JPH10176017A - Modifying agent for vinyl chloride resin and vinyl chloride resin composition produced by using the agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agent for modifying impact resistance and sliding property of a vinyl chloride resin, and a vinyl chloride resin composition having excellent impact resistance and sliding property by compounding a vinyl chloride resin with the modifying agent. SOLUTION: This modifying agent for vinyl chloride resin is composed of a rubber-modified thermoplastic resin produced by the graft polymerization of 99-20wt.% of at least two kinds of monomer components selected from an aromatic vinyl compound, a vinyl cyanide compound and an alkyl (meth)acrylate in the presence of 1-80wt.% of a polyorganosiloxane rubber polymer. The toluene-swelling ratio of the acetone insoluble fraction of the rubber-modified thermoplastic resin is 100-2,000wt.%. The vinyl chloride resin composition is composed mainly of 0.5-60wt.% of the modifying agent for vinyl chloride resin and 99.5-40wt.% of a vinyl chloride resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact resistance and slidability modifier for a vinyl chloride resin, and a chlorinated compound having excellent impact resistance and slidability obtained by blending the same with a vinyl chloride resin. The present invention relates to a vinyl resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive and have various excellent chemical and physical properties, so that they are used for a wide range of applications. However, a molded article made of a vinyl chloride resin alone has a disadvantage that it is inferior in impact resistance and slidability. For the purpose of improving impact resistance, a method in which a graft copolymer obtained by graft-polymerizing monomers such as styrene, acrylonitrile, and methyl methacrylate onto a rubbery polymer is mixed with a vinyl chloride resin is a special method. JP-B-56-22339, JP-B-57-26536 and JP-B-60-27689 have been proposed, but the impact resistance is improved to some extent, but the improvement in low-temperature impact resistance is sufficient. And the slidability is not improved.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is directed to an impact resistance and slidability modifier for a vinyl chloride resin and a vinyl chloride resin. An object of the present invention is to provide a vinyl chloride resin composition having excellent impact resistance and slidability blended in a resin.

[0004]

According to the present invention, there is provided a polyorganosiloxane rubber polymer in the presence of 1 to 80% by weight,
It is made of a rubber-modified thermoplastic resin obtained by graft-polymerizing 99 to 20% by weight of at least two types of monomer components selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and an alkyl (meth) acrylate, and is insoluble in acetone. Part of the vinyl chloride-based resin modifier having a toluene swelling ratio of 100 to 2,000% by weight, 0.5 to 60% by weight of the vinyl chloride-based resin modifier, and 99.5% of the vinyl chloride-based resin. The present invention relates to a vinyl chloride-based resin composition containing about 40% by weight as a main component.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The latex of a polyorganosiloxane rubbery polymer used in the present invention can be prepared by a known method, for example, as described in US Pat.
It can be obtained by the method described in 294725 and the like. As a preferred method, the organosiloxane is produced by shear-mixing with water using a homomixer or an ultrasonic mixer or the like in the presence of a sulfonic acid emulsifier such as an alkylbenzenesulfonic acid or an alkylsulfonic acid, and condensing the mixture. be able to. Alkyl benzene sulfonic acid is suitable because it acts as an emulsifier for the organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use a metal salt of an alkyl benzene sulfonic acid, a metal salt of an alkyl sulfonic acid or the like in combination, since it is effective in maintaining the polymer stably during graft polymerization. At this time, if necessary, a graft crosslinking agent and a crosslinking agent may be co-condensed within a range that does not impair the intended performance of the present invention.

Here, the organosiloxane used is, for example, a compound represented by the general formula R _m SiO _{(4-m) / 2} (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and m is 0 to 0). Which represents an integer of 3)
It has a linear, branched or cyclic structure, but is preferably an organosiloxane having a cyclic structure. Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting the same with a cyano group or the like. it can.

Specific examples of the organosiloxane include cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane. A chain or branched organosiloxane can be mentioned. These organosiloxanes can be used alone or in combination of two or more. This organosiloxane is condensed in advance, for example, has a weight average molecular weight of 500 in terms of polystyrene.
A polyorganosiloxane of about 10,000 to about 10,000 may be used. Further, when the organosiloxane is a polyorganosiloxane, its molecular chain terminals may be 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. Good. The above-mentioned organosiloxanes can be used alone or in combination of two or more.

