JP2001026694A - Vinyl chloride based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide vinyl chloride based resin compositions which enable the improvement on the flowability and the external appearance of molded surfaces in the low-temperature molding using a vinyl chloride based resin, particularly a vinyl chloride based resin having a high average degree of polymerization without adversely affecting impact resistance. SOLUTION: Vinyl chloride based resin compositions comprise (A) 100 pts.wt. vinyl chloride based resin, (B) 1-30 pts.wt. graft copolymer obtained by graft polymerization of (c) at least one monomer selected from an aromatic alkenyl compound, a (meth)acrylic ester, and a vinyl cyanide compound onto a polyorganosiloxane composite rubber composed of (a) a polyorganosiloxane and (b) an alkyl (meth)acrylate rubber, and (C) 0.5-20 pts.wt. copolymer having, as the constituting unit, at least one monomer selected from an aromatic alkenyl compound, a (meth)acrylic ester, and a vinyl cyanide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition which has high fluidity in low-temperature molding, is easy to process, and has an excellent molded surface appearance.
The present invention relates to a vinyl chloride resin composition having impact resistance.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive and have been used in a wide range of applications because of their excellent chemical and physical properties. When many vinyl chloride resins are used for hard compounding systems, the higher the average degree of polymerization, the better the physical properties such as impact resistance, tensile strength and heat resistance of the vinyl chloride resin alone. It is known that a large effect can be obtained even with a small amount of the impact modifier.
On the other hand, as the average degree of polymerization increases, the processability decreases, resulting in a decrease in fluidity and surface appearance required in high-speed molding such as calender molding, blow molding, extrusion molding, and injection molding. There is a method in which a vinyl chloride resin having a low average degree of polymerization is used to raise the molding temperature, and such a fluidity and a lack of molding appearance are compensated. However, when the average degree of polymerization of the vinyl chloride resin is high in the hard compounding system, it is necessary to raise the molding temperature until a satisfactory fluidity and molding surface appearance are obtained. However, when the molding temperature is increased to a state where satisfactory fluidity and appearance of the molding surface are obtained, the resin itself is deteriorated by heat, and physical properties that the resin originally should have cannot be exhibited. In addition, when a vinyl chloride resin having a low average degree of polymerization is used to improve the moldability, the fluidity and the appearance of the molded surface are improved, but the mechanical properties of the obtained molded article may be reduced. was there.

[0003] In recent years, from the viewpoint of improving productivity, by adding to a hard compounding system, a molding having good flowability and molding surface appearance even when using a vinyl chloride resin having a high average degree of polymerization under low molding temperature conditions. There is a need for additives that allow the product to be obtained. In the background, as mentioned above, thermal degradation of resin due to high temperature molding under high speed molding using vinyl chloride resin with low flowability and high average polymerization degree causes deterioration of physical properties and appearance of molded surface In addition, the contamination of the die and the cleaning of the die due to the filler and the like added during compounding hinder long-term continuous molding, and the cost is increased accordingly.

[0004] There have been many proposals for improving the flowability and appearance of molded surfaces of vinyl chloride resins without impairing impact resistance. For example, Japanese Patent Publication No. 48-57
846, JP-A-50-88170, JP-A-50-142661, and JP-A-60-179443.
JP, JP-A-6-313085, JP-A-6-3130
22208 and JP-A-6-322209. These are proposals for obtaining a vinyl chloride-based resin composition having excellent fluidity and molded surface appearance without impairing the impact resistance and the like of the vinyl chloride-based resin. However, in these conventional techniques, the aim is to improve the flowability and molding surface appearance of the vinyl chloride resin in high-temperature molding, and to improve the flowability and molding surface appearance of the vinyl chloride resin in low-temperature molding. Hard to say.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the flowability and surface appearance of a vinyl chloride resin, especially a vinyl chloride resin having a high average degree of polymerization, in low-temperature molding without impairing impact resistance. It is an object of the present invention to provide a flow modifier for a vinyl chloride resin, which enables the above, and a vinyl chloride resin composition using the same.

[0006]

That is, the present invention provides:
(A) 100 parts by weight of vinyl chloride resin, (B)
Polyorganosiloxane (a) and alkyl (meth)
Graft polymerization of at least one monomer (c) selected from aromatic alkenyl compounds, (meth) acrylates and vinyl cyanide compounds onto a polyorganosiloxane composite rubber comprising an acrylate rubber (b). The composite rubber ((a)
+ (B)) 100 to 100 parts by weight of the at least one monomer (c) is graft-polymerized in an amount of 65 to 400 parts by weight, and the insoluble content in the acetone solvent is 70 to 9 parts by weight.
9% by weight and acetone soluble matter at 25 ° C, 0.2g /
Graft copolymer 1 having a reduced viscosity of 100 cc N, N-dimethylformamide solution of 0.30 to 0.70 dl / g
To 30 parts by weight and (C) an aromatic alkenyl compound,
Copolymer containing at least one selected from (meth) acrylate and vinyl cyanide as a constituent unit.
The vinyl chloride resin composition contains 5 to 20 parts by weight.

[0007]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the vinyl chloride resin used as the component (A) is not particularly limited, and may be, for example, a vinyl chloride homopolymer, a post-chlorinated vinyl chloride polymer, or a partially crosslinked polymer. 30 vinyl chloride polymers or other vinyl compounds copolymerizable with vinyl chloride
Copolymers with vinyl chloride which are contained in an amount not exceeding the weight%, and mixtures thereof. Other vinyl compounds that can be copolymerized with vinyl chloride are not particularly limited, and specific examples thereof include, for example, fatty acid vinyl esters such as vinyl acetate and vinyl propionate; methacrylic acid such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Alkyl esters; alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; α-olefins such as ethylene, propylene and styrene; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; acrylic acid, methacrylic acid, anhydride Examples thereof include unsaturated carboxylic acids such as maleic acid, and acid anhydrides thereof, and these may be used alone or in combination of two or more.

If the copolymerizable amount of the other copolymerizable vinyl compound exceeds 30% by weight, the inherent characteristics of the vinyl chloride resin are likely to be impaired. These vinyl chloride resins may be used alone or in combination of two or more.

In the present invention, the vinyl chloride resin used as the component (A) has an average degree of polymerization of 500 to 5,000.
0, preferably 700 to 3,000. Those having an average degree of polymerization of less than 500 are inferior in impact resistance and heat resistance. On the other hand, if it exceeds 5,000, it is difficult to sufficiently knead, and the processability is reduced.

The method for producing the vinyl chloride resin (A) used in the present invention is not particularly limited, and may be an emulsion polymerization method, a suspension polymerization method,
Those produced by various polymerization methods such as a bulk polymerization method can be used.

