JP2003327762A - Method for accelerating gelation of polyvinyl chloride resin, and polyvinyl chloride resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for accelerating the gelation of a polyvinyl chloride resin for enhancing the molding processability without lowering productivity and mechanical characteristics, and a polyvinyl chloride resin composition. <P>SOLUTION: The method for accelerating the gelation of a polyvinyl chloride resin comprises mixing 100 mass pts. of a polyvinyl chloride resin (A) with 0.01-20 mass pts. of a carboxylic acid-containing copolymer (B) obtained by copolymerizing 0.1-40 mass% of a monomer containing a carboxylic acid and 99.9-60 mass% of a vinyl monomer copolymerizable therewith. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for promoting gelation of a polyvinyl chloride resin and a polyvinyl chloride resin composition.

[0002]

2. Description of the Related Art Polyvinyl chloride resins are inexpensive and have various excellent chemical and physical properties, so that they are produced in large quantities among synthetic resins and used in a wide range of applications. Generally, when a polyvinyl chloride resin is extrusion-molded, a polyvinyl chloride resin having a high average degree of polymerization is used. This is because when the average degree of polymerization is high, physical properties such as tensile strength and heat resistance are improved, and a large effect is exhibited even when the amount of the impact strength modifier added is small.

[0003]

However, when the average degree of polymerization increases, the moldability of the polyvinyl chloride resin,
In particular, there is a possibility that the kneadability may be lowered and the surface appearance of the molded product may be deteriorated. The processing temperature may be increased in order to compensate for such a decrease in molding processability, particularly kneading property. However,
When the processing temperature is raised, the resin itself deteriorates due to heat,
It has become difficult to exhibit the original physical properties of the polyvinyl chloride resin. Further, when the average degree of polymerization is lowered to improve the moldability, the fluidity and the surface appearance of the molded product are improved, but the mechanical properties may be deteriorated. Further, for the purpose of improving the molding processability of a polyvinyl chloride resin composition, Japanese Patent Publication No.
In Japanese Patent No. 33821, Japanese Patent Publication No. 52-781 and Japanese Patent Publication No. 52-3668, it is proposed to add an acrylic processing aid such as an acrylic high molecular weight polymer. It has also been proposed to improve the kneading property by adding high-density oxidized polyethylene having a gelation promoting effect. However, in any of the methods, gelation is promoted and kneading property is improved, but on the other hand, the motor load of the molding machine during the profile extrusion molding is increased and the productivity is decreased.
Further, addition of a liquid plasticizer was also investigated, but when the liquid plasticizer was added, there was a problem that the fluidity and the surface appearance of the molded product were improved, but the mechanical properties were lowered. The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a method for accelerating gelation of a polyvinyl chloride resin and a polyvinyl chloride resin composition which improve molding processability without lowering productivity and mechanical properties.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that when a high-molecular polymer containing an appropriate amount of carboxylic acid is added to a polyvinyl chloride resin, Gelation of vinyl chloride resin is promoted,
The inventors have found that molding processability is improved, and have invented the following method for promoting gelation of polyvinyl chloride resin and polyvinyl chloride resin composition. That is, the method for promoting gelation of a polyvinyl chloride resin according to the present invention is carried out by adding 0.1 to 40% by mass of a carboxylic acid-containing monomer to the polyvinyl chloride resin (A).
And a carboxylic acid-containing copolymer (B) obtained by copolymerizing 99.9 to 60% by mass of a vinyl monomer that is copolymerizable with the carboxylic acid-containing monomer as a structural unit. ) It is characterized in that 0.01 to 20 parts by mass is added to 100 parts by mass. Further, the polyvinyl chloride resin composition of the present invention comprises a polyvinyl chloride resin (A),
0.1 parts by weight per 100 parts by weight of polyvinyl chloride resin (A).
01 to 20 parts by mass of the carboxylic acid-containing copolymer (B), wherein the carboxylic acid-containing copolymer (B) is 0.1 to 40% by mass of the carboxylic acid-containing monomer and the carboxylic acid-containing copolymer. It is characterized in that 99.9 to 60 mass% of a vinyl monomer copolymerizable with the monomer is copolymerized as a constitutional unit.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION An example of the method for promoting gelation of a polyvinyl chloride resin and the polyvinyl chloride resin composition of the present invention will be described. This polyvinyl chloride resin composition is 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, based on 100 parts by mass of the polyvinyl chloride resin (A) and the polyvinyl chloride resin (A). Part of the carboxylic acid-containing copolymer (B). In such a polyvinyl chloride resin (A), the carboxylic acid of the carboxylic acid-containing copolymer (B) reacts at an appropriate reaction rate during the molding process to promote gelation of the polyvinyl chloride resin. Since the gelling time is shortened, the moldability is improved. Moreover, the addition of the carboxylic acid-containing copolymer does not reduce productivity and mechanical properties. When the content of the carboxylic acid-containing copolymer (B) deviates from the above range, the molding processability decreases.

