JP2651447B2 - Polyorganosiloxane-based thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for efficiently grafting a vinyl monomer,
The present invention relates to a polyorganosiloxane-based thermoplastic resin composition having remarkably excellent slidability, abrasion resistance, weather resistance, cold resistance and impact resistance.

[Conventional technology]

Conventionally, a technique of modifying with a rubber has been established in order to improve the impact strength of a thermoplastic resin.

For example, an ABS resin in which styrene-acrylonitrile resin (AS resin) is reinforced with butadiene rubber, an AAS resin in which AS resin is reinforced with acrylic rubber, and the like.

Silicone rubber can be considered as such a base rubber component. However, simply blending a polyorganosiloxane and a thermoplastic resin results in poor compatibility between these components, resulting in an impact resistance of the resulting compound. Insufficient.
Therefore, a technique of grafting a vinyl monomer to rubber is required as in the case of an ABS resin. However, polyorganosiloxane generally has poor reactivity with a vinyl monomer, and it is difficult to form a graft copolymer. Several methods have been disclosed for forming such graft copolymers. For example, Japanese Patent Application Laid-Open No. 50-109282 proposes to improve the impact strength by polymerizing a vinyl monomer in the presence of a vinyl or allyl group-containing polyorganosiloxane to form a graft copolymer. Have been.

JP-A-52-130885 proposes a method for improving the impact strength of a vinyl polymer by using a mercapto group-containing polyorganosiloxane instead of a vinyl or allyl group-containing polyorganosiloxane.

Further, JP-A-60-252613, JP-A-61-106614
JP-A 61-136510 and JP-A-61-136510 have high graft efficiency and excellent impact strength by polymerizing a vinyl monomer in an emulsion of polyorganosiloxane containing an acryl or methacryl group. It has been proposed to obtain a graft copolymer.

[Problems to be solved by the invention]

However, when a polyorganosiloxane containing a vinyl group or an allyl group is used, or when a polyorganosiloxane containing a mercapto group is used, graft reactivity between the polyorganosiloxane and a vinyl monomer is poor. Accordingly, the apparent graft ratio calculated from the gel formation amount, that is, the ratio of the vinyl polymer grafted to the polyorganosiloxane is small.

Therefore, there is a problem that the interfacial adhesion between the polyorganosilicone and the vinyl polymer is low and delamination is remarkable, and as a result, a good appearance and sufficient impact strength cannot be obtained in the obtained graft copolymer.

In addition, when a polyorganosiloxane containing an acryl group or a methacryl group is used, the impact strength of the obtained graft copolymer is improved, but the glossiness is small and a sufficient appearance is not obtained. Since the point is an ester bond, ester decomposition occurs at a high temperature or under acidic or alkaline conditions, resulting in a remarkable decrease in the graft ratio, and there is a problem in high-temperature molding characteristics and chemical resistance.

The present invention has been made in view of the problems of the prior art, and has a composition comprising a polyorganosiloxane-based thermoplastic resin having excellent graft reactivity, weather resistance, cold resistance, sliding properties, and abrasion resistance. The purpose is to provide.

[Means for solving the problem]

The present invention provides a compound represented by the general formula R ¹ _n SiO _{(4-n) / 2} , wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and n is 0 to 3
90 to 99.8% by weight of an organosiloxane (I) having a structural unit represented by the following formula (hereinafter sometimes referred to as “component (I)”): (Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a graft-linking agent (II) having both an unsaturated group represented by and an alkoxysilyl group (hereinafter referred to as “component (II)”). 10 to 0.2% by weight [however, (I) + (I
I) = 100% by weight] and at least one vinyl monomer (IV) to the modified polyorganosiloxane (III) (hereinafter sometimes referred to as “component (III)”).
(Hereinafter sometimes referred to as “component (IV)”), a polyorganosiloxane containing 5% by weight or more of a graft copolymer (V) (hereinafter sometimes referred to as “component (V)”) obtained by graft polymerization. The present invention provides a thermoplastic resin composition (hereinafter, may be simply referred to as “thermoplastic resin”).