The polyorganosiloxane (a) used for obtaining the graft copolymer used as the component (B) in the present invention is not particularly limited, but the polyorganosiloxane (a) containing a vinyl polymerizable functional group may be used. It is preferably an organosiloxane.

[0013] 0.3 to 3 mol% of a siloxane unit containing a vinyl polymerizable functional group and 97 to dimethylsiloxane unit
It is preferable that the silicon atom having 99.7 mol% and having three or more siloxane bonds is 1 mol% or less based on all silicon atoms in the polydimethylsiloxane.

When the amount of the siloxane unit having a vinyl polymerizable functional group in the polyorganosiloxane (a) is less than 0.3% by mole, the compounding with the alkyl (meth) acrylate rubber (b) tends to be insufficient. Further, the amount of the vinyl polymerizable functional group-containing siloxane unit in the polyorganosiloxane (a) is more than 3 mol% or silicon atoms having three or more siloxane bonds are based on all silicon atoms in the polyorganosiloxane (a). If it exceeds 1 mol%, the flowability and the molded surface appearance of the vinyl chloride resin composition containing the graft copolymer are reduced, and the impact resistance is liable to be lowered.

Further, considering both the fluidity and the appearance of the molded surface of the vinyl chloride resin composition containing the graft copolymer, the amount of the siloxane unit containing a vinyl polymerizable functional group in the polyorganosiloxane (a) is 0.5 to 0.5%. It is preferably 2 mol%, more preferably 0.5 to 1 mol%.

The amount of the polyorganosiloxane (a) in the composite rubber ((a) + (b)) constituting the graft copolymer in the present invention is preferably 1 to 20% by weight. If the amount is less than 1% by weight, the impact resistance tends to be low because the amount of the polyorganosiloxane (a) is small, and the amount is 20% by weight.
When the ratio exceeds the above range, the molding surface appearance of the resin composition containing the graft copolymer tends to decrease.

Further, considering the fluidity, molded surface appearance and impact resistance of the resin composition containing the graft copolymer,
The amount of polyorganosiloxane (a) in the composite rubber ((a) + (b)) is preferably 6 to 20% by weight, preferably 10 to 20% by weight.

The method for producing the polyorganosiloxane (a) includes a latex obtained by emulsifying a mixture of a dimethylsiloxane compound and a siloxane containing a vinyl polymerizable functional group or, if necessary, a mixture containing a siloxane-based crosslinking agent with an emulsifier and water. Is atomized using a homomixer that atomizes by shearing force due to high-speed rotation or a homogenizer that atomizes by jet power from a high-pressure generator, and then polymerized at high temperature using an acid catalyst, and then an alkaline substance. For neutralization. As a method of adding the acid catalyst used for the polymerization, a siloxane mixture,
There are a method of infiltrating with an emulsifier and water, and a method of dropping a latex in which a siloxane mixture has been finely divided into a high-temperature aqueous acid solution at a constant rate, and the like. In consideration of the above, a method of dropping the latex in which the siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant rate is preferable.

Although the size of the polyorganosiloxane (a) particles is not particularly limited, the weight average particle size is preferably 0.2 μm or less in consideration of the fluidity and the molded surface appearance of the resin composition containing the graft copolymer. , More preferably 0.1 μm or less.

The dimethylsiloxane compound used in the production of the polyorganosiloxane (a) includes a cyclic dimethylsiloxane having three or more member rings, preferably a three- to six-membered ring. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or as a mixture of two or more.

The siloxane containing a vinyl polymerizable functional group is a siloxane containing a vinyl polymerizable functional group and capable of bonding to a dimethyl siloxane compound via a siloxane bond. Considering the reactivity with the dimethyl siloxane compound, Various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane,
methacryloyloxysiloxanes such as γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloylpropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane, tetramethyltetravinylcyclotetrasiloxane, etc. And mercaptosiloxanes such as γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxymethylsilane. These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

As the siloxane crosslinking agent, a trifunctional or tetrafunctional silane crosslinking agent, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane and the like are used. .

The emulsifier used in the production of the polyorganosiloxane (a) is preferably an anionic emulsifier, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like. used. Particularly, sulfonic acid emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable. These emulsifiers are used in an amount of about 0.05 to 5 parts by weight based on 100 parts by weight of the siloxane mixture. If the amount is small, the dispersion state becomes unstable, and the emulsified state of the fine particle system cannot be maintained. If the amount is too large, the thermal stability of the resin composition may be reduced due to the emulsifier.

The method of mixing a siloxane mixture, an emulsifier, water and / or an acid catalyst includes mixing by high-speed stirring and mixing by a high-pressure emulsifier such as a homogenizer, and the method using a homogenizer includes polyorganosiloxane (a This is a preferred method because the particle size of the latex becomes smaller.

Examples of the acid catalyst used for the polymerization of the polyorganosiloxane (a) include sulfonic acids such as aliphatic sulfonic acid, fatty acid-substituted benzenesulfonic acid and fatty acid-substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. Can be These acid catalysts are used alone or in combination of two or more. Among these, fatty acid-substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable, since the polyorganosiloxane (a) latex also has excellent stability.
When n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, it is possible to reduce a decrease in the thermal stability of the resin composition caused by the emulsifier component of the polyorganosiloxane (a) latex.

The polymerization temperature of the polyorganosiloxane (a) is preferably 50 ° C. or higher, more preferably 80 ° C. or higher.

The polymerization time of the polyorganosiloxane (a) is preferably 2 hours or more, more preferably 5 hours when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water, and the mixture is agitated and polymerized. As described above, in the method of dropping the latex in which the siloxane mixture is finely divided into the aqueous solution of the acid catalyst, it is preferable to hold the latex for about 1 hour after the dropping of the latex is completed.

The termination of the polymerization can be carried out by cooling the reaction solution and neutralizing the latex with an alkaline substance such as caustic soda, caustic potash and sodium carbonate.

The alkyl (meth) acrylate rubber (b) constituting the graft polymer (B) is an alkyl (meth)
The composite rubber is a polymer of an acrylate and a polyfunctional alkyl (meth) acrylate, and the composite rubber is an alkyl (meth) acrylate component composed of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate in a polyorganosiloxane (a) latex. And then polymerized.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Examples thereof include alkyl acrylates such as ethylhexyl acrylate and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate, and use of n-butyl acrylate is particularly preferable.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and tri (meth) acrylate. Acryloyl cyanurate, tri (meth) acryloyloxy isocyanurate and the like can be mentioned. The amount of the polyfunctional alkyl (meth) acrylate used is preferably 0.1 to 20% by weight, more preferably 0.2 to 5% by weight, particularly preferably 0.2 to 5% by weight in the alkyl (meth) acrylate component. 1% by weight. Alkyl (meth) acrylates and polyfunctional alkyl (meth) acrylates are used alone or in combination of two or more.

