JPH0525226A - Polyorganosiloxane graft copolymer - Google Patents

Abstract

PURPOSE:To provide a polyorganosiloxane graft copolymer which is excellent in impact resistance, low-temperature properties and weathering resistance and can give a molding very excellent in adhesion of coating film. CONSTITUTION:A polyorganosiloxane graft copolymer which is a graft copolymer prepared by grafting at least one ethylenically unsaturated monomer containing at least one epoxy vinyl monomer onto a composite rubber prepared by inseparably integrating a polyorganosiloxane rubber with a polyalkyl (meth) acrylate rubber and in which the content of the component derived from the epoxy vinyl monomer is 1-30wt.% based on the entire graft copolymer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to impact resistance, low temperature characteristics,
The present invention relates to a polyorganosiloxane-based graft copolymer that gives a molded article having excellent weather resistance and excellent adhesion strength of a coating film during coating.

[0002]

2. Description of the Related Art As a thermoplastic resin having excellent impact resistance, low temperature characteristics, and weather resistance, a polyorganosiloxane obtained by graft-polymerizing a monomer having an ethylenically unsaturated bond such as acrylonitrile or styrene onto polyorganosiloxane rubber. Siloxane-based graft copolymer is disclosed in JP-A-61-16061.
No. 4 is disclosed. Further, a graft copolymer obtained by graft-polymerizing a specific amount of an epoxy-containing vinyl monomer and another vinyl monomer onto a polyorganosiloxane-based polymer obtained by copolymerizing a graft crossing agent is disclosed in JP-A-2-138360.
No.

However, the above-mentioned Japanese Patent Laid-Open No. 61-10664.
Although the copolymer disclosed in No. 1 is excellent in impact resistance, low temperature characteristics and weather resistance, an organosiloxane oligomer is by-produced during the production of this copolymer, and it is extremely difficult to remove this oligomer from the copolymer. Have difficulty. When this copolymer is used for molding, the oligomer oozes out on the surface of the molded product, so that when the molded product from this copolymer is coated, the adhesion strength of the coating film is low. I have a problem. Further, the graft copolymer disclosed in JP-A-2-138360 is also excellent in impact resistance, low temperature characteristics and weather resistance, and further the adhesion of the coating film when a molded article of this copolymer is coated is considerably improved. However, it does not yet give a sufficient level, and there is a problem that the adhesion of the coating film becomes completely poor when the content of the polyorganosiloxane polymer in the graft copolymer becomes large.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides impact resistance,
It is an object of the present invention to provide a polyorganosiloxane-based graft copolymer which has excellent low-temperature properties and weather resistance, and further has excellent adhesion of a coating film when a molded article of this copolymer is applied.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, the present inventors have earnestly sought to obtain a resin having excellent impact resistance, low temperature characteristics, weather resistance, and excellent adhesion of a coating film of a coated molded article. As a result of the study, a composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are inseparably integrated with each other, and one or more ethylenes containing at least one epoxy group-containing vinyl monomer A graft copolymer obtained by graft-polymerizing a monomer having a polyunsaturated bond, wherein the polyorganosiloxane-based graft copolymer containing a component derived from an epoxy group-containing vinyl monomer in a specific ratio is described above. The present invention has been achieved by finding that all the performances of 1) are satisfied. Furthermore, this polyorganosiloxane-based graft copolymer is also useful as an adhesive, and particularly, it has excellent adhesion when laminating an aromatic polymer such as polyester such as polyethylene terephthalate, polyphenylene oxide or polyphenylene sulfide. It demonstrates its performance.

That is, according to the present invention, a composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are inseparably integrated with each other contains at least one epoxy group-containing vinyl monomer. A graft copolymer in which monomers having one or more ethylenically unsaturated bonds are graft-polymerized, and the ratio of the components derived from the epoxy group-containing vinyl-based monomer in the entire graft copolymer is 1 to It is a polyorganosiloxane-based graft copolymer characterized by being 30% by weight.

The present invention will be described in detail. As described above, the polyorganosiloxane-based graft copolymer of the present invention is a composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are inseparably integrated with each other, and Since the body is graft-polymerized, each of these components will be described in order.

1. Polyorganosiloxane Rubber Component The polyorganosiloxane rubber is a cross-linking agent for organosiloxane and polyorganosiloxane rubber [hereinafter, simply referred to as cross-linking agent (I)] and optionally a graft crossing agent for polyorganosiloxane rubber [hereinafter, simply graft cross-linking agent. And (I)] can be obtained as fine particles by emulsion polymerization.

As the organosiloxane used for preparing the polyorganosiloxane rubber, a cyclic organosiloxane having three or more membered rings is used, and one having 3 to 6 membered rings is preferably used. Examples of such cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
Examples thereof include trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane and the like.