As the polyvinyl chloride resin (A), for example, polyvinyl chloride homopolymer, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, etc. Examples of the vinyl chloride-based copolymers include, but polyvinyl chloride homopolymers are particularly preferable because they are inexpensive and have excellent mechanical properties. The polyvinyl chloride resin (A) has an average degree of polymerization of 700 to 3000, preferably 800 to 1700.
The range of is preferable. If the average degree of polymerization is less than 700, impact resistance, heat resistance, etc. may be deteriorated.
If it exceeds 000, the moldability may deteriorate unless the temperature of the molten resin during molding is increased. When a polyvinyl chloride resin (A) having an average degree of polymerization of more than 3000 is used and the temperature of the molten resin is increased, thermal deterioration becomes severe and the original physical properties of the resin may be impaired.

The carboxylic acid-containing copolymer (B) comprises 0.1 to 40% by mass of the carboxylic acid-containing monomer and 99.9 to 60% by mass of a vinyl monomer copolymerizable with the carboxylic acid-containing monomer. % As a constituent unit. When the content of the carboxylic acid monomer in the carboxylic acid-containing copolymer (B) is less than 0.1% by mass, gelation of the polyvinyl chloride resin cannot be sufficiently promoted. On the other hand, if it exceeds 40% by mass, the latex obtained becomes unstable when the carboxylic acid-containing copolymer is produced by emulsion polymerization.

Examples of the carboxylic acid-containing monomer include:
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples thereof include acid group-containing monomers such as cinnamic acid, maleic anhydride, and butenetricarboxylic acid. Examples of the vinyl monomer copolymerizable with the carboxylic acid-containing monomer include esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate and propyl methacrylate, acrylic acid such as methyl acrylate, ethyl acrylate and butyl acrylate. , Styrenes such as styrene, α-methylstyrene and various halogen-substituted and alkyl-substituted styrenes, unsaturated nitriles such as acrylonitrile and methacrylonitrile, glycidyl acrylate,
Glycidyl methacrylate, vinyl-based monomers having a glycidyl group such as allyl glycidyl ether, and the like,
These can be used alone or in combination.

The method for producing the carboxylic acid-containing copolymer (B) is not particularly limited, but the emulsion polymerization method is preferable because it can be easily polymerized. The production by emulsion polymerization will be described below. Examples of the polymerization initiator at the time of polymerization include potassium persulfate, ammonium persulfate, persulfates such as sodium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, and diisopropylbenzene. Organic peroxides such as hydroperoxide,
Azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile can be used. Further, the above polymerization initiator may be used as a redox initiator by combining sulfite, hydrogen sulfite, thiosulfate, first metal salt, sodium formaldehyde sulfoxylate, dextrose and the like. The polymerization temperature depends on the kind of the polymerization initiator, but is usually in the range of 40 to 80 ° C. A known emulsifier can be appropriately used as the emulsifier. To the carboxylic acid-containing copolymer latex obtained in this manner, spray-drying (direct pulverization) with or without addition of an appropriate antioxidant, additive, etc. A copolymer (B) resin is obtained. Alternatively, in the carboxylic acid-containing copolymer latex,
Acid such as sulfuric acid, hydrochloric acid, phosphoric acid, and coagulants such as salts such as calcium chloride and sodium chloride are appropriately added for coagulation, heat treatment to solidify, dehydration, washing, drying and powdering. A carboxylic acid-containing copolymer (B) resin is obtained.

If necessary, various additives such as impact strength modifiers, stabilizers, lubricants, fillers, pigments, plasticizers, foaming agents, and UV stabilizers are added to the polyvinyl chloride resin composition of the present invention. Agents can be added. Among them, the polyvinyl chloride resin 1 has the further improved mechanical properties.
It is preferable to add 1 to 30 parts by mass of the impact strength modifier to 100 parts by mass.

As the impact strength modifier, a rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers copolymerizable with a rubber-based polymer, or
Chlorinated polyolefins may be mentioned. Here, as the rubber-based graft copolymer, a diene-based rubber graft copolymer in which a diene-based rubber copolymer is used as the rubber-like polymer, and an acrylic-based in which an acrylic-based rubber copolymer is used as the rubber-based polymer Examples thereof include a rubber graft copolymer and a silicone / acrylic rubber graft polymer using a silicone / acrylic rubber copolymer as a rubbery polymer.