The graft-crosslinking agent used within a range not to impair the object of the present invention is, for example, a compound having both an unsaturated group represented by the following general formula and an alkoxysilyl group. CH ₂ ＣC (R ¹ ) -φ- (CH ₂ ) _n- (wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, More preferably, a hydrogen atom or a methyl group, and n is 0
And an integer of from 12 to 12, preferably 0. )

Specific examples of the above compounds include p-vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane,
(P-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, 2- (m-vinylphenyl) ethylmethyldimethoxysilane, -(O-vinylphenyl) ethylmethyldimethoxysilane, 1- (p-vinylphenyl) ethylmethyldimethoxysilane, 1- (m-vinylphenyl) ethylmethyldimethoxysilane, 1- (o-vinylphenyl) ethylmethyldimethoxysilane Besides,
These mixtures can be mentioned. Of these grafting agents, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane are more preferable. Is p-vinylphenylmethyldimethoxysilane.

[0010] The proportion of the graft cross-linking agent used is such that the total amount of the organosiloxane, the graft cross-linking agent and the crosslinking agent is 1
0 to 10 parts by weight, more preferably 0.2 to 10 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight.
-5 parts by weight. If the amount of the grafting agent used is large,
The molecular weight of the grafted vinyl polymer decreases, and as a result, sufficient impact resistance cannot be obtained. In addition, oxidation degradation tends to proceed due to double bonds of the polyorganosiloxane-based rubbery polymer after grafting, and a graft copolymer (rubber-modified thermoplastic resin) having good weather resistance cannot be obtained.

The average particle size of the particles of the polyorganosiloxane rubbery polymer latex is preferably 5,
000 angstroms or less, more preferably 4,0
00 angstrom or less, particularly preferably 1,000
~ 4,000 angstroms. The average particle size can be easily controlled by the amounts of the emulsifier and water, the degree of dispersion when mixed using a homomixer or an ultrasonic mixer, or the method of charging the organosiloxane. If it exceeds 5,000 angstroms, the gloss is poor.

The polyorganosiloxane rubbery polymer thus obtained has a weight average molecular weight in terms of polystyrene of 30,000 to 1,000,000, preferably 50,000 to 300,000. If it is less than 30,000, the impact resistance of the obtained graft copolymer and the composition obtained by blending the same with a vinyl chloride resin are inferior. On the other hand, when it exceeds 1,000,000, the entanglement of the polymer chains is so strong that the rubber elasticity of the rubber particles is reduced, and the impact resistance is reduced. The weight average molecular weight can be easily adjusted by changing the polycondensation temperature and time during the preparation of the polyorganosiloxane rubbery polymer.
That is, the higher the polycondensation temperature and the longer the cooling time, the higher the molecular weight. The molecular weight can also be increased by adding a small amount of a crosslinking agent. The molecular chain terminals of the polyorganosiloxane rubbery polymer may be 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.

The amount of the emulsifier to be used is usually 0.1 to 5 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the total amount of the organosiloxane, the graft crosslinking agent and the crosslinking agent.
3 parts by weight. In this case, the amount of water used is determined by the total amount of the organosiloxane, the graft crosslinking agent, and the crosslinking agent, which is 1
The amount is usually 100 to 500 parts by weight, preferably 200 to 400 parts by weight, per 100 parts by weight. The condensation temperature is usually 5 to 100C.

In the production of the polyorganosiloxane rubbery polymer, a crosslinking agent may be added as a third component in order to improve the impact resistance of the obtained graft copolymer. Examples of the crosslinking agent include a trifunctional crosslinking agent such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and a tetrafunctional crosslinking agent such as tetraethoxysilane. These crosslinking agents can be used alone or in combination of two or more. Further, as these crosslinking agents, a crosslinked prepolymer which has been prepolymerized may be used. The amount of the cross-linking agent added is 1 in total of the organosiloxane, the graft cross-linking agent and the cross-linking agent.
10 parts by weight or less, more preferably 5 parts by weight or less, particularly preferably 0.01 to 5 parts by weight, per 100 parts by weight.
Parts by weight. If the amount exceeds 10 parts by weight, the flexibility of the polyorganosiloxane-based rubbery polymer is impaired, and the slidability and impact resistance are reduced.