The crosslinking agent (I) used for preparing the polyorganosiloxane rubber is a trifunctional or tetrafunctional silane, that is, a trialkoxyalkyl or aryl.
Rusilane or tetraalkoxysilane is used, and specific examples of such a crosslinking agent (I) include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. Can be illustrated. The cross-linking agent (I) used in the present invention is preferably tetraalkoxysilane, and tetraethoxysilane is particularly preferably used among the above.

The graft cross-linking agent (I) optionally used in the preparation of the polyorganosiloxane rubber has the following formula:

[0012]

[Chemical 1]

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

(Wherein 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 1 to 1).
Indicates an integer of 6. The compound etc. which can form the unit represented by these are used.

A unit represented by Chemical formula 1 can be formed (meta).
Acryloyloxyalkylsiloxane has a high grafting efficiency and therefore can efficiently form a grafted chain, which is advantageous from the viewpoint of developing impact resistance. Among the (meth) acryloyloxyalkylsiloxanes, methacryloyloxyalkylsiloxanes are preferable, and specific examples thereof include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, and γ- Examples thereof include methacryloyloxypropyltrimethoxydiethylsilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and δ-methacryloyloxybutyldiethoxymethylsilane.

Examples of the vinyl siloxane capable of forming the unit represented by Chemical formula 2 include vinylmethyldimethoxysilane and vinyltrimethoxysilane, and the mercaptosiloxane capable of forming the unit represented by Chemical formula 3 is γ-mercapto. Examples thereof include propyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldiethoxyethylsilane and the like. Further, as the compound capable of forming the unit represented by Chemical formula 4,
Examples thereof include p-vinylphenylmethyldimethoxysilane.

In the polyorganosiloxane rubber, the component derived from the cyclic organosiloxane is 60% by weight or more, preferably 70% by weight or more, and the amount of the component derived from the crosslinking agent (I) is 0.1 to 30% by weight. And the amount of the component derived from the graft crossing agent (I) is 0 to 10% by weight, and optionally 0.1 to 10% by weight.

In producing the latex of the polyorganosiloxane rubber component, for example, US Pat. No. 2891 is used.
The methods described in No. 920, No. 3294725, etc. can be used. In the practice of the present invention, a mixed solution of an organosiloxane, a cross-linking agent (I) and, if desired, a graft crossing agent (I) is added in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid, for example, a homogenizer. It is preferably produced by a method of shear mixing with water by using, for example. As the sulfonic acid-based emulsifier, alkylbenzene sulfonic acid is preferably used because it acts as an emulsifier of organosiloxane and at the same time acts 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, or the like, because it is effective in maintaining the emulsion state of the polymer stably during the graft polymerization.

2. Polyalkyl (meth) acrylate rubber component The polyalkyl (meth) acrylate rubber component constituting the composite rubber is an alkyl (meth) acrylate shown below and a crosslinking agent for polyalkyl (meth) acrylate rubber [hereinafter, It can be synthesized using a cross-linking agent (II)] and a graft crossing agent for polyalkyl (meth) acrylate rubber [hereinafter, simply referred to as graft crossing agent (II)]. Examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and other alkyl acrylates, and hexyl methacrylate. -, 2-ethylhexyl methacrylate, n-lauryl methacrylate and the like can be exemplified, and it is preferable to use n-butyl acrylate as the alkyl (meth) acrylate.

As the crosslinking agent (II), a polyfunctional (meth) acrylate can be used, and ethylene glycol dimethacrylate and propylene glycol dimethacrylate can be used.
1,3-butylene glycol dimethacrylate,
Specific examples thereof include 1,4-butylene glycol dimethacrylate and allyl methacrylate.

As the graft crossing agent (II), compounds having two kinds of unsaturated groups having different reactivities are used. Examples of such compounds are allyl methacrylate, triallyl cyanurate and triallyl. An isocyanurate etc. can be mentioned. (Although triallyl cyanurate and triallyl isocyanate have the same reactivity of three allyl groups, the second and third allyl groups after the reaction of the first allyl group are the same. Since the reactivity when reacts with is different from the reactivity when the first allyl group reacts,
It can be regarded as having an unsaturated group having different reactivity. Further, in the case of allyl methacrylate, the less reactive one of the two unsaturated groups reacts during one-part polymerization to act as a cross-linking site, and these all do not react during the polymerization. Therefore, the remaining unsaturated groups act as graft sites during the subsequent graft polymerization. )

These cross-linking agents (II) and graft crossing agents (II) can be used alone or in combination of two or more kinds. It is to be noted that allyl methacrylate serves both functions, that is, polyalkyl (meth) acrylate.
It is preferable to use allyl methacrylate as the crosslinking agent and the graft crossing agent for the rubber.