The diene rubber graft copolymer is a diene rubber copolymer graft-polymerized with methyl methacrylate. The diene rubber copolymer is obtained by polymerizing 1,3-butadiene alone or a monomer mixture containing 1,3-butadiene and less than 50% by mass of a vinyl monomer copolymerizable therewith. It was obtained by When 50% by mass or more of a vinyl-based monomer copolymerizable with 1,3-butadiene is added, the molding processability may be deteriorated and the appearance of the molded product may be deteriorated.

Examples of vinyl monomers copolymerizable with 1,3-butadiene include aromatic vinyl such as styrene and α-methylstyrene, methacrylic acid alkyl ester such as methyl methacrylate and ethyl methacrylate, ethyl acrylate, and the like. Acrylic acid alkyl esters such as n-butyl acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, methyl vinyl ether,
Vinyl ether such as butyl vinyl ether, vinyl chloride such as vinyl chloride and vinyl bromide, vinylidene chloride,
Examples thereof include vinylidene halides such as vinylidene bromide, glycidyl acrylate, glycidyl methacrylate, vinyl monomers having glycidyl such as allyl glycidyl ether and ethylene glycol glycidyl ether. Further, as a vinyl-based monomer copolymerizable with 1,3-butadiene, as a bifunctional crosslinkable monomer,
For example, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, trimethacrylic acid ester, triacrylic acid ester, allyl methacrylic acid acrylate. Allyl esters of carboxylic acids such as allyl, diallyl phthalate,
Examples thereof include di- and triallyl compounds such as diallyl sebacate and triallyl triazine. The above-mentioned vinyl-based monomer copolymerizable with 1,3-butadiene may be used alone or in combination of two or more. Further, the diene rubber copolymer is preferably produced by emulsion polymerization because it can be easily produced. At the time of polymerization, if necessary,
Chain transfer agents such as t-dodecyl mercaptan can also be used.

A bloatr can be added to the diene rubber copolymer, if necessary. The thickening agent is to enlarge the particle size of the diene rubber copolymer, for example, inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate, aluminum sulfate, calcium acetate, magnesium acetate, etc. And organic acids such as sulfuric acid and hydrochloric acid, organic acids such as acetic acid and succinic acid, organic acid anhydrides thereof, and carboxylic acid-containing polymer latex.

In the presence of the above diene rubber copolymer, a methyl methacrylate homomonomer or a monomer mixture containing methyl methacrylate and one or more vinyl monomers copolymerizable therewith is used. Graft polymerization can be performed to obtain a diene rubber graft copolymer. Vinyl-based monomers copolymerizable with methyl methacrylate include
For example, methacrylic acid esters such as ethyl methacrylate and propyl methacrylate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, styrenes such as styrene, α-methylstyrene and various halogen-substituted and alkyl-substituted styrenes, Acrylonitrile, unsaturated nitriles such as methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, vinyl monomers having a glycidyl group such as allyl glycidyl ether and the above-mentioned crosslinkable monomers, and these may be used alone or in combination. The above can be used together.

In the graft polymerization, the methyl methacrylate single monomer or the monomer mixture may be added at once to perform the polymerization, or the methyl methacrylate single monomer or the monomer mixture may be added twice or more. It may be added in portions and the graft polymerization may be carried out in several stages. An emulsion polymerization method is adopted for the graft polymerization. Examples of the polymerization initiator that can be used in the graft polymerization include potassium persulfate, ammonium persulfate, persulfate such as sodium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide. , Organic peroxides such as diisopropylbenzene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Further, the above-mentioned polymerization initiator may be used as a redox initiator by combining a sulfite, a hydrogen sulfite, a thiosulfate, a first metal salt, sodium formaldehyde sulfoxylate, dextrose and the like. The polymerization temperature of the graft polymerization depends on the kind of the polymerization initiator, but is usually in the range of 40 to 80 ° C. As the emulsifier, a known emulsifier can be appropriately used.

The diene rubber graft copolymer latex thus obtained may be spray-dried (directly powdered) with or without addition of an appropriate antioxidant or additive, and powdered. To obtain the diene rubber graft copolymer resin. Or, diene rubber graft copolymer latex, acid such as sulfuric acid, hydrochloric acid, phosphoric acid or calcium chloride,
Coagulate by adding a coagulant such as salt such as sodium chloride,
After heat treatment and solidification, dehydration, washing, and drying are performed to obtain a powdery diene rubber-based graft copolymer resin. The resulting diene rubber graft copolymer has a methyl methacrylate homomonomer or a monomer mixture containing methyl methacrylate of 10 to 80% by mass and a diene rubber copolymer of 2%.
It is preferably from 0 to 90% by mass.