The composite rubber ((a) + (b)) comprising the polyorganosiloxane (a) and the alkyl (meth) acrylate (b) used in the present invention is obtained by mixing the polyorganosiloxane (a) component into the latex. It is prepared by adding the above-mentioned alkyl (meth) acrylate component and polymerizing by reacting with a usual radical polymerization initiator. As a method of adding an alkyl (meth) acrylate,
There are a method of mixing with the latex of the polyorganosiloxane (a) component at a time and a method of dropping the latex of the polyorganosiloxane (a) component at a constant speed. In consideration of the impact resistance of the obtained resin composition containing the graft copolymer, a method in which the latex of the polyorganosiloxane (a) component is mixed at a time is preferable. As the radical polymerization initiator used for the polymerization, a peroxide, an azo-based initiator, or an oxidation-reduction-based initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferable, and a redox initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and hydroperoxide is particularly preferable.

By subjecting at least one monomer (c) selected from an aromatic alkenyl compound, a (meth) acrylate ester and a vinyl cyanide compound to radical polymerization in the presence of the composite rubber, a graft polymer is obtained. can get. The amount is not particularly limited, but is preferably 65 to 400 parts by weight, preferably 100 parts by weight of the composite rubber.
The amount is more preferably 100 to 250 parts by weight, and still more preferably 100 to 150 parts by weight. If the amount is less than 65 parts by weight, the surface appearance of the molded article of the resin composition containing the graft copolymer tends to decrease, and if it exceeds 400 parts by weight, the fluidity of the resin composition containing the graft copolymer tends to decrease. Is shown.

Examples of the aromatic alkenyl compound used in the component (c) include styrene, α-methylstyrene, and vinyltoluene. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl methacrylate. And the like. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
Among them, a mixture of styrene and acrylonitrile is preferable in consideration of compatibility with the vinyl chloride resin and fluidity of the resin composition containing the graft copolymer.

The graft polymerization is performed using a composite rubber ((a) +
(B) adding at least one monomer (c) selected from an aromatic alkenyl compound, a (meth) acrylate ester and a vinyl cyanide compound to the latex in one step or in multiple steps by a radical polymerization method; Is preferred. Further, as the radical polymerization initiator used for the polymerization, a peroxide, an azo-based initiator or an oxidation-reduction-based initiator obtained by combining an oxidizing agent and a reducing agent is preferable, and particularly, ferrous sulfate, disodium ethylenediaminetetraacetate, A redox initiator combining sodium formaldehyde sulfoxylate and hydroperoxide is preferred.

Further, various chain transfer agents for adjusting the molecular weight and the graft ratio of the graft polymer can be added to the monomers used in the graft polymerization.

The particle size of the graft copolymer prepared as described above is not particularly limited, but the fluidity, the molded surface appearance and the impact resistance of the resin composition containing the graft copolymer are not limited. Considering that the weight average particle size is 0.0
It is preferably from 7 to 0.5 μm, more preferably from 0.10 to 0.3 μm, and even more preferably from 0.10 to 0.1 μm.
15 μm.

In the method for producing a graft copolymer used in the present invention, it is necessary to add an additional emulsifier at a stage after the start of the production of the composite rubber and before the salting out and recovery of the graft copolymer latex. There is.

When the polymerization is carried out only with the emulsifier contained in the polyorganosiloxane (a) latex without adding an emulsifier, the stability of the polymerized latex against shearing force is low, Due to the shearing force of the pump for the later transfer of latex, etc.
It is not preferable because the latex is easily disintegrated, causing polymerization cullet or blockage of the pump.

In the production of the graft copolymer used in the present invention, a sulfonate or sulfate emulsifier (1) and a carboxylate emulsifier (2) are used in combination as the additional emulsifiers. It is not preferable to additionally add only the sulfonate or sulfate emulsifier (1) because the stability of the polymerized latex against the shearing force is insufficient and the moisture content after coagulation increases. To improve this, it is necessary to increase the amount of the emulsifier used. However, if the amount of the emulsifier is increased, the coagulation recovery of the latex and the thermal stability of the resin composition containing the graft copolymer are impaired.

On the other hand, when only the carboxylate emulsifier is additionally added, the thermal stability of the resin composition containing the graft copolymer is impaired.

Sulfonate or sulfate emulsifier (1)
Examples thereof include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate, sulfonate emulsifiers such as naphthalenesulfonic acid formalin condensate, and sodium lauryl sulfate, sodium stearyl sulfate, and polyoxyethylene alkyl. Examples thereof include sulfate emulsifiers such as phenyl ether sulfate, and one or more of these can be used. Among these, polyoxyethylene alkylphenyl ether sulfate is preferred in consideration of the thermal stability of the resin composition containing the graft copolymer.

On the other hand, examples of the carboxylate emulsifier (2) include various purified fatty acid soaps such as tallow fatty acid soap, coconut oil fatty acid soap, rosin acid soap, stearates and oleates, dipotassium alkenyl succinate and N
N-acyl sarcosine salts such as sodium lauroyl sarcosine, and the like. Among them, considering the stability to the shearing force of the polymerized latex and the moisture content after coagulation, and further considering the thermal stability of the resin composition containing the graft copolymer. And alkenyl succinic acid dipotassium salt is preferred.

The emulsifiers (1) and (2) are used in necessary amounts in consideration of the stability of the polymerized latex against the shearing force. The preferred range of the amount of the emulsifier (1) used is 0.01 to 5 parts by weight, more preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the solid content of the polymerized latex. The preferred range of the amount of the emulsifier (2) is 0.015 to 5 parts by weight per 100 parts by weight of the solid content in the polymerized latex.
Parts by weight, more preferably 0.1 to 1.0 parts by weight.

The method of adding the emulsifiers (1) and (2) is as follows.
Addition before impregnating and polymerizing poly (organosiloxane) (a) with alkyl (meth) acrylate, grafting at least one monomer selected from aromatic alkenyl compounds, (meth) acrylates or vinyl cyanide compounds It can be added at any time of addition before polymerization, addition until completion of graft polymerization, and addition at a stage before completion of graft polymerization and salting out. The order of adding the emulsifier (1) and the emulsifier (2) is not particularly limited.

In the method for producing a graft copolymer constituting the resin composition of the present invention, after graft polymerization is carried out, this polymerized latex is poured into an aqueous calcium salt solution and salted out, whereby the graft copolymer is obtained. Collect. Examples of the calcium salt to be used include water-soluble calcium salts such as calcium chloride, calcium acetate, calcium nitrate, and calcium bromide. Among them, calcium chloride and calcium acetate are preferable in consideration of coagulability and economy.

If a coagulant other than a calcium salt such as a magnesium salt or an aluminum salt is used as a coagulant, the heat stability of the obtained resin composition containing the graft copolymer may be reduced.