The organosiloxane (I) used in the present invention has a structural unit represented by the above general formula and has a linear, branched or cyclic structure, and is preferably an organosiloxane having a cyclic structure. is there.

Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane (I) include a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, and a substituted or unsubstituted halogen atom or cyano group. Examples include a hydrocarbon group.

In the average composition formula, the value of n is an integer of 0 to 3.

Specific examples of the organosiloxane (I) include, in addition to cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane, A chain or branched organosiloxane can be mentioned.

The organosiloxane (I) has a condensed, for example, polystyrene equivalent weight average molecule.
It may be about 500 to 10,000 polyorganosiloxane.

When the organosiloxane (I) is a polyorganosiloxane, its molecular chain ends are blocked with, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, or the like. May be.

Next, the graft crosslinking agent (II) used in the present invention comprises:
It is a compound having both an unsaturated group represented by the general formula and an alkoxysilyl group.

As R ^{2 in the} above general formula, a hydrogen atom or a carbon number 1 to
6 alkyl groups, but a hydrogen atom or a carbon number of 1 to 2
Is more preferred, and is more preferably a hydrogen atom or a methyl group.

Specific examples of these compounds include p-vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-
Vinylphenyl) ethylmethyldimethoxysilane, 2-
(M-vinylphenyl) ethylmethyldimethoxysilane, 2- (o-vinylphenyl) ethylmethyldimethoxysilane, 1- (p-vinylphenyl) ethylmethyldimethoxysilane, 1- (m-vinylphenyl) ethylmethyldimethoxysilane, 1- (o-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, 1- (p-vinylphenyl) -1,1-diphenyl-3-ethyl-3,3-diethoxydisiloxane, m-vinylphenyl- [ 3- (triethoxysilyl) propyl] diphenylsilane, [3- (p
-Isopropenylbenzoylamino) propyl] phenyldipropoxysilane and the like, and mixtures thereof.

As the grafting agent (II), p-vinylphenylmethyldimethoxysilane, 2- (m-vinylphenyl) ethylmethyldimethoxysilane, 2- (p-
Vinylphenyl) ethylmethyldimethoxysilane, 3-
(P-vinylbenzoyloxy) propylmethyldimethoxysilane, and more preferably p-vinylphenylmethyldimethoxysilane.

The proportion of the graft crosslinking agent used is (I) component and (I)
I) 0.2 to 10% by weight, preferably 0.5 to 10% by weight, based on the total amount of the components
If the amount is less than 0.2% by weight, a high graft ratio cannot be obtained in the graft polymerization of the resulting modified polyorganosiloxane (III) and the vinyl monomer (IV). As a result, the modified polyorganosiloxane (III) and The interfacial adhesive strength between the grafted vinyl polymers is reduced, delamination occurs, and the graft copolymer (V) cannot have sufficient impact strength.

On the other hand, when the proportion of the graft-linking agent (II) exceeds 10% by weight, the graft ratio increases, but the polymerization of the grafted vinyl polymer decreases with the increase of the graft-linking agent (II). Molecular weight, and as a result, a sufficient impact strength cannot be obtained.

The modified polyorganosiloxane (III) is obtained by shear-mixing the organosiloxane (I) and the graft-linking agent (II) with a homomixer or the like in the presence of an emulsifier such as an alkylbenzenesulfonic acid, and condensing the modified polyorganosiloxane (III). Can be manufactured. This emulsifier acts as an emulsifier for the organosiloxane (I) and also serves as a condensation initiator.

The amount of the emulsifier to be used is generally 0.1 to 5% by weight, preferably 0.1 to 5% by weight, based on the total amount of the components (I) and (II).
It is about 0.3 to 3% by weight.

The amount of water used at this time depends on the components (I) and (I)
The amount is usually 100 to 500 parts by weight, preferably 200 to 400 parts by weight, per 100 parts by weight of the component (I).

 The condensation temperature is usually 5 to 100C.