The acrylic rubber graft copolymer is an acrylic rubber copolymer graft-polymerized with methyl methacrylate. The acrylic rubber copolymer is an acrylic acid ester homomonomer, or 50% by mass of an acrylic acid ester and a vinylic monomer copolymerizable therewith.
It is obtained by polymerizing a monomer mixture containing less than. The acrylic acid ester constituting the acrylic rubber copolymer is an acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms, and examples thereof include ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. Can be mentioned. Examples of vinyl monomers copolymerizable with acrylic acid ester include styrene and aromatic vinyl such as α-methylstyrene,
Methyl methacrylate, alkyl methacrylate such as ethyl methacrylate, unsaturated nitrile such as acrylonitrile and methacrylonitrile, vinyl ether such as methyl vinyl ether and butyl vinyl ether, vinyl halide such as vinyl chloride and vinyl bromide Vinylidene chloride, vinylidene bromide, etc. Vinylidene halides such as vinylidene halide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. Further, as a vinyl-based monomer copolymerizable with an acrylic ester and a bifunctional crosslinkable monomer, for example, an aromatic polyfunctional vinyl compound such as divinylbenzene or divinyltoluene, ethylene glycol diethylene, etc. Methacrylate, polyhydric alcohol such as 1,3-butanediol diacrylate, trimethacrylic acid ester or triacrylic acid ester, allyl acrylate, allyl ester of carboxylic acid such as allyl methacrylate, diallyl phthalate, diallyl sebacate, triallyl Examples thereof include di- and triallyl compounds such as triazine. The vinyl-based monomer copolymerizable with the above-mentioned acrylic ester,
One kind or two or more kinds can be used. Further, since the acrylic rubber copolymer can be easily produced,
It is preferably produced by emulsion polymerization. During the polymerization, a chain transfer agent such as t-dodecyl mercaptan can also be used if necessary.

In the presence of the acrylic rubber copolymer,
Acrylic rubber graft copolymer can be obtained by graft-polymerizing a methyl methacrylate homomonomer or a monomer mixture containing methyl methacrylate and one or more vinyl-based monomers copolymerizable therewith. it can. Examples of vinyl monomers copolymerizable with methyl methacrylate include methacrylic acid esters such as ethyl methacrylate and propyl methacrylate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, styrene and α-. Styrenes such as methylstyrene and various halogen-substituted and alkyl-substituted styrenes, unsaturated nitriles such as acrylonitrile and methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, vinyl monomers having a glycidyl group such as allyl glycidyl ether, and the aforementioned crosslinking Examples of the polymerizable monomer include those which can be used alone or in combination of two or more kinds.

In the graft polymerization, the methyl methacrylate homomonomer or the monomer mixture may be added at once to carry out the polymerization, or the monomer or the monomer mixture may be divided into two or more times. Then, the graft polymerization may be carried out in several stages. An emulsion polymerization method is adopted for the graft polymerization. Examples of the polymerization initiator that can be used in the graft polymerization include potassium persulfate, ammonium persulfate, persulfate such as sodium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide. , Organic peroxides such as diisopropylbenzene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Further, the above-mentioned polymerization initiator may be used as a redox initiator by combining a sulfite, a hydrogen sulfite, a thiosulfate, a first metal salt, sodium formaldehyde sulfoxylate, dextrose and the like. The polymerization temperature of graft polymerization depends on the type of polymerization initiator,
It is in the range of about 40 to 80 ° C. As the emulsifier, a known emulsifier can be appropriately used.

The acrylic rubber graft copolymer latex thus obtained is spray-dried (direct powdering) with or without addition of a suitable antioxidant or additive, etc. To obtain the acrylic rubber-based graft copolymer resin. Alternatively, to the acrylic rubber graft copolymer latex, a coagulant such as an acid such as sulfuric acid, hydrochloric acid or phosphoric acid or a salt such as calcium chloride or sodium chloride is added to coagulate, and after heat treatment to solidify, It is dehydrated, washed and dried to obtain a powdery acrylic rubber-based graft copolymer resin. The obtained acrylic rubber graft copolymer is preferably 10 to 80% by mass of a methyl methacrylate homomonomer or a monomer mixture containing methyl methacrylate, and 20 to 90% by mass of an acrylic rubber polymer. .

The silicone / acrylic rubber graft copolymer is a silicone / acrylic rubber copolymer graft-polymerized with methyl methacrylate. The silicone / acrylic rubber copolymer contains a polyorganosiloxane component and a polyalkyl (meth) acrylate component. In the two components constituting the silicone / acrylic rubber copolymer, the polyorganosiloxane rubber component is 1 to 99% by mass, and the polyalkyl (meth) acrylate component is 99 to 1% by mass (however,
The total amount of both components is preferably 100% by mass. Although the silicone / acrylic rubber copolymer may be produced by any method, it is most preferably produced by the emulsion polymerization method because it can be easily produced. In the production of a silicone / acrylic rubber copolymer by an emulsion polymerization method, first, a polyorganosiloxane latex is prepared, and then, an alkyl (meth) acrylate monomer is impregnated into particles of the polyorganosiloxane latex, and then polymerization is performed. To do.