The amounts of these cross-linking agent (II) and graft cross-linking agent (II) used are respectively polyalkyl (meth) acrylate.
It is 0.1 to 10% by weight in the rubber component. Cross-linking agent (II)
And allyl methacrylate as a graft crossing agent (II)
When used in an amount of 0.2 to 20% by weight in the polyalkyl (meth) acrylate rubber component, the effect of not using any other crosslinking agent (II) or graft crossing agent (II) is obtained.

3. Composite rubber Composite rubber is a polyorganosiloxane rubber latex containing the above alkyl (meth) acrylate and a crosslinking agent (II).
And a graft crossing agent (II) are added and polymerized to form a polyalkyl (meth) acrylate rubber component. The addition at this time may be a batch addition or a drop addition to the polymerization system. As the polymerization progresses, the polyalkyl (mer) acrylate rubber component and the polyorganosiloxane rubber component are entangled with each other at the interface between them to form an integrated crosslinked network, and a grafting agent (I) is used for the polymerization of the polyorganosiloxane rubber component. 2) is used, grafting of the polyalkyl (meth) acrylate rubber component to the polyorganosiloxane rubber component also occurs, and in any case, a composite rubber latex in which both rubber components are substantially inseparable from each other is obtained.

In this composite rubber, the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are partially entangled and integrated, and since they are crosslinked in that state, they are extracted with an ordinary organic solvent such as acetone or toluene. It cannot be separated. In the composite rubber used in the present invention, the component derived from the cyclic organosiloxane of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the alkyl (meth) acrylate of the polyalkyl (meth) acrylate rubber component is n. -Butyl acrylate is preferred.

The composite rubber used in the present invention includes a polyorganosiloxane rubber component of 1 to 99% by weight and a polyalkyl (meth) acrylate rubber component of 99 to 1% by weight.
% Is used so that the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component is 100% by weight.

When a polyorganosiloxane rubber component exceeding 99% by weight is used as the composite rubber, the adhesion strength of the coating film to the molded article obtained by molding the obtained graft copolymer is lowered, and the polyalkyl (meth) is also used. If the acrylate rubber component exceeds 99% by weight, the resulting graft copolymer has low impact resistance. Therefore, as the composite rubber used in the present invention, both of the two rubber components constituting the composite rubber must be in the range of 1 to 99% by weight (however, the total amount of both rubber components is 100% by weight). Preferably, the polyorganosiloxane rubber component is 5 to 80% by weight, and the polyalkyl (meth) acrylate rubber component is 95 to 20% by weight.

The composite rubber as a constituent of the present invention is preferably produced by an emulsion polymerization method. First, a polyorganosiloxane rubber is prepared by an emulsion polymerization method, and then, in the presence of this polyorganosiloxane rubber latex. It is preferable to emulsion-polymerize a monomer for synthesizing an alkyl (meth) acrylate rubber. The composite rubber thus obtained can be graft-copolymerized with a monomer having an ethylenically unsaturated bond, particularly a vinyl-based monomer.

4. Graft Copolymer The polyorganosiloxane-based graft copolymer of the present invention is a monomer having one or more ethylenically unsaturated bonds containing at least one epoxy group-containing vinyl monomer in the above composite rubber. Is obtained by graft polymerization.
In this graft copolymer, the component derived from the epoxy group-containing vinyl-based monomer is 1 to 1 in the graft copolymer.
The content is 30% by weight, preferably 2 to 30% by weight. Then, if the component derived from the epoxy group-containing vinyl-based monomer is contained in the above-mentioned amount, a monomer having an ethylenically unsaturated bond other than the epoxy group-containing vinyl-based monomer is graft-polymerized together. You may let me.

As the epoxy group-containing vinyl monomer,
Glycidyl methacrylate, glycidyl acrylate,
Vinyl glycidyl ether, allyl glycidyl ether, hydroxyalkyl (meth) acrylate glycidyl ether, polyalkylene glycol (meth) acrylate glycidyl ether, glycidyl itacone
And the like, which can be used alone or
Used in combination of two or more species. Of these, glycidyl methacrylate is more preferably used.

Examples of the monomer having an ethylenically unsaturated bond which can be copolymerized with the epoxy group-containing vinyl monomer include styrene, halogen-substituted styrene, α-methylstyrene,
Aromatic alkenyl compounds such as vinyltoluene and vinylpyridine Methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; acrylonitrile and methacrylic acid. Vinyl cyanide compounds such as ronitrile can be exemplified, and these can be used alone or in combination of two or more kinds.