In the production of the modified polyorganosiloxane (III), in order to improve the impact resistance of the obtained resin, a third
A crosslinking agent may be added as a component. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, tetraethoxysilane, 1,3-bis [2- (dimethoxymethylsilyl) ethyl] benzene,
1,4-bis [2- (dimethoxymethylsilyl) ethyl]
Benzene, 1,3-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -3 Examples include tetrafunctional crosslinking agents such as-[2- (dimethoxymethylsilyl) ethyl] benzene and 1- [1- (dimethoxymethylsilyl) ethyl] -4- [2- (dimethoxymethylsilyl) ethyl] benzene. it can. The amount of the crosslinking agent to be added is usually 10% by weight or less, preferably 5% by weight, based on the total amount of the organosiloxane (I) and the graft crosslinking agent (II).
Below.

The weight average molecular weight in terms of polystyrene of the modified polyorganosiloxane (III) thus obtained is as follows:
Usually 30,000-1,000,000, preferably 50,000-300,000
It is about.

Next, the modified polyorganosiloxane (III) thus obtained is graft-polymerized with a vinyl monomer (IV), whereby the polyorganosiloxane-based thermoplastic resin of the present invention containing the graft copolymer (V) is obtained. Is obtained.

The vinyl monomer (IV) used in the present invention includes:
For example, styrene, α-methylstyrene, aromatic alkenyl compounds such as sodium styrenesulfonate; methacrylates such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, butyl methacrylate, allyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate; Acrylic acid esters such as hydroxyethyl methacrylate and dimethylaminoethyl methacrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; olefins such as ethylene and propylene; conjugated diolefins such as butadiene, isoprene and chloroprene; and vinyl acetate, vinyl chloride, Vinylidene chloride, triallyl isocyanurate, acrylic acid, methacrylic acid, N-phenyl Maleimide, N- cyclohexyl maleimide, include maleic anhydride, which are used alone or in combination.

Among these vinyl monomers (IV), 65-75% by weight of styrene and 65% by weight are used for the purpose of further improving the impact resistance of the polyorganosiloxane-based thermoplastic resin of the present invention.
Those containing 35 to 25% by weight of acrylonitrile are preferred.

The charge composition for graft polymerization of the vinyl monomer (IV) to the modified polyorganosiloxane (III) is as follows:
(III) component 5 to 80% by weight, preferably 10 to 60% by weight,
(IV) The component is 95 to 20% by weight, preferably 90 to 40% by weight (provided that (III) + (IV) = 100% by weight);
If the component is less than 5% by weight, sufficient impact strength cannot be obtained, while if it exceeds 80% by weight, the proportion of the vinyl polymer to be graft-bonded decreases, and as a result, between the modified polyorganosiloxane (III) and the vinyl polymer, Insufficient interfacial adhesive strength is obtained, resulting in poor appearance of the thermoplastic resin and reduction in impact strength.

The graft ratio of the graft copolymer (V) thus obtained is usually about 20% by weight or more, preferably about 80% by weight or more, and more preferably about 100% by weight or more. As described above, when the graft ratio of the graft copolymer (V) is high, the interfacial adhesive force between the graft copolymer (V) and the vinyl polymer that has not been directly grafted increases, so that The modified polyorganosiloxane (III) is uniformly dispersed, and a thermoplastic resin having a good appearance and excellent impact strength can be obtained.

Furthermore, the thermoplastic resin of the present invention contains, in addition to the graft copolymer (V) thus obtained, a vinyl polymer which is a polymer of a non-grafted vinyl monomer (IV). It contains 5% by weight or more, preferably 10% by weight or more of the graft copolymer (V).

In producing the thermoplastic resin of the present invention, the modified polyorganosiloxane (III) is added to the vinyl monomer (IV).
Is graft-polymerized by ordinary radical polymerization to obtain a composition containing the graft copolymer (V).

Here, depending on the type of the radical polymerization initiator, it is necessary to neutralize the latex of the modified polyorganosiloxane (III) which has been acidified by the alkylbenzene sulfonic acid as described above with an alkali. As the alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine, triethylamine and the like are used.