The polyorganosiloxane rubber component can be synthesized by emulsion polymerization using the following organosiloxane and crosslinking agent (a-1). At that time, a graft crossing agent (b-1) can also be used in combination.
Examples of the organosiloxane include various cyclic members having 3 or more membered rings, and among them, 3 to 6 are preferably used.
It is a member's ring. Examples of the 3- to 6-membered ring organosiloxane include hexamethylcyclotrisiloxane and
Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane,
Tetramethyltetraphenylcyclotetrasiloxane,
Octaphenylcyclotetrasiloxane and the like,
These may be used alone or in combination of two or more. The content of the organosiloxane is preferably 50% by mass or more, more preferably 70% by mass or more based on the polyorganosiloxane component.

As the crosslinking agent (a-1), a trifunctional or tetrafunctional silane-based crosslinking agent, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n- Propoxysilane, tetrabutoxysilane, etc. are used.
In particular, a tetrafunctional crosslinking agent is preferable, and among these, tetraethoxysilane is particularly preferable. The content of the cross-linking agent (a-1) is preferably 0.1 to 30 mass% in the polyorganosiloxane component.

As the graft crossing agent (b-1), compounds capable of forming the units represented by the following formulas (s-1) to (s-4) are used.

[0026]

[Chemical 1] (In the formula, R ¹ is a methyl group, an ethyl group, a propyl group, or a phenyl group, R ² is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is a number of 1 to 6.)

The (meth) acryloyloxysiloxane capable of forming the unit of the above formula (s-1) has a high grafting efficiency at the time of graft polymerization and therefore can form an effective graft chain, thus exhibiting impact resistance. Is advantageous in that. Note that methacryloyloxysiloxane is particularly preferable as the unit capable of forming the unit of the above formula (s-1).
Specific examples of methacryloyloxysiloxane include β
-Methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldisilane Examples thereof include ethoxymethylsilane and γ-methacryloyloxybutyldiethoxymethylsilane.

Examples of those capable of forming the unit of the above formula (s-2) include vinyl siloxane, and specific examples thereof include tetramethyltetravinylcyclotetrasiloxane. Examples of the unit capable of forming the unit of the above formula (s-3) include p-vinylphenyldimethoxymethylsilane. Examples of those capable of forming the unit of the above formula (s-4) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane and the like. The content of the graft crossing agent (b-1) as described above is preferably 0 to 10 mass% in the polyorganosiloxane component, and more preferably 0.5 to 5 mass%.

The polyorganosiloxane latex component can be produced by the method described in, for example, US Pat. Nos. 2,891,920 and 3,294,725. Specifically, in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid, water, an organosiloxane, a cross-linking agent (a-1) and, if necessary, a graft crossing agent (b-1). It is preferable that the mixed solution containing a) is shear-mixed using, for example, a homogenizer. Here, alkylbenzene sulfonic acid is preferable because it acts as an emulsifying agent for the organosiloxane and at the same time serves as a polymerization initiator, which is efficient. Further, since the polymer can be stably maintained during the graft polymerization, it is preferable to use an alkylbenzene sulfonic acid metal salt, an alkyl sulfonic acid metal salt or the like in combination.

The polyalkyl (meth) acrylate component can be synthesized by using the following alkyl (meth) acrylate, crosslinking agent (a-2) and graft crossing agent (b-2). Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Methacrylate and the like can be mentioned, and the use of n-butyl acrylate is particularly preferable. Crosslinking agent (a-2)
As, for example, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-
Examples thereof include butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate. Examples of the graft crossing agent (b-2) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a cross-linking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total content of the crosslinking agent and the graft crossing agent is preferably 0.1 to 20% by mass in the polyalkyl (meth) acrylate component.

The above-mentioned alkyl (meth) acrylate,
The cross-linking agent and the graft crossing agent are added to the polyorganosiloxane latex neutralized by the addition of an aqueous alkaline solution such as sodium hydroxide, potassium hydroxide or sodium carbonate, and after impregnating the polyorganosiloxane particles, the usual It is polymerized by acting a radical polymerization initiator. By this polymerization, a latex of a silicone / acrylic rubber copolymer in which a polyorganosiloxane component and a polyalkyl (meth) acrylate component are composited is obtained. In the silicone / acrylic rubber copolymer, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane and the main skeleton of the polyalkyl (meth) acrylate component has a repeating unit of n-butyl acrylate. A composite rubber having is preferably used. The silicone / acrylic rubber copolymer preferably has a gel content of 80% by mass or more as measured by extraction with toluene at 90 ° C. for 4 hours.