In the graft copolymer, the proportion of the components derived from the grafted monomer having an ethylenically unsaturated bond is 5 to 95% by weight when the weight of the graft copolymer is 100%. Preferably, 10-90
More preferably, it is 10% by weight, and most preferably 10% by weight.

The polyorganosiloxane-based graft copolymer of the present invention has an average particle size of 0.08-0.
It is preferably in the range of 6 μm, and the average particle diameter is 0.
When it is less than 08 μm, it becomes difficult to obtain sufficient impact strength, and when it is more than 0.6 μm, the surface appearance of the molded product from the obtained copolymer may be deteriorated. The polyorganosiloxane-based graft copolymer having such an average particle size is an emulsion graft of one or more monomers including an epoxy group-containing vinyl-based monomer in a single stage or multiple stages in the presence of the above composite rubber latex. It can be obtained by polymerization. When a monomer other than the epoxy group-containing vinyl-based monomer is also used as one or more kinds of monomers including the epoxy group-containing vinyl-based monomer, and the graft polymerization is performed in multiple stages, the epoxy group is used in the final stage. It is preferable to add a vinyl-based monomer.

In the graft polymerization, a component corresponding to a branch of the graft copolymer (here, a component derived from a monomer having one or more kinds of ethylenically unsaturated bonds including an epoxy group-containing vinyl monomer) is used. A so-called free polymer obtained by polymerizing alone with a branch component alone without grafting to a trunk component (composite rubber in this case) is also produced as a by-product and is obtained as a mixture of a graft copolymer and a free polymer. In the present invention, both of them are collectively referred to as a graft copolymer.

The polyorganosiloxane-based graft copolymer of the present invention is excellent in impact resistance, low temperature characteristics and weather resistance, and when it is molded and coated, the adhesion of the coating film becomes extremely excellent, Further, it is also useful as an adhesive and can be used for adhesion of metals such as aluminum, wood, paper, glass, etc., and adhesion of various structural laminated products, especially for adhesion of aromatic polymer molded products. It is useful as a melt type adhesive. Examples of the aromatic polymer include polyethylene terephthalate, polybutylene terephthalate,
Polyethylene terephthalate / isophthalate, polyethylene-2,6-naphthalene dicarboxylate, polyphenylene terephthalate, bisphenol A / terephthalic acid polycondensate, bisphenol A / terephthalic acid / isophthalic acid Aromatic polyester such as copolycondensate,
Examples include substituted or unsubstituted polyphenylene oxide and substituted or unsubstituted polyphenylene sulfide. Among these, polyethylene terephthalate, polybutylene terephthalate, substituted or unsubstituted polyphenylene oxide, and substituted or unsubstituted polyphenylene sulfide can be mentioned as preferable objects to be adhered by the graft copolymer of the present invention.

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following examples. In the examples and comparative examples, “parts” and “%” represent parts by weight and% by weight, unless otherwise specified.
In addition, the adhesion of the coating film is obtained by molding a flat plate, applying a two-component acrylic urethane paint (reaction product of tolylene diisocyanate and acrylic polyol) on the surface, and drying it to 1 mm on the coated surface. Make 10 vertical and horizontal cuts at intervals of 10
Adhesion of the coating film was evaluated by making 0 cross-cuts, adhering a cellophane adhesive tape thereto, and peeling the tape in the vertical direction to determine the number of peeled-off coating films. The number of peeled coating films was 10 or less, ⊚, 11 to 20 were ◯, 21 to 40 were Δ, and 41 or more were x.

Izod impact strength was measured according to ASTM D 256 using 1/4 "notched specimens.
Weather resistance is 1000 in a sunshine weather meter.
After exposure for a period of time, the change in color tone was visually evaluated, and those that did not change were evaluated as ◯, those that slightly yellowed were △, those that yellowed were ×.
And The average particle size is determined by the quasi-elastic light scattering method (MALVER
The latex was diluted with water according to N SYSTEM 4600, measurement temperature 25 ° C., scattering angle 90 °) to measure as a sample solution.

Example 1 (Preparation of polyorganosiloxane latex) 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. Got Sodium dodecylbenzene sulfonate and dodecylbenzene sulfonic acid 1 each
10 parts of the above-mentioned mixed siloxane in 200 parts of distilled water
Add 0 parts and use a homomixer at 10,000 rpm
After pre-stirring with a homogenizer, 300 Kg /
It was emulsified at a pressure of cm ² to obtain an organosiloxane latex. This latex was transferred to a separable flask equipped with a condenser and a stirring blade and stirred while mixing.
After heating at 0 ° C. for 5 hours and then standing at 20 ° C. for 48 hours, the polymerization is completed by neutralizing the pH of this latex to 7.0 with an aqueous sodium hydroxide solution, and the polyorganosiloxane latex (polyorganosiloxane) Latex-1) was obtained. The conversion rate of the obtained polyorganosiloxane rubber was 89.7%, and the average particle size of the polyorganosiloxane rubber was 0.16 μm.