The graft copolymer, which is a component of the resin composition of the present invention, preferably contains 70 to 99% by weight of an insoluble content in an acetone solvent, and contains 0.1% of an acetone-soluble content.
The reduced viscosity measured as a 2 g / 100 cc N, N-dimethylformamide solution at 25 ° C. is 0.30 to 0.7.
It is 0 dl / g.

70% by weight insoluble in acetone solvent
When the amount is less than 100%, the impact resistance of the resin composition containing the graft copolymer tends to slightly decrease. On the other hand, when the amount exceeds 99% by weight, the fluidity of the resin composition including the graft copolymer tends to decrease. Show.

Also, 0.2 g / 100 cc of acetone-soluble matter
When the reduced viscosity of the N, N-dimethylformamide solution measured at 25 ° C. is less than 0.30 dl / g, the impact resistance of the resin composition containing the graft copolymer tends to decrease slightly. When the viscosity exceeds 0.70 dl / g, the fluidity and the surface appearance of the resin composition containing the graft copolymer in low-temperature molding tend to decrease.

In consideration of the flowability, molded surface appearance and impact resistance of the vinyl chloride resin composition according to the present invention, a more preferable range of the acetone-insoluble content is 75 to 95% by weight,
More preferably, the reduced viscosity is 80 to 95% by weight, and the more preferable range of the reduced viscosity measured at 25 ° C. as a 0.2 g / 100 cc N, N-dimethylformamide solution of acetone-soluble component is 0.50 to 0.70 dl / g, more preferably in the range of 0.55 to 0.65 dl / g.

The method for producing the graft copolymer in the above range of the acetone-insoluble content and the solution viscosity of the acetone-soluble component is not particularly limited, but preferred examples thereof include aromatic alkenyl compounds and methacrylic compounds. When at least one monomer (c) selected from an acid ester, an acrylate ester and a vinyl cyanide compound is graft-polymerized, the amount of a polymerization initiator (ferrous sulfate, disodium ethylenediaminetetraacetate, In the case of a redox initiator combining sodium formaldehyde sulfoxylate and hydroperoxide, the amount of ferrous sulfate and disodium ethylenediaminetetraacetic acid used, the amount of sodium formaldehyde sulfoxylate used, or the use of hydroperoxide Limit) To a method or grafting an aromatic alkenyl compound used in the polymerization, methacrylic acid esters, acrylic acid esters and vinyl cyanide compounds, ~
A method of mixing and using a chain transfer agent such as various mercaptans and styrene dimer in at least one kind of selected monomer (c), a method of controlling the polymerization temperature, and the like.
Considering the ease of controlling the amount of acetone-insoluble component and the solution viscosity of acetone-soluble component, the amount of polymerization initiator (ferrous sulfate, disodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate) In the case of an oxidation-reduction initiator which is a combination of acetic acid and hydroperoxide, the amount of ferrous sulfate disodium ethylenediaminetetraacetate or the amount of sodium formaldehyde sulfoxylate or the amount of hydroperoxide is limited. The method is preferred.

The content of the graft copolymer in the vinyl chloride resin composition according to the present invention is not particularly limited, but it is necessary to consider the fluidity, the molded surface appearance and the impact resistance of the resin composition. Then, the amount is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 1 part by weight, the effect of improving the fluidity and impact resistance cannot be obtained, and if it exceeds 30 parts by weight, various properties such as the molding surface appearance, fluidity and tensile strength of the resin composition tend to decrease.

The copolymer used as the component (C) in the present invention is an aromatic alkenyl compound having at least one selected from aromatic alkenyl compounds, (meth) acrylates and vinyl cyanide as constituent units. Examples thereof include styrene, α-substituted styrene, nuclear-substituted styrene and derivatives thereof, for example, α-methylstyrene, chlorostyrene, vinyltoluene and the like.

The methacrylic acid ester has an alkyl group having 1 to 13 carbon atoms, and the alkyl group of the methacrylic acid ester may be a linear or branched alkyl group or a cyclic alkyl group. good. Specifically, those having a linear alkyl group include methyl methacrylate, ethyl methacrylate, and n-methacrylic acid.
Butyl, lauryl methacrylate, tridecyl methacrylate and the like. Examples of a compound having a branched alkyl group include i-butyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate. Examples of the compound having a cyclic alkyl group include cyclohexyl methacrylate and the like, but the present invention is not limited to such specific examples. Examples of the acrylate include those having an alkyl group having 1 to 13 carbon atoms. The alkyl group of the acrylate may be linear or branched, or may be a cyclic alkyl group. Specifically, those having a linear alkyl group include methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, and the like. Examples of the compound having a branched alkyl group include 2-ethylhexyl acrylate. Furthermore, examples of those having a cyclic alkyl group include cyclohexyl acrylate and the like, but the present invention is not limited to only such specific examples. If the number of carbon atoms exceeds 13, when added to the vinyl chloride resin, the melting and kneading of the vinyl chloride resin are hindered. This leads to a reduction in impact. Further, when the number of carbon atoms exceeds 13, the polymerization rate is reduced, so that the polymerizability is poor and a problem may occur in productivity.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

In the present invention, one or more of these aromatic alkenyl compounds, (meth) acrylates and vinyl cyanide compounds can be used depending on the purpose of use.

Other monomers copolymerizable therewith include vinyl esters such as vinyl acetate; dicarboxylic anhydrides such as maleic anhydride; polyfunctional monomers such as divinylbenzene and allyl methacrylate. Is mentioned.

Among these, a mixture of styrene and acrylonitrile is preferable in consideration of compatibility with the vinyl chloride resin and fluidity of the resin composition containing the copolymer.

The copolymer (C) used in the present invention comprises 1
It can be obtained by staged or multistage polymerization.

Further, the weight average molecular weight (Mw) of the copolymer (C) used in the present invention measured by gel permeation chromatography is 5,000.
５，5,000,000, preferably 10,0
More preferably, it is 00 to 3,000,000.

The copolymer (C) has a weight average molecular weight of 5,0
If it exceeds 000, the fluidity of the resin composition containing the copolymer during low-temperature molding may be significantly reduced. When the weight average molecular weight is less than 5,000, the fluidity of the resin composition containing the copolymer is improved, but there is a possibility that various physical properties of the molded article, particularly, impact resistance, heat resistance, and the like may be significantly reduced. is there.

Examples of the polymerization method of the copolymer (C) include an emulsion polymerization method, a suspension polymerization method and a solution polymerization method, and the application of the emulsion polymerization method is most preferable.

The emulsifier that can be used here is not particularly limited, and a known emulsifier can be used. For example, anionic surfactants such as fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl phosphate esters, dialkyl sulfosuccinates; polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan acid fatty esters, Nonionic surfactants such as glycerin fatty acid esters; and cationic surfactants such as alkylamine salts can be used. These emulsifiers can be used alone or in combination.