Next, the polyorganosiloxane-based rubbery polymer thus obtained is added to an aromatic vinyl compound,
By modifying at least two kinds of monomer components selected from the group consisting of a vinyl cyanide compound and an alkyl (meth) acrylate, the rubber-modified thermoplastic resin of the present invention is modified for a vinyl chloride resin by graft polymerization. Agent is obtained. Here, among the monomer components used in the present invention, examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, monobromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, Sodium styrenesulfonate, etc., which may be used alone or
Mixtures of more than one species can be used. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and the like. These can be used alone or in combination of two or more. Further, examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, butyl methacrylate, allyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, and dimethylaminoethyl methacrylate. These can be used alone or in combination of two or more.

As the above monomer component, at least two kinds selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and an alkyl (meth) acrylate are used. If only one of the above monomer components is used, the slidability is poor. A preferred combination is a monomer component mainly composed of the following. Styrene / acrylonitrile Styrene / methyl methacrylate α-methylstyrene / acrylonitrile More preferably, styrene / acrylonitrile, and the ratio is styrene / acrylonitrile = 85-85.
65 / 15-35% by weight is particularly preferred.

The charge composition for graft polymerization of the above monomer component to the polyorganosiloxane rubbery polymer is as follows:
1 to 80% by weight, preferably 5 to 80% by weight, more preferably 10 to 80% by weight of the polyorganosiloxane rubbery polymer
To 70% by weight, 99 to 20% by weight of the above monomer component, preferably 95 to 20% by weight, more preferably 90 to 30% by weight.
% Of polyorganosiloxane rubbery polymer + monomer component = 100% by weight. When the amount of the polyorganosiloxane-based rubbery polymer is less than 1% by weight, the impact resistance is reduced due to a small amount of rubber. On the other hand, when the amount exceeds 80% by weight, the proportion of the vinyl-based polymer to be graft-bonded is reduced. , A sufficient interfacial adhesion between the polyorganosiloxane-based rubbery polymer and the vinyl-based polymer cannot be obtained, and the resulting graft copolymer has a reduced impact resistance;
As a result, the impact resistance after blending the vinyl chloride resin is poor.

The rubber-modified thermoplastic resin (graft copolymer) of the present invention comprises a polyorganosiloxane-based rubbery polymer having a graft polymer obtained by grafting a monomer component and a graft polymer having no monomer component grafted (copolymer). ) Polymerized matrix components. Here, the graft ratio of the rubber-modified thermoplastic resin of the present invention is not particularly limited, but is preferably 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 30 to 120% by weight. If the graft ratio is less than 10% by weight, the compatibility with the matrix component is reduced due to insufficient graft, and the impact resistance is reduced. On the other hand, if it exceeds 120% by weight, the fluidity, impact resistance and slidability may decrease. Here, the graft ratio can be generally measured by a known method in which an acetone-soluble portion and an insoluble portion are separated by a centrifugal separator.
The adjustment of the graft ratio is based on the amount of the graft crossing agent in the polyorganosiloxane-based rubbery polymer used in the production of the rubber-modified thermoplastic resin, the type and amount of the graft initiator used in the production of the rubber-modified thermoplastic resin, or the amount charged. It can be adjusted by appropriately selecting the ratio of the amount of rubber / the monomer component.

Further, the intrinsic viscosity of the matrix component (methyl ethyl ketone, 3
(Measured at 0 ° C.) is preferably 0.2 to 2 dl / g. When the intrinsic viscosity of the matrix component is less than 0.2 dl / g, the impact resistance of the obtained rubber-modified thermoplastic resin decreases, while when it exceeds 2 dl / g, the fluidity decreases. Here, the adjustment of the limiting viscosity can be easily adjusted by changing the kind and amount of the chain transfer agent used in the synthesis of the rubber-modified thermoplastic resin, or by changing the ratio of the graft polymerization initiator / monomer component. it can.