In the presence of the above silicone / acrylic rubber copolymer, at least one monomer selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters and vinyl cyanide compounds is graft-polymerized to produce silicone. / Acrylic rubber graft copolymer can be obtained. Here, as the graft-polymerizable vinyl-based monomer, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate, Examples thereof include acrylic acid esters such as n-butyl acrylate; various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Among these vinyl monomers, methyl methacrylate, butyl acrylate, acrylonitrile and styrene are preferably used.

In the graft polymerization, a monomer or a mixture of monomers may be added at once to carry out the polymerization, or the monomer or the mixture of monomers may be added in two or more portions. The graft polymerization may be carried out in several stages. An emulsion polymerization method is adopted for the graft polymerization. Examples of the polymerization initiator that can be used in the graft polymerization include potassium persulfate, ammonium persulfate, persulfate such as sodium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and the like.
Examples thereof include organic peroxides such as lauroyl peroxide and diisopropylbenzene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Further, the above-mentioned polymerization initiator may be used as a redox initiator by combining a sulfite, a hydrogen sulfite, a thiosulfate, a first metal salt, sodium formaldehyde sulfoxylate, dextrose and the like. The polymerization temperature of the graft polymerization is in the range of about 40 to 80 ° C., though it depends on the kind of the polymerization initiator. As the emulsifier, a known emulsifier can be appropriately used.

Powder is obtained by spray-drying (direct powdering) with or without addition of a suitable antioxidant or additive to the silicone / acrylic rubber graft copolymer latex obtained by graft polymerization. A silicone / acrylic rubber graft copolymer resin in the form of a rubber is obtained. Alternatively, a silicone / acrylic rubber graft copolymer latex is added with an acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like and a coagulant such as a salt such as calcium chloride or sodium chloride to coagulate and heat-treated to solidify. Then, dehydration, washing and drying are performed to obtain a powdery silicone / acrylic rubber graft copolymer resin. The obtained silicone / acrylic rubber graft copolymer is
30 to 95% by mass of silicone / acrylic rubber copolymer, aromatic alkenyl compound, methacrylic acid ester,
At least one monomer selected from acrylic acid esters and vinyl cyanide compounds is preferably 5 to 70% by mass.

The chlorinated polyolefin is obtained by chlorinating the below-mentioned polyolefin powder in an aqueous suspension or an organic solvent solution. Above all, a polyolefin powder obtained by chlorinating an aqueous suspension is preferable. The polyolefin used as a raw material is an ethylene homopolymer, or has at most 40% by mass (preferably 20% by mass or less) and 12 or less carbon atoms (preferably 3 to 8) with ethylene.
Of these, ethylene-based copolymers obtained by copolymerizing with α-olefin are preferable, and among them, ethylene homopolymers are preferable. Specific examples of the α-olefin constituting the ethylene copolymer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and the like. The chlorine content in the chlorinated polyolefin is preferably 30 to 40% by mass, more preferably 30 to 35% by mass. When the chlorine content is less than 30% by mass, the compatibility with the polyvinyl chloride resin is poor, so that the surface appearance of the molded product may be deteriorated. On the other hand, when the chlorine content exceeds 40% by mass, the fluidity may be deteriorated and the moldability may be deteriorated.

The stabilizer is not particularly limited as long as it is added to the polyvinyl chloride resin. For example, lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate; metals such as potassium, magnesium, barium, zinc, cadmium, and lead, and 2-
Metal soap-based stabilizers derived from fatty acids such as ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; alkyl groups, Organotin stabilizers derived from ester groups and fatty acid salts, maleates, and sulfides; Ba-
Zn-based, Ca-Zn-based, Ba-Ca-Sn-based, Ca-M
g-Sn system, Ca-Zn-Sn system, Pb-Sn system, Pb
-Ba-Ca-based complex metal soap-based stabilizers; metal groups such as barium and zinc; branched fatty acids such as 2-ethylhexanoic acid, isodecanic acid and trialkylacetic acid; and oleic acid, ricinoleic acid, linoleic acid and the like Metal salt stabilizers usually derived from two or more kinds of organic acids such as saturated fatty acids, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acids, benzoic acid, salicylic acid, and substituted derivatives thereof; Soluble in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, etc., and further phosphites, epoxy compounds, color-developing agents, transparency improvers, light stabilizers, antioxidants, plate-out inhibitors, lubricants, etc. Examples of the metal-based stabilizer include a metal salt liquid stabilizer prepared by blending the above-mentioned stabilization aid.