(Preparation of Composite Rubber Latex) 150 parts of this polyorganosiloxane latex-1 was sampled and placed in a separable flask equipped with a stirrer, and distilled water 185
Parts, and after nitrogen substitution, the temperature was raised to 50 ° C., 45 parts of n-butyl acrylate, 0.9 parts of allyl methacrylate and tert-butyl hydroperoxide 0.10.
Eight parts of the mixture was added and stirred for 30 minutes to allow these components to penetrate into the polyorganosiloxane rubber particles. Then, a mixed solution of 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.108 part of Rongalit and 10 parts of distilled water was added thereto to carry out radical polymerization. Then, the internal temperature was kept at 70 ° C. for 2 hours to complete the polymerization and obtain a composite rubber latex. Butyl acryl
The polymerization rate of the rubber component was 98.8%.

(Production of Graft Copolymer) 40 parts of this composite rubber latex was sampled, 260 parts of distilled water and 0.5 part of sodium dodecylbenzenesulfonate were added thereto,
Glycidyl methacrylate 10 parts, acrylonitrile 2
After adding a mixed solution of 4 parts, 56 parts of styrene and 0.216 part of tert-butylhydroperoxide, the temperature was raised to 50 ° C. after nitrogen replacement, and further ferrous sulfate 0.001
Parts, ethylenediaminetetraacetic acid disodium salt 0.003
Solution, 0.108 parts of Rongalit and 10 parts of distilled water were added thereto to carry out radical polymerization. Then, the internal temperature was kept at 70 ° C. for 4 hours to complete the graft polymerization on the composite rubber. The polymerization rate of glycidyl methacrylate, acrylonitrile and styrene was 97.5%, and the average particle size of the graft polymer latex was 0.20 μm. The obtained graft copolymer latex was coagulated with an aqueous calcium chloride solution, filtered and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-1).

S-1 was extruded with an extruder having a barrel temperature of 230 ° C. to form pellets, which were then injected into an injection molding machine (Toshiba Machine Co., Ltd.).
Manufactured by IS-100), a flat plate of 100 mm × 100 mm × 3 mm was prepared at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. Degrease the surfaces of these plates with methanol,
It was painted with an acrylic urethane-based paint and a peeling test of the coating film was performed. Further, a test piece for impact strength evaluation was molded under the same injection condition, and impact resistance was evaluated. The results are shown in Table 1.

Example 2 As a monomer composition for graft polymerization on a composite rubber latex, a mixture of 10 parts of glycidyl methacrylate and 80 parts of styrene was used instead of 10 parts of glycidyl methacrylate, 24 parts of acrylonitrile and 56 parts of styrene. A polyorganosiloxane-based graft copolymer (hereinafter referred to as S-2) having an average particle size of 0.20 μm was obtained in the same manner as in Example 1 except for the above. The results of evaluating this graft copolymer in the same manner as in Example 1 are shown in Table 1.

Comparative Example 1 33 parts of the polyorganosiloxane latex-1 obtained according to Example 1 was sampled, 267 parts of distilled water and 0.5 part of sodium dodecylbenzenesulfonate were added thereto, and glycidyl methacrylic acid was further added. -10 parts, acrylonitrile 24 parts, styrene 56 parts and tert-butylhydroperoxide 0.216 parts were added, and after nitrogen substitution, the temperature was raised to 50 ° C, and further ferrous sulfate 0.001
Parts, ethylenediaminetetraacetic acid disodium salt 0.003
Solution, 0.108 parts of Rongalit and 10 parts of distilled water were added thereto, and radical polymerization was carried out. Then, the internal temperature was kept at 70 ° C. for 4 hours to complete the graft polymerization on the polyorganosiloxane rubber. Glycidyl methacrylate
And the polymerization rate of acrylonitrile and styrene are 96.3.
%, Average particle size of graft polymer latex 0.21 μm
Met. The obtained graft copolymer latex is coagulated with an aqueous calcium chloride solution, filtered and dried to give a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-3).
Got dry powder of. The results of evaluating S-3 in the same manner as in Example 1 are shown in Table 1.

Example 3 10 parts of glycidyl methacrylate and 24 parts of acrylonitrile as a monomer composition for graft polymerization on a composite rubber,
Glycidyl methacrylate 2 instead of 56 parts of styrene
An average particle size of 0.2 was obtained in the same manner as in Example 1 except that a mixture of 0 part, 21 parts of acrylonitrile and 49 parts of styrene was used.
A 0 μm polyorganosiloxane-based graft copolymer (hereinafter referred to as S-4) was obtained. The results of evaluating this graft copolymer in the same manner as in Example 1 are shown in Table 1.