The rubber-modified thermoplastic resin of the present invention comprises:
It may be obtained by graft-polymerizing the above monomer component in the presence of a polyorganosiloxane-based rubbery polymer, or the above-mentioned monomer may be added thereto in the absence of a polyorganosiloxane-based rubbery polymer. A polymer obtained by appropriately polymerizing the components may be used.

The graft polymerization of the rubber-modified thermoplastic resin of the present invention is obtained by radical polymerization. The radical polymerization at this time is preferably an emulsion polymerization. For the emulsion polymerization, a radical polymerization initiator, an emulsifier, a chain transfer agent 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, paramenthane hydroperoxide, t-butylperoxylaurate, and sugar-containing iron pyrophosphate. Redox initiators in combination with reducing agents such as formulations, sulfoxylate formulations, and mixed formulations of sugar-containing iron pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisiso Azo compounds such as butyronitrile, dimethyl-2,2'-azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide; Preferably the above redo It is a hex-based initiator.
The amount of the radical polymerization initiator to be used is generally about 0.05 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, based on 100 parts by weight of the monomer component used.

Examples of the emulsifier include anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenylether disulfonate and sodium dialkaliester succinate; and polyoxyethylene alkyl esters and polyoxyethylene alkyl allyl ethers. Nonionic emulsifiers can be used, and these can be used alone or in combination of two or more. The amount of the emulsifier to be used is usually 0.5 to 5 parts by weight based on 100 parts by weight of the monomer component.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, and tetraethyl. Thiuram sulfide, carbon tetrachloride, ethylene bromide,
Examples thereof include hydrocarbon salts such as pentanephenylethane, terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and α-methylstyrene dimer. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0.02 to 1 part by weight based on 100 parts by weight of the monomer component.

In the graft polymerization, in addition to a radical polymerization initiator, an emulsifier, a chain transfer agent, etc., if necessary, various electrolytes, a pH adjuster and the like are used in combination to form a monomer component 1
Usually, 100 to 500 parts by weight of water and 100 to 500 parts by weight of the above-mentioned radical polymerization initiator, emulsifier, chain transfer agent and the like are used in an amount within the above range.
The emulsion polymerization is carried out at a temperature of preferably from 50 to 90 ° C and a polymerization time of from 0.1 to 10 hours. In the presence of a polyorganosiloxane-based rubbery polymer, when the above monomer component is graft-polymerized, the monomer component may be added or polymerized at once, divided or continuously added or polymerized, Further, the polymerization may be carried out by a method combining these.

The rubber-modified thermoplastic resin of the present invention is purified by coagulating a latex obtained by the above-mentioned emulsion polymerization by a conventional method, washing the obtained powder with water, and drying it. The obtained rubber-modified thermoplastic resin is
It can be pelletized by a kneading machine such as an extruder. In order to achieve the object of the present invention, the toluene swelling ratio of the acetone-insoluble portion of the rubber-modified thermoplastic resin is 100%.
2,000 wt%, preferably 200-1,800 wt%, more preferably 300-1,600 wt%, particularly preferably 400-1,300 wt%. If the toluene swelling ratio is less than 100% by weight, the composition containing the vinyl chloride resin has poor impact resistance and slidability, while if it exceeds 2,000% by weight, the impact resistance is poor.

Here, the toluene swelling ratio is measured by the following method or the like. That is, after dissolving the rubber-modified thermoplastic resin in acetone, take out the insoluble portion by centrifugation,
After thoroughly drying this insoluble part (gel) with a vacuum dryer,
The gel is weighed, placed in toluene and left for 3 days, then filtered through a 200 mesh wire gauze, left for 10 minutes, and the weight of the swelled product is measured to calculate the swelling ratio by the following formula. Swelling ratio (%) = (gel weight after swelling / gel weight before swelling measurement) × 100

The above-mentioned toluene swelling ratio can be determined by changing the amount of the graft crosslinking agent or the cross-linking agent used in the production of the polyorganosiloxane-based rubbery polymer, or the amount of the radical polymerization initiator in the production of the rubber-modified thermoplastic resin. Can be adjusted by varying. Further, it can also be adjusted by blending a known amount of a silane coupling agent, a peroxide, or the like with the rubber-modified thermoplastic resin and kneading with heat.

