] Acrylic rubber-based graft copolymer S-15
Manufacturing of:

58.8 parts of n-butyl acrylate, 1.8 parts of allyl methacrylate and tert-butyl hydroperoxide
A mixed solution consisting of 0.1 parts was emulsified in 120 parts of distilled water in which 2 parts of dodecylbenzenesulfonic acid was dissolved, and after nitrogen substitution, 6
The temperature was raised to 0 ° C., and a redox radical initiator was added to initiate polymerization. After the polymerization of butyl acrylate was completed, a mixed solution containing 40 parts of styrene and 0.1 part of tert-butyl peroxide was added dropwise to carry out graft copolymerization. After completion of the graft polymerization, coagulation, washing and drying were carried out to obtain a graft copolymer (S-15).

This composite rubber-based graft copolymer S-15
Was extruded at a cylinder temperature of 230 ° C and shaped, and the resulting pellets were molded into a No. 1 dumbbell at 230 ° C using an injection molding machine (Promat 165/75 type: Sumitomo Heavy Industries, Ltd.), and the tensile modulus was measured. And gloss results were 7300 kg / cm ² and 81%. From this result, it is understood that the rubber graft polymer composed only of n-butyl acrylate has a high tensile elastic modulus and does not exhibit good impact resistance.

[0071]

Example 6 An example in which the impact resistant resins prepared in Examples 1 to 5 and Comparative Examples 1 to 8 are used as impact modifiers for the modified PPE resin is shown.

Graft copolymers S-1 to S-10, S-12 to S-1 prepared in Examples 1 to 5 and Comparative Examples 1 to 8
5 and 9.0% by weight respectively, and 43.7% by weight of poly (2,6-dimethyl-1,4-phenylene) ether having a reduced viscosity (ηsp / C) of 0.59 dl / g measured in chloroform.
And a melt index of 3 at 200 ° C with a load of 5 kg
0 g / 10 min of polystyrene and 47.3% by weight of polystyrene were each mixed to prepare a resin composition. A twin-screw extruder (manufactured by Werner Faudler Co., ZSK-30
Molds), melt and knead at a cylinder temperature of 280 ° C., dry each pellet, and then injection molding machine (Meiki Seisakusho, SJ
(-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 evaluation of various physical properties using these various test pieces.

[0073]

[Table 2]

In Experiment Nos. 1 to 6, the graft copolymer has a tensile elastic modulus of 3500 kg / cm ² or less, and when it is used as a modified PPE resin composition, it shows excellent impact resistance. But,
When the polyorganosiloxane of Experiment Nos. 7 to 14 and polybutyl acrylate are not made into a composite rubber, the tensile modulus of the graft copolymer is high and the impact resistance of the resin composition is deteriorated, or It can be seen that the gloss is lowered and it is defective.

[0075]

As described above in detail, the composite rubber-based graft copolymer particles of the present invention can be added to various resins without causing delamination, and have impact resistance, heat resistance, mechanical strength and surface appearance. Can give a molded product excellent in moldability and can be made into a resin composition excellent in moldability and fluidity, and therefore its industrial value is extremely large.

Claims (1)

[Claims] 1. A polyorganosiloxane rubber component 10-9.
Polyalkyl (meth) acrylate rubber component 90 obtained by polymerizing 0% by weight of an alkyl (meth) acrylate, a cross-linking agent for polyalkyl (meth) acrylate rubber and a graft crossing agent for polyalkyl (meth) acrylate rubber
0.08% to 10% by weight having 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. Composite rubber-based graft copolymer particles, wherein one or more vinyl-based monomers are graft-polymerized to a composite rubber of ˜0.6 μm.