Example 4 The amount of the composite rubber latex collected in the graft copolymerization on the composite rubber was 80 parts, and the amount of distilled water added thereto was 230.
Parts, glycidyl methacrylate 10 as a monomer composition
Parts, a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-5) was obtained in the same manner as in Example 1 except that a mixture of 21 parts of acrylonitrile and 49 parts of styrene was used. Evaluated. The results are shown in Table 1. The polymerization rate of glycidyl methacrylate, acrylonitrile, and styrene was 98.1%, and the average particle size of the graft copolymer latex was 0.21 μm.

Example 5 The amount of the composite rubber latex collected in the graft copolymerization on the composite rubber was 120 parts, and the amount of distilled water added thereto was 200.
Parts, glycidyl methacrylate 10 as a monomer composition
Parts, a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-6) was obtained in the same manner as in Example 1 except that a mixture of 18 parts of acrylonitrile and 42 parts of styrene was used. Evaluated. The results are shown in Table 1. The polymerization rate of glycidyl methacrylate, acrylonitrile and styrene was 98.1%, and the average particle size of the graft copolymer latex was 0.20 μm.

Comparative Example 2 Polyorganosiloxane latex-1 obtained in Example 1
99 parts of which was added 218 parts of distilled water and 0.5 part of sodium dodecylbenzenesulfonate, 10 parts of glycidyl methacrylate, 18 parts of acrylonitrile and 42 parts of styrene, and 0.216 of tert-butyl hydroxyperoxide. Part of the mixed solution was introduced to infiltrate these components into the polyorganosiloxane rubber particles, and after nitrogen substitution, the temperature was raised to 50 ° C., and further 0.001 part of ferrous sulfate was added,
0.003 parts of ethylenediaminetetraacetic acid disodium salt,
A mixture of 0.108 parts of Rongalit and 10 parts of distilled water was added to carry out graft polymerization on a polyorganosiloxane rubber. Then, the internal temperature was maintained at 70 ° C. for 4 hours to complete the graft polymerization, and a latex of a polyorganosiloxane-based graft copolymer was obtained. This was coagulated with an aqueous solution of calcium chloride, filtered, and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-7). This was evaluated in the same manner as in Example 1. The results are shown in Table 1. The polymerization rate of glycidyl methacrylate, acrylonitrile and styrene was 96.3%, and the average particle size of the graft copolymer latex was 0.20 μm.

Example 6 The amount of the composite rubber latex collected in the graft copolymerization on the composite rubber was 160 parts, and the amount of distilled water added to this was 170 parts.
Parts, glycidyl methacrylate 10 as a monomer composition
Parts, a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-8) was obtained in the same manner as in Example 1 except that a mixture of 15 parts of acrylonitrile and 35 parts of styrene was used. Evaluated. The results are shown in Table 1. The polymerization rate of glycidyl methacrylate, acrylonitrile and styrene was 98.1%, and the average particle size of the graft copolymer latex was 0.20 μm.

Example 7 In a graft copolymerization onto a composite rubber, the amount of the composite rubber latex collected was 200 parts, and the amount of distilled water added thereto was 140.
Parts, glycidyl methacrylate 10 as a monomer composition
Parts, a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-9) was obtained in the same manner as in Example 1 except that a mixture of 12 parts of acrylonitrile and 28 parts of styrene was used. Evaluated. The results are shown in Table 1. The polymerization rate of glycidyl methacrylate, acrylonitrile and styrene was 97.8%, and the average particle size of the graft copolymer latex was 0.18 μm.

Example 8 In a graft copolymerization onto a composite rubber, the amount of the composite rubber latex collected was 240 parts, and the amount of distilled water added thereto was 110.
Parts, glycidyl methacrylate 10 as a monomer composition
Parts, a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-10) was obtained in the same manner as in Example 1 except that a mixture of 9 parts of acrylonitrile and 21 parts of styrene was used. Evaluated. The results are shown in Table 1. The polymerization rate of glycidyl methacrylate, acrylonitrile and styrene was 98.2%, and the average particle size of the graft copolymer latex was 0.18 μm.