The modifier for a vinyl chloride resin comprising the rubber-modified thermoplastic resin of the present invention is contained in the resin composition in an amount of 0.5 to 0.5%.
When it is blended with the vinyl chloride resin in an amount of 60% by weight, preferably 3 to 40% by weight, a vinyl chloride resin composition having excellent impact resistance and slidability can be obtained. If the amount of the modifier for the vinyl chloride resin in the composition is less than 0.5% by weight, the effect of improving the impact resistance and the sliding property of the vinyl chloride resin is small, while the amount exceeds 60% by weight. Even if
Although impact resistance and slidability are good, they are not economical and are not preferred.

The vinyl chloride resin used in the present invention refers to a vinyl chloride homopolymer or a copolymer of 80% by weight or more of vinyl chloride and 20% by weight or less of another monomer copolymerizable therewith. Such as coalescence. Here, other copolymerizable monomers include vinyl acetate, ethylene, acrylate, vinyl bromide and the like. Further, chlorinated polyvinyl chloride and chlorinated polyethylene are also included, and a preferred polymer is a homopolymer of vinyl chloride. The mixing of the vinyl chloride-based resin modifier of the present invention with the vinyl chloride-based resin is generally carried out using a known kneading machine, for example, a mixing roll, a calender roll, a Banbury mixer,
It is carried out by kneading at a melting temperature of 120 to 220 ° C. using an extruder, a kneader or the like.

The vinyl chloride resin composition of the present invention may contain, if necessary, a dye, a pigment, a heat stabilizer, an antioxidant, a weather (light) agent, an organic / inorganic reinforcing agent, an organic / inorganic filler, Flame retardant, antibacterial / antifungal agent, ultrahigh molecular weight AS resin with molecular weight of 1,000,000 or more, ultrahigh molecular weight PMMA, ultrahigh molecular weight PTFE
Processing aids, such as a foaming agent, a plasticizer, and a lubricant.

The vinyl chloride resin composition of the present invention thus obtained can be obtained by sheet / film extrusion, foam extrusion, profile extrusion, blow molding, inflation molding, injection molding, vacuum molding, compression molding, and rotation. A product can be obtained by a molding method such as molding. Products obtained by the molding method can be widely used as parts in various fields such as a building material field, a vehicle field, an OA / home electric appliance field, a sanitary field, and miscellaneous goods.

[0032]

EXAMPLES The present invention will now be described more specifically with reference to examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified. During the implementation, various measurement items were as described below.

[0033] The average particle diameter electron micrograph of the latex, measuring the particle diameters of the n = 100, and the average value was defined as the average particle size. The toluene-swelling ratio rubber-modified thermoplastic resin is put into acetone, shaken for 6 hours with a shaker, and after dissolving the free copolymer,
Using a centrifuge, 60 rpm at 23,000 rpm
The mixture was centrifuged for 1 minute to separate an insoluble portion from a soluble portion. Next, the insoluble portion was sufficiently dried with a vacuum dryer to obtain an acetone insoluble portion of the rubber-modified thermoplastic resin. About 0.2g of this insoluble part
Is weighed (W ₁ ) and placed in 50 ml of toluene.
Leave for 3 days, then filter with 200 mesh mold,
After standing for 10 minutes, the weight (W ₂ ) of the toluene swell was measured, and the toluene swell ratio was measured by the following equation. Toluene swelling ratio (%) = (W ₂ / W ₁ ) × 100

According to ASTM D256, a 1/4 inch thick test piece was used to measure notched Izod impact strength at 23 ° C.