Examples of the radical polymerization initiator include an oxidizing agent composed of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide, a sugar-containing iron pyrophosphate formulation, a sulfoxysheet formulation, and a Redox initiators in combination with reducing agents such as a mixture of iron sugar pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, dimethyl-2, 2'-
Examples include azo compounds such as azobisisobutyrate and 2-carbamoylazaisobutyronitrile; and organic peroxides such as benzoyl peroxide and lauroyl peroxide. Preferred are the redox-based initiators.

The amount of the radical polymerization initiator used is usually 0.05 to 100 parts by weight of the vinyl monomer (IV) used.
It is about 5 parts by weight, preferably about 0.1 to 3 parts by weight.

The radical polymerization at this time is preferably carried out by emulsion polymerization or solution polymerization.

In the emulsion polymerization, a known emulsifier, the above-mentioned radical initiator, a chain transfer agent and the like are used.

Here, as the emulsifier, anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenylether disulfonate, sodium succinate dialkali ester sulfonate,
Alternatively, one or more nonionic emulsifiers such as polyoxyethylene alkyl ester and polyoxyethylene alkyl allyl ether can be used.

The amount of the emulsifier used is based on the vinyl monomer (IV).
Usually, it is about 0.5 to 5% by weight.

Examples of the chain transfer agent include t-dodecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan,
Mercaptans such as n-hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide are usually used in an amount of 0.02 to 1% by weight based on the vinyl monomer (IV).

In the emulsion polymerization, a radical polymerization initiator, an emulsifier,
In addition to chain transfer agents, various electrolytes and pH
Usually, 100 to 500 parts by weight of water and 100 parts by weight of water and 100 parts by weight of the radical polymerization initiator, emulsifier, chain transfer agent and the like are added to the vinyl monomer (IV) in an amount within the above range, together with an adjuster. Used, polymerization temperature 5-100 ° C, preferably 50-90 ° C
The emulsion polymerization is carried out at a temperature of 0.1 ° C. for a polymerization time of 0.1 to 10 hours.

In the case of emulsion polymerization, the organosiloxane (I)
It can also be carried out by adding a vinyl monomer (IV) and a radical initiator to a latex containing a modified organopolysiloxane (III), which is obtained by condensation of the polymer with a graft crosslinking agent (II).

On the other hand, in the case of solution polymerization, the modified polyorganosiloxane (III) and vinyl monomer (IV) are dissolved in an organic solvent, and a radical initiator, a chain transfer agent and, if necessary, various additives are added thereto. Polymerize.

Examples of the organic solvent used in the solution polymerization include toluene, n-hexane, cyclohexane, chloroform, tetrahydrofuran and the like.

In the case of solution polymerization, a vinyl monomer (IV) is used in combination with a radical polymerization initiator and, if necessary, a chain transfer agent.
With respect to 100 parts by weight, usually, the organic solvent is used in an amount of 80 to 500 parts by weight and the radical polymerization initiator, the chain transfer agent and the like in the above-mentioned range, and the polymerization temperature is 5 to 150 ° C., preferably 50 to 50 ° C.
Solution polymerization is carried out under the conditions of ~ 130 ° C and a polymerization time of 1 to 10 hours.

In the case of this solution polymerization, impurities can be significantly reduced as compared with the case of emulsion polymerization.

The polyorganosiloxane-based thermoplastic resin of the present invention,
When produced by emulsion polymerization, it is coagulated by a usual salt coagulation method, and the obtained powder is purified by washing with water and drying.

In the case of solution polymerization, after unreacted monomers and a solvent are distilled off by steam distillation, the resulting resin mass is finely crushed and dried to be purified.

The thermoplastic resin of the present invention containing the graft copolymer (V) obtained by these methods can be pelletized by a kneading machine such as an extruder.

At this time, depending on the required performance, other known polymers are usually appropriately blended in an amount of about 99% by weight or less, preferably about 90% by weight or less, and a thermoplastic resin composition (hereinafter simply referred to as “thermoplastic resin composition”) is used. Object).