When the pH of the polymerization system becomes alkaline depending on the type of the emulsifier to be used, a suitable pH regulator can be used to prevent hydrolysis of methacrylic acid esters and acrylic acid esters. Examples of usable pH regulators include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, and citric acid-
Potassium hydrogen citrate, sodium dihydrogen phosphate-boric acid, disodium hydrogen phosphate-citric acid and the like can be used.

The polymerization initiator may be a water-soluble initiator or an oil-soluble initiator alone or may be an oxidation-reduction initiator. Examples of the water-soluble initiator include ordinary persulfates such as sodium persulfate. , A potassium persulfate, an inorganic initiator such as ammonium persulfate alone or a redox initiator by a combination with a sulfite, a hydrogen sulfite, a thiosulfate, a first metal salt, sodium formaldehyde sulfoxylate, etc. Can also be used.

Examples of the oil-soluble initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-hydroperoxide and cumene hydroperoxide;
The azo compound can be used alone or in combination with a first metal salt, sodium formaldehyde sulfoxylate, or the like, but can be used as a redox initiator, but is not limited to such specific examples.

The weight average molecular weight (Mw) of the copolymer (C) can be arbitrarily adjusted by a known chain transfer agent such as n-octyl mercaptan or t-dodecyl mercaptan, polymerization conditions and the like.

The copolymer (C) may be recovered, for example, when obtained by an emulsion polymerization method, after cooling the obtained polymer latex, acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like, or aluminum chloride, The polymer can be precipitated by acid coagulation or salting out with a salt electrolyte such as calcium chloride, magnesium sulfate, aluminum sulfate, or calcium acetate, and then further filtered, washed and dried. The coagulant in the case of acid coagulation or salting out is not limited to these specific examples, and any known coagulant can be used. In addition, a known recovery method such as a spray drying method or a freeze drying method can also be used.

The content of the copolymer (C) in the resin composition according to the present invention is not particularly limited. However, considering the fluidity, molding surface appearance and impact resistance of the resin composition. The amount is preferably 0.5 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.5 part by weight, the effect of improving fluidity and tensile strength cannot be obtained, and if it exceeds 20 parts by weight, the impact resistance may be reduced.

The addition of the graft copolymer (B) and the copolymer (C) to the vinyl chloride resin (A) can be carried out by a known mixing method, for example, a Henschel mixer, a Banbury mixer, a mixing roll, a calender roll, or the like. It is performed by an extruder or the like. Further, the resin composition of the present invention can be used in any form of powder or pellet.

The resin composition of the present invention can be formed into a desired shape by molding by calendering, extrusion, injection molding, blow molding or the like.

As long as the effects of the present invention are not impaired, known heat stabilizers, lubricants, processing aids, rubber-like elastic materials, plasticizers, heat-resistant improvers, fillers, and the like may be added to the resin composition of the present invention as long as the effects of the present invention are not impaired. ,
Various additives such as a release agent, a foaming agent, a pigment, an ultraviolet stabilizer, an antifogging agent, an antibacterial agent, an antistatic agent, a surfactant, and a flame retardant can be added together.

Examples of the heat stabilizer include tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, lead silicate,
Lead-based stabilizers such as potassium, magnesium, barium,
Metals such as zinc, cadmium and lead and 2-ethylhexanoic acid,
Metal soap-based stabilizers derived from fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; alkyl groups, ester groups and fatty acids Organotin-based stabilizers derived from salts, maleates, and sulfides; Ba-Zn-based, Ca-Zn-based,
Ba-Ca system, Ca-Mg-Sn system, Ca-Zn-Sn
, Pb-Sn-based, Pb-Ba-Ca-based composite metal soap-based stabilizers; metals such as barium and zinc; branched fatty acids such as 2-ethylhexanoic acid, isodecanoic acid and trialkylacetic acid; oleic acid and ricinoleic acid , Unsaturated fatty acids such as linoleic acid, aliphatic acid such as naphthenic acid, carboxylic acid, benzoic acid, salicylic acid, metal salts derived from two or more organic acids such as aromatic acids such as substituted derivatives thereof. Stabilizers; these stabilizers can be used as petroleum hydrocarbons,
A metal salt that is dissolved in an organic solvent such as a glycerin derivative and further contains a stabilizing aid such as a phosphite, an epoxy compound, a color inhibitor, a transparency improver, a light stabilizer, an antioxidant, and a lubricant. Metal-based stabilizers such as liquid stabilizers; epoxy compounds such as epoxy resins, epoxidized soybean oil, epoxidized vegetable oils, and epoxidized fatty acid alkyl esters;
Phosphorus is substituted by an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, etc., and a dihydric alcohol such as propylene glycol, hydroquinone, bisphenol A
And non-metallic stabilizers such as organic phosphites having an aromatic compound such as these, and these may be used alone or in combination of two or more.

Examples of the lubricant include pure hydrocarbons such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, and low-molecular-weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxy fatty acids; fatty acid amides; Fatty acid amides such as fatty acid amides; lower alcohol esters of fatty acids; polyhydric alcohol esters of fatty acids such as glyceride; polyglycol esters of fatty acids; ester systems such as fatty alcohol esters of fatty acids (ester wax); metal soaps, fatty alcohols; Examples include polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, fatty acids and polyglycols, and partial esters of polyglycerol.

Further, examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, 2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate Phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, normal hexyl normal decyl phthalate, normal octyl normal decyl Phthalate plasticizers such as phthalate; Ruhosufeto, tri-2-ethylhexyl phosphate, triphenyl phosphate,
Phosphate plasticizers such as 2-ethylhexyl diphenyl phosphate and cresyl diphenyl phosphate;
Adipic ester plastics such as di-2-ethylhexyl adipate, diisodecyl adipate, normal octyl-normal decyl adipate, normal heptyl-normal nonyl adipate, diisooctyl adipate, diisonormal octyl adipate, dinormal octyl adipate, and didecyl adipate Agents: Sebacate plasticizers such as dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, and butyl benzyl sebacate; di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate Azelaic acid ester plasticizers such as triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tri-2-ethyl acetyl citrate; Citric acid ester plasticizers such as sil; glycolic acid ester plasticizers such as methylphthalylethyl glycolate, ethylphthalylethyl glycolate and butylphthalylbutyl glycolate; tributyl trimellitate and tri-normal hexyl trimellit Tate, tri-2-ethylhexyl trimellitate, tri-
Trimellitate plasticizers such as normal octyl trimellitate, tri-isooctyl trimellitate and tri-isodecyl trimellitate; phthalic acid isomers such as di-2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate Ester plasticizers; ricinoleate plasticizers such as methyl acetyl ricinolate and butyl acetyl ricinolate; polyester plasticizers such as polypropylene adipate, polypropylene sebacate and modified polyesters thereof; epoxidized soybean oil, epoxy butyl steer , Epoxy (2-ethylhexyl) stearate, epoxidized linseed oil, 2-
Epoxy plasticizers such as ethylhexyl epoxy tolate and the like can be mentioned, and these can be used alone or in combination of two or more as necessary.