Sliding characteristics For the sliding characteristics, a Suzuki-type sliding tester was used, and steel (S45C) was used as a mating material. The test piece has an outer diameter of 2
A hollow cylindrical member having a size of 5.6 mm and an inner diameter of 20.0 mm was used, and a mating member having the same shape was used. The conditions of the sliding test were as follows: a room temperature of 23 ° C. and a humidity of 50%, a load of 2 k.
g, running speed 500 mm / sec, running time = 10 hours, running distance = 18 km. The measurement of the amount of abrasion was calculated by (test specimen weight before test)-(test specimen weight after test), and the dynamic friction coefficient was calculated by the following equation. mu = [3 × F × R × (r 2 2 -r 1 2) ] / [P × (r ₂ ³ -
During r ₁ ^3)] expression, mu is the dynamic friction coefficient, F is given by the load cell force, R
Is the arm length to the load cell, r ₁ is the inside diameter of the test piece, r ₂ is the outside diameter of the test piece, and P is the load.

Reference Example 1 (Preparation of polyorganosiloxane rubbery polymer latex R-1 to R-6) Preparation of R-1; 1.3 parts of p-vinylphenylmethyldimethoxysilane and 98.7 of octamethylcyclotetrasiloxane The mixture was added to 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved, and the mixture was emulsified and dispersed by stirring with a homogenizer for 3 minutes. This 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 kept at 5 ° C. for 24 hours to complete the condensation. The condensation rate of the obtained polyorganosiloxane rubbery polymer was 93%. This latex was neutralized to pH 7 with an aqueous sodium carbonate solution. The average particle size of the obtained polyorganosiloxane rubbery polymer latex was 3,000 angstroms.

Preparation of R-2: In the preparation of R-1, p
-Latex R-2 was obtained in the same manner as R-1, except that 2.5 parts of vinylphenylmethyldimethoxysilane and 97.5 parts of octamethylcyclotetrasiloxane were used. The condensation ratio was 93%, and the average particle size was 3,000 angstroms. Preparation of R-3: The preparation of R-1 was repeated except that 1.0 part of p-vinylphenylmethyldimethoxysilane, 1.5 parts of tetraethoxysilane and 97.5 parts of octamethylcyclotetrasiloxane were used. In the same way as 1,
Latex R-3 was obtained. The condensation ratio was 93%, and the average particle size was 3,000 angstroms.

Preparation of R-4: In the preparation of R-1, p
-Latex R-4 was obtained in the same manner as R-1, except that 0.3 parts of vinylphenylmethyldimethoxysilane and 99.7 parts of octamethylcyclotetrasiloxane were used. The condensation ratio was 93%, and the average particle size was 3,000 angstroms. Preparation of R-5: R-1 was prepared except that p-vinylphenylmethyldimethoxysilane was not used and 0.3 parts of tetraethoxysilane and 99.7 parts of octamethylcyclotetrasiloxane were used. In the same way as
Latex R-5 was obtained. The condensation ratio was 93%, and the average particle size was 3,000 angstroms.

Preparation of R-6: In the preparation of R-1, p
-Except for using 8 parts of vinylphenylmethyldimethoxysilane, 8 parts of tetraethoxysilane and 84 parts of octamethylcyclotetrasiloxane,
Latex R-6 was obtained. The condensation ratio was 93%, and the average particle size was 3,000 angstroms.

Example 1 (Preparation of Rubber-Modified Thermoplastic Resin P-1) In an autoclave equipped with a stirrer, 100 ion-exchanged water was added.
Parts, sodium dodecylbenzenesulfonate 0.5 part,
0.01 parts of potassium hydroxide, 4 parts of the above latex R-1
0 parts (in terms of solid content), 15 parts of styrene, and 5 parts of acrylonitrile were added. After the replacement with nitrogen, the temperature was raised while stirring. When the internal temperature reaches 45 ° C., 0.2 part of sodium pyrophosphate, 0.25 part of glucose, 0.004 part of ferrous sulfate, and 0.1 part of cumene hydroperoxide.
15 parts were added, and the reaction was continued for 2 hours (first stage). Thereafter, a component consisting of 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.02 part of potassium hydroxide, 0.2 part of cumene hydroperoxide, 30 parts of styrene and 10 parts of acrylonitrile is continuously added over 4 hours. Polymerization occurred (second stage). After completion of the addition, the mixture was reacted for 1 hour while continuing to stir, and then 2,2-methylene-bis- (4-ethylene-6-t-butylphenol) 0.2
Was added in an emulsified state to terminate the reaction. The product was coagulated using potassium chloride, dehydrated, washed with water and dried to obtain resin P-1. The toluene swelling ratio of the acetone-insoluble portion of the resin P-1 was 680%.