Comparative Example 3 200 parts of polyorganosiloxane latex-1 obtained in the same manner as in Example 1 was sampled and distilled water was added to 150 parts thereof.
Parts, 0.5 parts of sodium dodecylbenze sulfonate, 10 parts of glycidyl methacrylate, 9 parts of acrylonitrile and 21 parts of styrene, and 0.15 parts of tert-butyl hydroxyperoxide were charged, and these components were added to polyorgano After permeating into the siloxane rubber particles and replacing with nitrogen, the temperature was raised to 50 ° C.
Parts, ethylenediaminetetraacetic acid disodium salt 0.003
And 0.1 part of Rongalit and 10 parts of distilled water were added to carry out graft polymerization on the polyorganosiloxane rubber. Then, the internal temperature was maintained at 70 ° C. for 4 hours to complete the graft polymerization, and a latex of a polyorganosiloxane-based graft copolymer was obtained. This was coagulated with an aqueous solution of calcium chloride, filtered, and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-11). This was evaluated in the same manner as in Example 1. The results are shown in Table 1. The polymerization rate of glycidyl methacrylate, acrylonitrile and styrene was 96.5%, and the average particle size of the graft copolymer latex was 0.21 μm.

COMPARATIVE EXAMPLE 4 As a monomer composition to be graft-polymerized on a composite rubber latex, 10 parts of glycidyl methacrylate, 24 parts of acrylonitrile, and 56 parts of styrene were used instead of a mixture of 27 parts of acrylonitrile and 63 parts of styrene. A polyorganosiloxane-based graft copolymer (hereinafter referred to as S-12) was obtained in the same manner as in Example 1. The results of evaluating this graft copolymer in the same manner as in Example 1 are shown in Table 1.

[0055]

[Table 1]

In Table 1, PDMS is polydimethylsiloxane, PBA is polybutyl acrylate, GMA is glycidyl methacrylate, AN is acrylonitrile,
St represents styrene, respectively. In addition, N. B. Indicates that it was not destroyed.

Example 9 290 parts of the composite rubber latex obtained according to Example 1 was sampled, and after nitrogen substitution, the temperature was raised to 50 ° C., and 0.00025 parts of ferrous sulfate and disodium ethylenediaminetetraacetate were added. 0.0075 parts, Rongalit 0.025 parts, and distilled water 10 parts were added, and a mixture of glycidyl methacrylate 10 parts and tert-butyl hydroperoxide 0.024 parts was added dropwise over 30 minutes. Inner temperature 70
Graft polymerization on the composite rubber was carried out by holding at 4 ° C. for 4 hours. The obtained graft copolymer latex was coagulated with a calcium chloride aqueous solution, then filtered and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-13). The polymerization rate of glycidyl methacrylate is 9
8.5%, the average particle size of the graft polymer latex is 0.
It was 20 μm.

Two pieces of polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name: Lumina,
Scissors with a film thickness of 100 μm), 200 ° C., 10 Kg / cm
Thermocompression bonding was performed at ² for 10 minutes to prepare a three-layer sheet having an intermediate layer of 20 μm. A test piece having a width of 10 mm was cut out from this sheet and peeled at 180 ° at 23 ° C and 0 ° C to measure the interlayer adhesive strength. The results are shown in Table 2.

Example 10 210 parts of the polyorganosiloxane latex-1 obtained according to Example 1 was sampled, and the amount of distilled water added to this was 1
43 parts and the addition amount of n-butyl acrylate is 27
Parts, allyl methacrylate and tert-butyl hydroperoxide were added at 0.454 parts and 0.
The amount of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, and Rongalit was adjusted to 065 parts, and the addition amount was 0.00
A composite rubber latex was obtained in the same manner as in Example 1 except that 037 parts, 0.00111 parts and 0.089 parts were added, and 10 parts of glycidyl methacrylate and 0.024 part of tert-butyl hydroperoxide were added to the rubber latex. The mixed solution of was added dropwise over 30 minutes and the internal temperature was kept at 70 ° C. for 4 hours to complete the graft polymerization on the composite rubber. The polymerization rate of glycidyl methacrylate was 98.1%, and the average particle size of the graft polymer latex was 0.20 μm. The obtained graft copolymer latex was coagulated with a calcium chloride aqueous solution, then filtered and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-14).
The results of evaluating S-14 in the same manner as in Example 9 are shown in Table 2.

Example 11 The amount of polyorganosiloxane latex-1 collected was 90.
Parts, the addition amount of distilled water is 227 parts, n-butyl acrylate
, Allyl methacrylate and tert-butyl hydroperoxide were added at 63 parts, 1.26 parts and 0.151 parts, respectively, and the addition amounts of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and rongalit were each 0. .0
A dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-15) was obtained in the same manner as in Example 10 except that the amounts were 0073 parts, 0.0022 parts and 0.18 parts, and were carried out in the same manner as in Example 9. evaluated. The results are shown in Table 2.
The polymerization rate of glycidyl methacrylate is 97.2.
%, Average particle size of graft polymer latex 0.21 μm
Met.