As the rubbery elastic body, polybutadiene,
Polyisoprene, polychloroprene, fluorine rubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene graft copolymer, acrylonitrile-styrene-butadiene copolymer Polymer rubber, acrylonitrile-styrene-butadiene-based graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene-ethylene-butylene-styrene copolymer rubber, ethylene- Propylene copolymer rubber, ethylene-
Examples include propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, and silicone rubber.

As the diene of the ethylene-propylene-diene copolymer rubber (EPDM), 1,4-hexanediene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene and the like are used. These impact modifiers can be used alone or in combination of two or more.

In addition, flame retardants such as aluminum hydroxide, antimony trioxide, halogen compounds and phosphorus compounds can be used arbitrarily according to the purpose, as long as the effects of the present invention are not impaired.

Although the compounds that can be blended have been described above, the present invention is not limited to only these specific examples.

Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to these specific examples. In the description, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

(1) Measurement of weight average particle diameter of polyorganosiloxane and graft copolymer in latex: The weight average particle diameter of polyorganosiloxane and graft copolymer in latex is DLS-700 type (Otsuka Electronics ( (Manufactured by K.K.).

(2) Measurement of stability of polymer latex against shearing force: polymer latex 300 placed in beaker
g was kept at 50 ° C., and this was mixed with a homomixer (TK AUTO homomixer manufactured by Tokushu Rika Kogyo Co., Ltd.) to 1000 g.
Stirring was performed under the condition of 0 revolutions / second, and the shear force caused by this stirring destroyed the latex, and the time required for the flow to stop by solid analysis was measured.

(3) Measurement of acetone-insoluble matter: The amount of acetone-insoluble matter in the graft copolymer in the examples was determined by measuring about 2.5 g (weighed) of the graft copolymer in a flask equipped with a condenser and a heater. Add 80 ml of acetone,
After performing heat extraction at 65 ° C. for 3 hours with a heater, and after cooling, the inner solution is treated with a centrifuge (manufactured by Hitachi Koki Co., Ltd.) at 15,000 rpm for 30 minutes. Then, the precipitate after removing the supernatant liquid after removing the acetone-insoluble matter was dried, and the weight was measured and calculated by the following formula.

Acetone-insoluble matter (% by weight) = (dry weight of precipitate after separation treatment / weight of graft copolymer before acetone extraction) × 100 (4) Measurement of reduced viscosity of acetone-soluble matter: The measurement of the reduced viscosity of the acetone-soluble component in the polymer is performed by extracting the above graft copolymer with an acetone solvent,
Next, the acetone solvent in the supernatant obtained by separation of the acetone-insoluble matter by centrifugation was evaporated under reduced pressure to precipitate and recover the acetone-soluble component. Then, 0.2 g of the acetone-soluble component was added to 100 cc of N, N-dimethylformamide. The viscosity of the solution dissolved in the solution is automatically measured with an automatic viscometer (SAN DENSHI
Was measured at 25 ° C. using the AVL-2 type (manufactured by Corporation), and the reduced viscosity of the acetone-soluble component was determined from the solvent viscosity measured under the same conditions.

(5) Measurement of weight average molecular weight of copolymer (C): Measurement of the weight average molecular weight (Mw) of copolymer (C) in Examples was performed by dissolving 0.05 g of copolymer in 10 cc of chloroform. The resulting solution was subjected to gel permeation chromatography (LC-10A system manufactured by Shimadzu Corporation) and column (GPC manufactured by Showa Denko KK)
KF-806L).

(6) Fluidity evaluation: screw diameter 25 mm
JIS. Extruder at cylinder temperature 160 ° C
Dimensions based on K-7110 (12.7 mm × 6.35)
The flowability was evaluated by the extrusion discharge amount (g) per minute at the time of extrusion molding of the square rod of (mm).

(7) Evaluation of molding surface appearance: L-shape molding at a cylinder temperature of 160 ° C. using a square bar immediately after coming out of the extruder and an extruder having a screw diameter of 25 mm in the evaluation of the above item (6). The products were extruded, and the appearance of both molded surfaces was visually evaluated according to the following criteria.

：: Both the square bar and the L-shaped molded product have no edge at the end of the molded product and have excellent surface gloss and smoothness.

△: There are no scabs at the four corners of the square bar, and the surface gloss and smoothness are good.

Although the edge of the L-shaped molded product is not squeezed, either the surface gloss or the smoothness is inferior.

×: Neither the square bar nor the L-shaped molded product has an edge at the end of the molded product, but is inferior in surface gloss and smoothness.

XX: Both the square bar and the L-shaped molded product are inferior in surface gloss and smoothness, and both the square bar and the L-shaped molded product have scabs.

(8) Impact resistance evaluation: Using the square bar obtained in the evaluation of the above item (6), JIS K-7110 was used.
The impact strength at 23 ° C and -20 ° C was measured in accordance with

[0094]

The present invention will be described below with reference to examples.

Example 1 In the production of a polyorganosiloxane latex, 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this, 300 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added, and the mixture was passed through a homomixer once at a pressure of 200 kg / cm ² to obtain a stable premixed organosiloxane latex.

On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer.
A 0% dodecylbenzenesulfonic acid aqueous solution was prepared.

While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour and cooled.
The reaction was then neutralized with aqueous sodium hydroxide.

The latex thus obtained was mixed with 17
When the solid content was determined by drying at 0 ° C. for 30 minutes, 17.
7%. The weight average particle diameter of the polyorganosiloxane in the latex was 0.05 μm.

The graft copolymer (B) was prepared by placing 45.2 parts of the prepared polyorganosiloxane latex, polyoxyethylene alkylphenyl ether sulfate 0 in a reaction vessel equipped with a reagent injection vessel, a cooling pipe, and a stirrer. After collecting and mixing 148.5 parts of distilled water, 42 parts of butyl acrylate, 0.3 part of allyl methacrylate, 0.1 part of 1,3-butylene methacrylate and t-butyl hydroperoxide were obtained. 0.11 part of the mixture was added.

The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal liquid temperature reaches 60 ° C., ferrous sulfate 0.00
0075 parts, an aqueous solution obtained by dissolving 0.000225 parts of ethylenediaminetetraacetic acid disodium salt and 0.2 parts of sodium formaldehyde sulfoxylate in 10 parts of distilled water were added, and radical polymerization was started. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component, thereby obtaining a composite rubber latex of polyorganosiloxane and butyl acrylate rubber.