Example 2 (Preparation of Rubber-Modified Thermoplastic Resin P-2) In the preparation of resin P-1, t-butyl peroxylaurate was replaced with 1 part of cumene hydroperoxide.
Resin P-2 was obtained in the same manner as P-1, except that 0.25 / 0.15 part of the stage / 2 stage was used. Resin P-
The toluene swelling ratio of the acetone-insoluble part of No. 2 was 520%. Example 3 (Preparation of rubber-modified thermoplastic resin P-3) Resin P-3 was prepared in the same manner as P-1 except that R-2 was used instead of R-1 in the preparation of resin P-1. I got The toluene swelling ratio of the acetone-insoluble portion of the resin P-3 is:
It was 580%.

Example 4 (Preparation of Rubber-Modified Thermoplastic Resin P-4) Resin P-1 was prepared in the same manner as in the preparation of resin P-1, except that R-3 was used instead of R-1. P-4 was obtained. The toluene swelling ratio of the acetone-insoluble portion of the resin P-4 is:
480%. Example 5 (Preparation of Rubber-Modified Thermoplastic Resin P-5) In the preparation of resin P-1, styrene and acrylonitrile were obtained by mixing styrene / methyl methacrylate = 10/10 parts,
Resin P-5 was obtained in the same manner as P-1, except that styrene / methyl methacrylate = 20/20 parts was used instead of styrene and acrylonitrile in the second stage. Resin P
The toluene swelling ratio of the acetone-insoluble part of -5 was 680%.

Example 6 (Preparation of Rubber-Modified Thermoplastic Resin P-6) In the preparation of resin P-1, the amount of R-1 used was changed to 60 parts (in terms of solid content), styrene / acrylonitrile at the first stage = 10 Resin P-6 was obtained in the same manner as P-1, except that 0.0 / 3.33 parts was replaced with styrene / acrylonitrile in the second stage = 20 / 6.67 parts. The toluene swelling ratio of the acetone-insoluble portion of the resin P-6 was 700%.

Example 7 (Preparation of Rubber-Modified Thermoplastic Resin P-7) In the preparation of resin P-1, the amount of R-1 used was changed to 20 parts (in terms of solid content), styrene / acrylonitrile in the first stage = 20 0.0 / 6.67 parts, except that styrene / acrylonitrile in the second stage was changed to 40.0 / 13.33 parts.
In the same manner as -1, resin P-7 was obtained. The toluene swelling ratio of the acetone-insoluble portion of the resin P-7 was 650%.

Comparative Example 1 (Preparation of Resin P-8) Resin P-8 was prepared in the same manner as in Preparation of Resin P-1, except that R-4 was used instead of R-1. Obtained. The toluene swelling ratio of the acetone-insoluble portion of the resin P-8 is:
It was 2,500%. Comparative Example 2 (Preparation of Resin P-9) Resin P-9 was obtained in the same manner as in Preparation of Resin P-1, except that R-5 was used instead of R-1. The toluene swelling ratio of the acetone-insoluble portion of the resin P-6 is:
2,400%.

Comparative Example 3 (Preparation of Resin P-10) Resin P-O was prepared in the same manner as in P-1 except that methyl methacrylate was used instead of styrene / acrylonitrile used in the preparation of resin P-1. 10 was obtained. Resin P
The toluene swelling ratio of the acetone-insoluble part of −10 is 680%.
Met. Comparative Example 4 (Preparation of Resin P-11) In the preparation of Resin P-1, the amount of R-1 used was 0.5 part (in terms of solid content), styrene / acrylonitrile in the first stage = 24.88 / 8. 28 parts, except that the second-stage styrene / acrylonitrile was replaced by 49.75 / 16.59 parts.
Resin P-11 was obtained in the same manner as P-1. Resin P-1
The toluene swelling ratio of the acetone-insoluble portion of No. 1 was 630%.