Example 12 Example 9 except that the amount of the composite rubber latex collected was 360 parts and a mixture of 5 parts of glycidyl methacrylate and 5 parts of butyl acrylate was used instead of 10 parts of glycidyl methacrylate. Graft polymerization to a composite rubber is carried out in the same manner as described above to obtain a latex of a graft copolymer, which is coagulated with an aqueous solution of calcium chloride and then filtered and dried to give a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-16). Obtained). The polymerization rate of glycidyl methacrylate and butyl acrylate was 97.3%, and the average particle size of the graft polymer latex was 0.20 μm. S-1
Table 2 shows the results of evaluation of 6 in the same manner as in Example 9.

Example 13 Methyl methacrylate instead of 5 parts of butyl acrylate
A latex of a graft copolymer was obtained in the same manner as in Example 12 except that 5 parts of polyorganosiloxane-based graft copolymer (S-1) was used.
7) was obtained and evaluated in the same manner as in Example 9. The results are shown in Table 2. The polymerization rate of glycidyl methacrylate and methyl methacrylate was 97.
8%, average particle size of graft polymer latex is 0.21
was μm.

Example 14 The sampling amount of the composite rubber latex was 240 parts, and instead of 10 parts of glycidyl methacrylate, 20 parts of glycidyl methacrylate, 10 parts of butyl acrylate and 10 parts of methyl methacrylate were used. Using the mixture, graft polymerization was performed on the composite rubber in the same manner as in Example 9 except that the addition amount of tert-butylhydroperoxide was changed to 0.096 parts to obtain a latex of a graft copolymer, which was chlorinated. After coagulation with an aqueous calcium solution, it was filtered and dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (hereinafter referred to as S-18). The polymerization rate of glycidyl methacrylate, butyl acrylate and methyl methacrylate was 98.8%, and the average particle size of the graft polymer latex was 0.21 μm. The results of evaluating this in the same manner as in Example 9 are shown in Table 2.

Example 15 Table 2 shows the results of evaluation using the polyorganosiloxane graft copolymer S-6 obtained in Example 5 in the same manner as in Example 9.

Example 16 Table 2 shows the results of evaluation using the polyorganosiloxane graft copolymer S-8 obtained in Example 6 in the same manner as in Example 9.

Example 17 A latex of a graft copolymer was obtained in the same manner as in Example 13 except that 5 parts of glycidyl acrylate was used in place of 5 parts of glycidyl methacrylate, which was coagulated and filtered. Then, it was dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (referred to as S-19). The polymerization rate of glycidyl acrylate and methyl methacrylate is 97.2.
%, The average particle size of the graft copolymer latex is 0.21
It was μ. Table 2 shows the results of evaluations performed in the same manner as in Example 9.

Example 18 A latex of a graft copolymer was obtained in the same manner as in Example 13 except that 5 parts of diglycidyl itaconate was used instead of 5 parts of glycidyl methacrylate, and the latex was coagulated and filtered. Then, it was dried to obtain a dry powder of a polyorganosiloxane-based graft copolymer (referred to as S-20). The polymerization rate of diglycidyl itaconate and methyl methacrylate is 98.0.
%, The average particle size of the graft copolymer latex is 0.20
It was μ. Table 2 shows the results of evaluation performed in the same manner as in Example 9.

Comparative Example 5 A composite rubber latex obtained in the same manner as in Example 1 was used as 360
A part of the mixture was sampled, a mixed solution of 10 parts of methyl methacrylate and 0.024 part of tert-butyl hydroperoxide was added, and the mixture was kept at an internal temperature of 70 ° C. for 4 hours to perform graft polymerization on the composite rubber. The polymerization rate of methyl methacrylate is 98.
8%, average particle size of graft polymer latex is 0.20
was μm. The obtained latex was coagulated with an aqueous calcium chloride solution and then filtered and dried to obtain a polyorganosiloxane-based graft copolymer (referred to as S-21) as a dry powder. Table 2 shows the results of evaluation performed in the same manner as in Example 9.

Comparative Example 6 Ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., trade name Bondfast-E: S-2)
2) was used to prepare a 3-layer laminated sheet in the same manner as in Example 9 and evaluated in the same manner. The results are shown in Table 2.

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[Table 2]

[0071]

The polyorganosiloxane-based graft copolymer of the present invention is excellent in impact resistance, low temperature characteristics and weather resistance,
Further, the molded product can be coated with a coating film having extremely excellent adhesion strength.

Claims (1)

Claim: What is claimed is: 1. A composite rubber in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are inseparably integrated with each other and at least one epoxy group-containing vinyl monomer. Is a graft copolymer obtained by graft-polymerizing one or more monomers having an ethylenically unsaturated bond containing, and the ratio of components derived from the epoxy group-containing vinyl-based monomer in the entire graft copolymer. Is 1 to 30% by weight, a polyorganosiloxane-based graft copolymer.