After the liquid temperature inside the reactor has dropped to 70 ° C.,
Sodium formaldehyde sulfoxylate 0.25
An aqueous solution of 10 parts of distilled water was added, and then 2.5 parts of acrylonitrile, 7.5 parts of styrene and t-
A mixture of 0.05 parts of butyl hydroperoxide was added to 2
It was added dropwise over time to polymerize. After the completion of dropping, temperature 60
C. for 1 hour, then ferrous sulfate 0.001
Parts, disodium ethylenediaminetetraacetate 0.003
And 0.2 parts of sodium formaldehyde sulfoxylate and 0.2 parts of polyoxyethylene alkylphenyl ether sulfate, an aqueous solution of 10 parts of distilled water was added, and then 10 parts of acrylonitrile,
A mixed solution of 30 parts of styrene and 0.2 part of t-butyl hydroperoxide was dropped and polymerized over 2 hours. After completion of the dropping, the temperature of 60 ° C. was maintained for 0.5 hour, 0.05 part of cumene hydroperoxide was added, and the temperature of 60 ° C. was further maintained for 0.5 hour, followed by cooling. Dipotassium alkenyl succinate was added to this latex to obtain a polymerized latex of a graft copolymer obtained by graft-polymerizing acrylonitrile and styrene onto a composite rubber composed of a polyorganosiloxane and butyl acrylate.

The weight average particle diameter of the graft copolymer in the latex determined by the dynamic light scattering method was 0.12 μm.

The stability of this polymerized latex against shearing force was 5 minutes in a homomixer test.

Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 1% was heated to 60 ° C. and stirred. 100 parts of the latex of the graft copolymer was gradually dropped into this, and solidified. Then, the precipitate was separated, washed, and then centrifuged (H-130E manufactured by Domestic Centrifuge Co., Ltd.) for 1 hour.
A dehydration treatment was performed for 2 minutes at a condition of 800 rotations per second.

The resulting graft copolymer had an acetone-insoluble content of 85%, and the acetone-soluble component had a reduced viscosity of 0.58 dl / g.

The method for producing the copolymer is as follows. 300 parts of distilled water and 1.0 part of dipotassium alkenylsuccinate are collected in a reaction vessel equipped with a reflux condenser and a stirrer, and then a nitrogen stream is introduced into the reaction vessel. To replace the atmosphere with nitrogen. Thereafter, when the temperature was raised to 75 ° C. and the internal temperature reached 75 ° C., 0.001 part of ferrous sulfate,
An aqueous solution in which 0.003 part of disodium ethylenediaminetetraacetate and 1.0 part of sodium aldehyde sulfoxylate were dissolved in 10 parts of distilled water was added. Then, a mixture of 30 parts of acrylonitrile, 70 parts of styrene, 0.4 part of t-dodecyl mercaptan and 0.6 part of t-butyl hydroperoxide was added dropwise over 2 hours,
Radical polymerization was performed. After the dropwise addition, 1.5
After holding for a time, the mixture was cooled to obtain a copolymer latex. After adding calcium chloride to this copolymer latex to salt out the polymer, washing and drying it,
An acrylonitrile-styrene copolymer was obtained.

Weight average molecular weight (Mw) of the copolymer measured by gel permeation chromatography
Was 110,000.

Next, the following composition was prepared, and an evaluation test was conducted on fluidity, molded surface appearance and impact resistance.

Vinyl chloride homopolymer having an average polymerization degree of 1,000 (TK-1000, manufactured by Shin-Etsu Chemical Co., Ltd.) 10
In 0 parts, 1.5 parts of dibutyltin mercaptide (T-17MJ, manufactured by Katsuta Kako Co., Ltd.), 1.2 parts of calcium stearate (SAK-CS-G, manufactured by Shinagawa Kako Co., Ltd.)
Glycerin monostearate (Rikemar S-100A, manufactured by Riken Vitamin Co., Ltd.) 0.5 part, polyethylene wax (Mitsui Chemicals, Hi-wax220M)
P) 0.2 parts, calcium carbonate (Shiroishi Calcium Co., Ltd.)
5.0 parts, titanium oxide (Ishihara Sangyo Co., Ltd.)
R-830), 1.0 part of the graft copolymer (B) and the copolymer (C) were mixed with a Henschel mixer until the temperature reached 110 ° C., and the mixture was cooled to room temperature and chlorided. A vinyl resin composition was obtained.

8 parts of the graft copolymer (B) and 4 parts of the copolymer (C) were added to the above composition.
The results obtained are shown in Table 1.

[Example 2] The copolymer (C) of Example 1 was replaced with methacrylate P-
501A (manufactured by Mitsubishi Rayon Co., Ltd.). The weight average molecular weight of the copolymer measured by gel permeation chromatography was 940,000.

An evaluation test was carried out in the same manner as in Example 1 except that the amount of the copolymer added was changed to 2 parts. The results are shown in Table 1.

Example 3 The copolymer (C) of Example 1 was replaced with methacrylic acid ester-based copolymer
530A (manufactured by Mitsubishi Rayon Co., Ltd.). The weight average molecular weight of the copolymer measured by gel permeation chromatography was 3,890,000.

An evaluation test was carried out in the same manner as in Example 1 except that the amount of the copolymer was changed to 1 part, and the results are shown in Table 1.

[Example 4] 100 parts of the vinyl chloride homopolymer (TK-1700, manufactured by Shin-Etsu Chemical Co., Ltd.) having an average degree of polymerization of 1700 was obtained by the following method. An evaluation test was carried out in the same manner as in Example 1 except that 7 parts of the obtained copolymer was blended as copolymer (C), and the results are shown in Table 1.

260 parts of distilled water and 1.0 part of dipotassium alkenylsuccinate were collected in a reaction vessel equipped with a reflux condenser and a stirrer. Next, nitrogen replacement was carried out by passing a nitrogen stream into the reaction vessel with stirring, and then 20 parts of methyl methacrylate and 6 parts of ethyl methacrylate were used as the component (a).
A mixture consisting of 0 parts and 4.0 parts of n-octylmercaptan was charged, and the temperature was raised to 70 ° C. with stirring. When the internal temperature reaches 50 ° C., ammonium persulfate 0.15
, When the internal temperature was 55 ° C, 0.30 part of sodium sulfite was added. Then, after heating and polymerizing at 70 ° C for 2 hours, 20 parts of methyl methacrylate as a component (b), n-
0.06 parts of octyl mercaptan was added over 30 minutes. After completion of the addition, the mixture was kept at 70 ° C. for 2 hours, and then cooled to obtain a copolymer latex having a conversion of 99.9% or more.

Calcium chloride was added to the obtained copolymer latex to cause salting out, followed by washing and drying.
A copolymer was obtained.