As the stabilizer, epoxy resin, epoxidized soybean oil, epoxidized vegetable oil, epoxy compound such as epoxidized fatty acid alkyl ester, phosphorus is substituted with an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group or the like, And dihydric alcohol such as propylene glycol; organic phosphite having an aromatic compound such as hydroquinone and bisphenol A; hindered phenol such as bisphenol dimerized with BHT, sulfur or methylene group, salicylate, benzophenone , UV absorbers such as benzotriazole; UV stabilizers such as hindered amine or nickel complex light stabilizers, carbon black, rutile titanium oxide; trimerol propane, pentaerythritol, sorbitol, mannitol Which polyhydric alcohol; nitrogen-containing compounds such as β-aminocrotonic acid ester, 2-phenylindole, diphenylthiourea, dicyandiamide; sulfur-containing compounds such as dialkylthiodipropionic acid ester; acetoacetic acid ester, dehydroacetic acid, β-diketone And non-metal-based stabilizers such as organosilicon compounds and borate esters. These stabilizers may be used alone or in combination of two or more.

As the lubricant, polyethylene wax, ester wax of fatty acid and polyhydric alcohol, liquid paraffin, natural paraffin, microwax, synthetic paraffin, low molecular weight polyethylene and the like pure hydrocarbon type; halogenated hydrocarbon type; higher grade Fatty acids such as fatty acids and oxyfatty acids; fatty acid amides such as fatty acid amides and bis fatty acid amides; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (esters Waxes, etc .; higher fatty acid metal salts such as sodium, calcium or magnesium salts of lauric acid, palmitic acid, oleic acid or stearic acid, fatty alcohols, polyhydric alcohols, polyglycols, polyglycero Le, partial esters of fatty acids with polyhydric alcohols, fatty acid and polyethylene glycol, partial esters of polyglycerol and the like; polymeric lubricants, and the like, such as polyalkyl (meth) acrylate copolymer.

The filler is used for improving physical properties and
For example, metal powder, oxides, hydroxides, silicic acid or silicates, carbonates, silicon carbide, vegetable fibers, animal fibers, synthetic fibers and the like can be used. Specific examples of these are aluminum powder, copper powder, iron powder, alumina, natural wood, paper, calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin,
Calcium sulfate, barium sulfate, aluminum hydroxide,
Magnesium hydroxide, silica, clay, zeolite, and recycled filler materials such as waste wood materials, waste paper, wood powder, paper powder, leather powder, acetate powder, silk powder, aramid fiber, azodicarbonamide, graphite, etc. Can be mentioned.

Examples of the pigment include titanium white, titanium yellow, red iron oxide, cobalt blue, carbon black and ultramarine blue, and these can be used alone or in admixture of two or more.

As the plasticizer, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-secondary butyl phthalate, di-heptyl phthalate, C7.
To C9 (alphanol) phthalate, di-normal octyl phthalate, di-isooctyl phthalate, di-
3,5,5-trimethylhexyl phthalate, normal octyl normal decyl phthalate, isooctyl isodecyl phthalate, di-isodecyl phthalate, di-methoxyethyl phthalate, di-butoxyethyl phthalate, di-butyl phthalate, di-hexyl phthalate,
Phthalates such as bis (diethyl glycol monomethyl ether) phthalate, di-isobutyl adipate, di-2-ethylhexyl adipate, di-isooctyl adipate, normal octyl normal decyl adipate, isooctyl isodecyl adipate, di-isodecyl adipate, Adipate such as di-butoxyethyl adipate, di-3,5,5-trimethylhexyl adipate, di-normal butyl sebacate, di-
Sebacic acid esters such as secondary butyl sebacate, di-2-ethylhexyl sebacate, di-alphanol sebacate, di-cyclohexyl sebacate, di-secondary butyl azelate, di-2-ethylhexyl azelate, di- Azelaic acid esters such as isooctyl azelate, tri-2-ethylhexyl phosphate, tri-butoxyethyl phosphate, tri-cresyl phosphate, tri-orthocresyl phosphate, tri-metacresyl phosphate, tri- Phosphoric acid esters such as para-cresyl phosphate, phenyl dicresyl phosphate, xylenyl dicresyl phosphate, cresyl dixylenyl phosphate, trimellitic acid ester, polyester polymer plasticizer, epoxidized soybean oil, epoxy Epoxy plasticizer such as linseed oil Etc., and the like.