Comparative Example 5 (Preparation of Resin P-12) In the preparation of Resin P-1, the amount of R-1 used was changed to 90 parts (in terms of solid content), first stage styrene / acrylonitrile = 2.5 / 0. Resin P-12 was obtained in the same manner as P-1, except that 0.83 parts was replaced with 5.0 / 1.67 parts of styrene / acrylonitrile in the second stage. The toluene swelling ratio of the acetone-insoluble portion of the resin P-12 was 760%. Comparative Example 6 (Preparation of Resin P-13) Resin P-13 was obtained in the same manner as in Preparation of Resin P-1, except that R-6 was used instead of R-1. The toluene swelling ratio of the acetone-insoluble portion of the resin P-13 was 70%.

Reference Example 2 (Styrene-acrylonitrile copolymer resin) Styrene / acrylonitrile = 75 /
A copolymer resin (A-1) consisting of 25% was obtained.

Examples 8 to 17, Comparative Examples 7 to 12 A polyvinyl chloride resin (PVC) having a degree of polymerization of 700 and the modifier obtained in Examples 1 to 5, Comparative Examples 1 and 2, and Reference Example 2 were They were mixed at the ratios shown in Tables 1-3. To 100 parts of the obtained mixture, 3 parts of dibutyltin maleate, 1 part of butyl stearate, 0.5 part of stearyl alcohol, and 0.2 part of a lubricant (Roxyl G-47, manufactured by Henkel Co.) were added, and the mixture was added with a Henschel mixer. The mixture was kneaded with a mixing roll at a low temperature of 165 ° C. and a high temperature of 195 ° C. for 7 minutes.
Then, a test piece was formed by pressure molding at 180 ° C. and a pressure of 100 kg / cm ² , and evaluated by the above evaluation method. The results are shown in Tables 1 to 3.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

As apparent from Tables 1 and 2, Examples 8 to
Reference numeral 17 denotes the vinyl chloride resin composition of the present invention, which has excellent impact resistance and slidability. On the other hand, as is clear from Table 3, Comparative Examples 7 and 8 are examples in which the toluene swelling ratio of the acetone-insoluble portion of the rubber-modified thermoplastic resin is large outside the range of the present invention, and the impact resistance is poor. Comparative Example 9 is an example in which only one type of monomer was used during the production of the rubber-modified thermoplastic resin, which was out of the range of the present invention, and was inferior in slidability. Comparative Example 10 is an example in which the amount of the polyorganosiloxane-based rubbery polymer in the rubber-modified thermoplastic resin is small outside the range of the present invention, and is inferior in impact resistance and slidability. Comparative Example 11 is an example in which, contrary to Comparative Example 10, a polyorganosiloxane-based rubbery polymer having a large amount outside the range of the present invention is used, and is inferior in impact resistance. Comparative Example 12
Is an example using a rubber-modified thermoplastic resin in which the toluene swelling ratio of the acetone-insoluble portion is small outside the range of the present invention, and is inferior in impact resistance and slidability.

[0054]

When the impact resistance and slidability modifier of the present invention is blended with a vinyl chloride resin, a remarkable effect of improving the impact resistance and slidability can be obtained.

 ──────────────────────────────────────────────────の Continued from the front page (72) Inventor Shinobu Fukumura 1-18-1 Kyobashi, Chuo-ku, Tokyo Inside Techno Polymer Co., Ltd.

Claims (2)

[Claims] 1. The method of claim 1, wherein the polyorganosiloxane rubbery polymer is present in an amount of from 1 to 80% by weight in the presence of at least two kinds of aromatic vinyl compounds, vinyl cyanide compounds and alkyl (meth) acrylates. Monomer component 9
The rubber-modified thermoplastic resin obtained by graft polymerization of 9 to 20% by weight has a toluene swelling ratio of 100% insoluble in acetone.
Up to 2,000% by weight of a vinyl chloride resin modifier. 2. The modifier for a vinyl chloride resin according to claim 1, wherein the vinyl chloride resin is 0.5 to 60% by weight.
A vinyl chloride resin composition containing 5 to 40% by weight as a main component.