Such polymers include, for example, polybutadiene,
Diene rubbers such as butadiene-styrene polymer, acrylonitrile-butadiene copolymer, polyisoprene and natural rubber; acrylic rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, chlorinated butyl rubber, chlorinated polyethylene Styrene rubber such as styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-
Aromatic vinyl-conjugated diene block copolymers such as butadiene-styrene radial tere block copolymers; hydrides of the block copolymers; polypropylene, polyethylene, polystyrene, styrene-acrylonitrile copolymers, rubber-reinforced polystyrene (HIPS ), Acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylenepropylene-styrene resin (AES
Resin), methyl methacrylate-butadiene-styrene resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin, acrylonitrile-n
-Butyl acrylate-styrene resin (AAS resin), polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutyl terephthalate, polyacetal, polyamide, epoxy resin, polyvinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer, PP
S resin, polyether ether ketone, PPO resin, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, rubber-modified PPO resin, styrene-maleimide copolymer, rubber-modified styrene-maleimide copolymer Coalescence, polyamide-based elastomer, polyester-based elastomer and the like.

The pelletized thermoplastic resin (composition) is processed and molded by ordinary means such as compression molding and injection molding.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified.

 In the examples, various measurement items were as follows.

That is, the graft ratio and the graft efficiency were determined by the following methods.

A constant weight (x) of the graft polymerization product is put into acetone, shaken for 2 hours with a shaker to dissolve the free copolymer, and centrifuged at 23,000 rpm for 30 minutes using a centrifuge. Separate to obtain insolubles. Next, it was dried at 120 ° C. for 1 hour using a vacuum drier to obtain an insoluble content weight (y), and the graft ratio and graft efficiency were calculated by the following equations.

The evaluation of the physical properties of the thermoplastic resin (composition) was performed according to the following evaluation method (a) or (b).

Evaluation method (b) * Drop weight impact strength Using a Dupont impact tester, R
= 1/2 ″ and dropped from a height of 50 cm, and the falling weight impact strength of a 3.2 mm Atsumi molded article was measured.

 The unit is kg · cm.

* Sliding characteristics In the friction and wear test, a Suzuki-type sliding tester was used, and the same material or steel (S45C) was used as a mating material. The test piece used was a hollow cylindrical one having an outer diameter of 25.6 mm and an inner diameter of 20.0 mm, and the mating member used was of the same shape.

The measurement conditions of the dynamic friction coefficient were a load of 5 kg and a running speed of 3.75 cm / sec in an atmosphere at room temperature of 23 ° C. and humidity of 50%.

 The dynamic friction coefficient is calculated by the following equation.

(Where μ is the dynamic friction coefficient, F is the force applied to the load cell,
P is the load, R is the arm length to the load cell, r ₁ is the inner diameter,
r ₂ represents the outer diameter. The conditions for measuring the wear coefficient are as follows: In the atmosphere of room temperature 23 ° C and humidity 50%, when the same material is used, load 5kg, running speed 3.75cm / sec, 12,6
00 revolutions (running speed 0.24km)
In the case of C), the measurement was performed at a load of 10 kg, a traveling speed of 15 cm / sec, and 80,000 revolutions (a traveling speed of 6 km).

 The friction coefficient is calculated by the following equation.

(Where A is the coefficient of friction, ΔW is the weight change of the sample, P
Is the load, l is the running distance, and α is the density of the sample. * Weather resistance test method Sunshine weather meter (Toyo Rika Co., Ltd.
WE-USN-HC type), 200 hours exposure (63 ℃, with rain)
Thereafter, the Izod impact strength was measured.

Example 1 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane were mixed, put into 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved, and stirred for 3 minutes with a homomixer. And emulsified and dispersed.

The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 90 ° C. for 6 hours while stirring and mixing, and cooled at 5 ° C. for 24 hours to complete the condensation.

The condensation rate of octamethylcyclotetrasiloxane in the obtained modified polyorganosiloxane (III) was 92.8%.

This modified polyorganosiloxane latex was neutralized to pH 7 with an aqueous sodium carbonate solution.