The weight average molecular weight of the copolymer measured by gel permeation chromatography was 2
It was 0000.

Example 5 Eight parts of the graft copolymer (B) obtained in Example 1 was used, and methablene C-methyl-methacrylate-styrene-butadiene-based graft copolymer was used.
223 (manufactured by Mitsubishi Rayon Co., Ltd.) and 4 parts of methacrylic acid ester-based copolymer, Metablen P-570A, were added and evaluated as the copolymer (C) in the same manner as in Example 1. The tests were performed and the results are shown in Table 1.

The weight average molecular weight of the copolymer measured by gel permeation chromatography was 27
It was 0000.

Example 6 8 parts of the graft copolymer (B) obtained in Example 1 was mixed with acrylonitrile-styrene-
Butadiene graft copolymer (rubber content 60%)
The evaluation test was carried out in the same manner as in Example 1 except that 4 parts of the copolymer (C) obtained in Example 1 was added and blended. The results are shown in Table 1.

Example 7 The vinyl chloride homopolymer of Example 1 was obtained in Example 1 with 100 parts of vinyl chloride homopolymer having an average degree of polymerization of 600 (TK-600, manufactured by Shin-Etsu Chemical Co., Ltd.). 4 parts of the obtained graft copolymer (B), and the copolymer obtained by the following method was used as a copolymer (C).
An evaluation test was conducted in the same manner as in Example 1 except that 7 parts were added. The results are shown in Table 1.

The method for producing the copolymer is as follows. 300 parts of distilled water, 1.0 part of dipotassium alkenylsuccinate, 30 parts of acrylonitrile and 70 parts of styrene are collected in a reaction vessel equipped with a reflux condenser and a stirrer. The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reaction vessel. Thereafter, when the temperature was raised to 50 ° C. and the internal temperature became 50 ° C., an aqueous solution in which 0.15 part of ammonium persulfate was dissolved in 10 parts of distilled water was added. Then, after heating polymerization at the same temperature for 3 hours, the mixture was cooled to obtain a copolymer latex. After calcium chloride was added to the copolymer latex to salt out the polymer, the polymer was washed and dried to obtain an acrylonitrile-styrene copolymer.

The weight average molecular weight of the copolymer measured by gel permeation chromatography was 2,
790,000.

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that the graft copolymer (B) was not added and only 8 parts of the copolymer (C) obtained in Example 1 was blended and added. The tests were performed and the results are shown in Table 1.

Comparative Example 2 An evaluation test was carried out in the same manner as in Example 1 except that the amount of the graft copolymer (B) obtained in Example 1 was changed to 45 parts. Shown in

Comparative Example 3 In the preparation of the graft copolymer (B) in Example 1, the amount of acrylonitrile and styrene to be graft-polymerized was 100 with respect to 100 parts by weight of the composite rubber of polyorganosiloxane and butyl acrylate rubber. Parts by weight were used.

The resulting graft copolymer had an acetone-insoluble content of 80%, and the reduced viscosity of the acetone-soluble component was 0.51 dl / g. An evaluation test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 4 In the preparation of the graft copolymer (B) in Example 1, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate and t-butyl hydroperoxide were used during the graft polymerization. All the amounts of oxide were doubled.

The resulting graft copolymer had an acetone-insoluble content of 64%, and the reduced viscosity of the acetone-soluble component was 0.27 dl / g. An evaluation test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 5 In the preparation of the graft copolymer (B) in Example 1, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate and t-butyl hydroperoxide were used during the graft polymerization. The amount of all oxides was halved.

The obtained graft copolymer had an acetone-insoluble content of 95%, and the reduced viscosity of the acetone-soluble component was 0.92 dl / g. An evaluation test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 6 In the production of the copolymer (C) in Example 1, the amount of sodium formaldehyde sulfoxylate and t-butyl hydroperoxide was increased by 3 times, and the amount of t-dodecyl mercaptan was increased by 6 times. did.

The weight average molecular weight of the copolymer measured by gel permeation chromatography was 4,
800. An evaluation test was conducted in the same manner as in Example 1 except that the amount of the copolymer added was changed to 8 parts. The results are shown in Table 1.

Comparative Example 7 The copolymer (C) in Example 1 was obtained by the following method.

In a reaction vessel equipped with a reflux condenser and a stirrer, 300 parts of distilled water, 0.8 part of dipotassium alkenylsuccinate, 30 parts of acrylonitrile and 70 parts of styrene are collected. Next, the inside of the reaction vessel was replaced with nitrogen while stirring through a nitrogen stream.

After the completion of the nitrogen replacement, the temperature is raised to 50 ° C. When the internal temperature reached 45 ° C. in the course of the temperature increase, 1.0 part of sodium formaldehyde sulfoxylate and 1.0 part of t-butyl hydroperoxide were added, and heat polymerization was performed at 50 ° C. for 3 hours. Thereafter, the polymerization was terminated to obtain a copolymer latex. After calcium chloride was added to this copolymer latex for salting out, washing and drying were performed to obtain a copolymer.

The weight average molecular weight of the copolymer measured by gel permeation chromatography was 5,
556,000. An evaluation test was performed in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative Example 8] An evaluation test was carried out in the same manner as in Example 1 except that the blending amount of the copolymer (C) obtained in Example 1 was changed to 30 parts. Show.

[0140]

[Table 1]

[0141]

According to the vinyl chloride resin composition of the present invention, it is possible to obtain a molded article having excellent fluidity and surface appearance in low-temperature molding and excellent impact resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (Reference) C08L 33:20)

Claims (2)

[Claims] 1. An aromatic compound is added to 100 parts by weight of (A) a vinyl chloride resin and 100 parts by weight of a composite rubber comprising (B) a polyorganosiloxane (a) and an alkyl (meth) acrylate rubber (b). At least one monomer (c) selected from an alkenyl compound, a (meth) acrylic acid ester and a vinyl cyanide compound is used in an amount of 65 to 40
A graft copolymer obtained by graft polymerization of 0 parts by weight, wherein the insoluble content of the graft copolymer in an acetone solvent is 70 to 99% by weight and the acetone-soluble content is 25%.
C., 1 to 30 parts by weight of a graft copolymer having a reduced viscosity of 0.2 g / 100 cc N, N-dimethylformamide solution of 0.30 to 0.70 dl / g, (C) an aromatic alkenyl compound, and (meth) A vinyl chloride resin composition comprising 0.5 to 20 parts by weight of a copolymer having at least one selected from an acrylate ester and a vinyl cyanide compound as a constitutional unit. 2. The vinyl chloride resin according to claim 1, wherein the weight average molecular weight (Mw) of the copolymer (C) measured by gel permeation chromatography is from 5,000 to 5,000,000. Composition.