35 parts by weight of this modified polyorganosiloxane latex in terms of solid content and sodium dodecylbenzenesulfonate
0.5 parts and 140 parts of distilled water were mixed and transferred to a separable flask equipped with a dropping bottle, a condenser, a nitrogen inlet, and a stirrer. Further, 15.81 parts of styrene equivalent to 34% of the total styrene amount and 15.81 parts of total acrylonitrile amount 6.29 parts of acrylonitrile corresponding to 34%, 0.2 parts of sodium pyrophosphate,
0.25 parts of glucose, 0.004 parts of ferrous sulfate and 0.074 parts of cumene hydroperoxide were added, and the temperature was raised to 70 ° C. while flowing nitrogen. After polymerization for 1 hour, the remaining styrene 3
A mixture of 0.69 parts, the remaining 12.21 parts of acrylonitrile, 1.084 parts of sodium dodecylbenzenesulfone, 42 parts of distilled water, 0.12 parts of cumene hydroperoxide and 0.06 parts of t-dodecylmercaptan was added over 3 hours using a dropping bottle. After the completion of the dropping, a polymerization reaction was carried out for 1 hour. After the polymerization was completed, the mixture was cooled.

The obtained graft copolymer latex was poured into warm water in which 2 parts of calcium chloride dihydrate was dissolved, and subjected to salt-solidification to separate a thermoplastic resin containing the graft copolymer. After thoroughly washing this thermoplastic resin with water,
Drying for 16 hours completed the purification.

Next, 57% of the thermoplastic resin powder was mixed with 43% of a copolymer (AS resin) obtained by emulsion polymerization at a weight ratio of monomers of styrene and acrylonitrile of 75:25 to obtain a thermoplastic resin composition. Was prepared. This thermoplastic resin composition is heated at a cylinder temperature using a twin-screw extruder.
Extruded at 230 ° C to obtain pellets.

The obtained thermoplastic resin composition was excellent in cold resistance, weather resistance, slidability, impact resistance, and appearance. Table 1 shows the evaluation results.

Examples 2 to 3 and Comparative Examples 1 and 2 Example 1 was repeated except that the mixing ratio of the polyorganosiloxane (I) and the grafting agent (II) in Example 1 was changed.
A thermoplastic resin containing a modified polyorganosiloxane latex and a graft copolymer was prepared in the same manner as in Example 1, and a thermoplastic resin composition was prepared in the same manner as in Example 1 using this thermoplastic resin.

 The results are shown in Table 1.

In Comparative Example 1, the amount of the graft crossing agent was 0.1%, the graft ratio was reduced, and sufficient impact strength was not obtained.
In Comparative Example 2, the amount of the graft crossing agent was 15%.
The molecular weights of the vinyl polymer grafted to the modified polyorganosiloxane and the vinyl polymer not grafted were reduced, and sufficient impact strength was not obtained.

Comparative Examples 3 to 5 During the preparation of the modified polyorganosiloxane (III),
-Instead of vinylphenylmethyldimethoxysilane,
The same procedure as in Example 1 was repeated except that 1.5 parts of vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, or γ-methacryloxypropylmethyldimethoxysilane was used, and the modified polyorganosiloxane latex, graft copolymer (V ) Was prepared, and a thermoplastic resin composition was prepared.

Table 1 shows the results of the evaluation of these thermoplastic resins in the same manner as in Example 1.

In all of Comparative Examples 3 and 4, a high graft ratio was not obtained, and sufficient impact strength was not obtained.

In Comparative Example 5, impact strength equivalent to that of Example 1 was obtained, but the appearance was poor and sufficient gloss was not obtained.

Examples 4 to 6 Except that the vinyl monomer (IV) grafted to the modified polyorganosiloxane (III) is changed as shown in Table 1, and the resin blended with the obtained thermoplastic resin is changed as shown in Table 1. In the same manner as in Example 1, a thermoplastic resin composition was prepared and evaluated. The results are shown in Table 1.

As is clear from Table 1, the graft copolymer (V)
Has a high graft ratio and a thermoplastic resin composition having good impact strength and appearance.

Examples 7 to 8 A thermoplastic resin and a thermoplastic resin composition were prepared and evaluated in the same manner as in Example 1 except that the graft crosslinking agent was changed as shown in Table 1.

 The results are shown in Table 1.

As is clear from Table 1, the graft copolymer (V)
Has a high graft ratio and a thermoplastic resin composition having good impact strength and appearance.

Example 9 and Comparative Example 6 In Example 9, a thermoplastic resin composition comprising 51% of the thermoplastic resin obtained in Example 1 and 49% of the AS resin used in Example 1 was prepared in the same manner as in Example 1. It is a resin formed and processed by the method described above.

The content of the modified polyorganosiloxane (III) in the thermoplastic resin composition of Example 9 was 17.85%.

On the other hand, in Comparative Example 6, ABS resin (Nippon Synthetic Rubber Co., Ltd.)
JSR ABS12), and the content of butadiene rubber in this resin was 17.8%.

Using these resins, the evaluation methods (a) and (b)
The physical properties were compared according to the following.

 The results are shown in Table 2.

The thermoplastic resin of the present invention has particularly excellent cold resistance, weather resistance, and sliding properties as compared with the existing ABS resin, and has the same or higher other physical properties, and has extremely excellent performance. I understand.

Examples 10 to 11 In this example, the thermoplastic resin of the present invention was molded and evaluated without being blended with another resin. The polymerization conditions, molding conditions, and evaluation conditions are the same as in Example 1. The results are shown in Table 3.

As is clear from Table 3, a graft copolymer having a high graft ratio was obtained, and a thermoplastic resin having good impact strength and appearance was obtained.

(Effect of the Invention) The thermoplastic resin of the present invention uses a modified polyorganosiloxane to which a specific graft-crosslinking agent is bonded, and is obtained by graft-polymerizing a vinyl monomer, and is more vinyl than the conventional polyorganosiloxane. The graft copolymer of the monomer is apt to occur, and the graft ratio and the graft efficiency are higher, so that the thermoplastic resin containing the graft copolymer of the present invention or the resin composition composed of the thermoplastic resin and the other resin is used. The material has an excellent balance of physical properties, especially weather resistance, cold resistance, sliding properties,
It has excellent abrasion resistance. Among them, the sliding property and abrasion resistance are higher than those of polyacetal and polyamide, which are known as sliding materials. The other physical properties are the same as or better than those of the ABS resin which is known to have harmonized physical properties.

Since the thermoplastic resin of the present invention has these excellent performances, it can be applied to new application fields such as sliding parts, parts for cold regions, parts for outdoor use, etc., and its industrial significance is extremely large It is.

──────────────────────────────────────────────────の Continuing on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08F 220: 06) (72) Inventor Yuji Yamamoto 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Gosei Inside Rubber Co., Ltd. (72) Inventor Junichiro Watanabe 133 Nishishinmachi, Ota City, Gunma Prefecture Inside Toshiba Siricorn Corporation (72) Inventor Makoto Matsumoto 133 Nishishinmachi, Ota City, Gunma Prefecture Inside Toshiba Siricorn Corporation (72) Invention Person: Akita Kurita 133 Nishishinmachi, Ota City, Gunma Prefecture Toshiba Siri Cone Corporation (72) Inventor: Yuichi Funabashi 133 Nishishinmachi Town, Ota City, Gunma Prefecture Toshiba Siri Cone Corporation

Claims (1)

(57) [Claims] 1. A compound represented by the general formula: R ¹ _n SiO _{(4-n) / 2} (wherein, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and n is 0 to 3)
90-99.8% by weight of an organosiloxane (I) having a structural unit represented by the following general formula: (Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) by condensation of 10 to 0.2% by weight of a graft crosslinking agent (II) having an unsaturated group represented by the formula (1) and an alkoxysilyl group. Modified polyorganosiloxane (III) obtained by
5% by weight of a graft copolymer (V) obtained by graft-polymerizing at least one vinyl monomer (IV).
A polyorganosiloxane-based thermoplastic resin composition containing the above.