Examples of the foaming agent include inorganic foaming agents, volatile foaming agents, decomposable foaming agents and the like. Examples of the inorganic foaming agent include carbon dioxide, air and nitrogen. Also,
Volatile blowing agents include aliphatic hydrocarbons such as propane, n-butane, isobutane, pentane, hexane, halogenated trichlorofluoromethane, dichlorofluoromethane, dichlorotetrafluoroethane, methyl chloride, ethyl chloride, methylene chloride, etc. Examples include hydrocarbons. Examples of the decomposition type foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrilyl, sodium bicarbonate and the like. Furthermore, these foaming agents can be appropriately mixed and used. When a foaming agent is used, a cell regulator may be further added to the melt-kneaded product of the thermoplastic resin composition. Examples of the cell regulator include inorganic powders such as talc and silica, acidic salts of polyvalent carboxylic acids, and reaction mixtures of polyvalent carboxylic acids with sodium carbonate or sodium bicarbonate.

In order to obtain the above-mentioned polyvinyl chloride resin composition, the polyvinyl chloride resin (A) is mixed with 0.01 to 20 parts by mass of a carboxylic acid-containing resin based on 100 parts by mass of the polyvinyl chloride resin. Add polymer. After adding
Mixing is preferred. There is no particular limitation on the mixing method, for example, Henschel mixer, tumbler mixer,
It can be mixed using a single-screw extruder or a twin-screw extruder. The method for molding the polyvinyl chloride resin composition thus obtained is not particularly limited, and for example, it can be molded by any molding method such as extrusion molding, injection molding, calender molding and the like. The molding processing temperature at the time of molding is usually 170 to 210 ° C.

[0044]

The present invention will be described below with reference to examples, but the present invention is not limited thereto. In addition, "part" described below means "part by mass", and "%" means "% by mass". [Reference Example-1] Production of carboxylic acid-containing copolymer (B-1) In a separable flask equipped with a cooling pipe and a stirrer,
200 parts of deionized exchanged water was added and 3 parts of semi-cured beef fatty acid soap and 0.6 part of potassium persulfate were dissolved. Then, to this separable flask, a mixture of 45 parts of ethyl acrylate, 45 parts of methyl methacrylate and 10 parts of methacrylic acid was added dropwise while stirring at 70 ° C. for 4 hours, and then maintained for 3 hours to polymerize. A carboxylic acid-containing copolymer (B-1) latex was obtained. An aqueous sulfuric acid solution was added to the obtained carboxylic acid-containing copolymer (B-1) latex to cause coagulation, and the coagulated product was obtained by heat treatment and solidification at 90 ° C. Then, the coagulated product was washed with warm water and further dried to obtain a carboxylic acid-containing copolymer (B-1) powder.

[Reference Example-2] Production of carboxylic acid-containing copolymer (B-2) In a separable flask equipped with a cooling pipe and a stirrer,
Charge 1.0 part of sodium dodecylbenzene sulfonate and 188 parts of deionized water, and in a water bath under a nitrogen atmosphere, 6
Heated to 0 ° C. Then, in this separable flask, 0.0004 parts of ferrous sulfate, 0.0012 parts of ethylenediaminetetraacetic acid disodium salt and 0.48 parts of Rongalit were added.
Parts were dissolved in 6 parts of distilled water and added, and then 55 parts of methyl methacrylate and 2-ethylhexyl acrylate 2 parts
5 parts A mixture of 20 parts of methacrylic acid, 0.25 parts of cumene hydroperoxide and 1.5 parts of n-octyl mercaptan was added dropwise over 90 minutes. Then, the mixture was stirred for 60 minutes and polymerized to obtain a carboxylic acid-containing copolymer (B-2). The obtained latex was poured into a calcium chloride aqueous solution, and the resulting precipitate was dried to obtain a carboxylic acid-containing copolymer (B-2) powder. Its mass average molecular weight (Mw) was 10,000.

[Reference Example-3] Production of carboxylic acid-containing copolymer (B-3) In a separable flask equipped with a cooling pipe and a stirrer,
200 parts of deionized water was added to dissolve 3 parts of semi-cured beef fatty acid soap and 0.6 part of potassium persulfate. Then, a mixture of 30 parts of ethyl acrylate, 25 parts of methyl methacrylate, and 45 parts of methacrylic acid was added dropwise to this separable flask over 4 hours while maintaining at 70 ° C. with stirring, and then maintained for 3 hours to polymerize. A carboxylic acid-containing copolymer (B-3) latex was obtained. An aqueous sulfuric acid solution was added to the obtained carboxylic acid-containing copolymer (B-3) latex to cause coagulation, and the coagulated product was obtained by heat treatment and solidification at 90 ° C. Then, the coagulated product was washed with warm water and further dried to obtain a carboxylic acid-containing copolymer (B-3) powder.

Reference Example 3 Production of Acrylic High Molecular Weight Polymer (C) In a reactor equipped with a stirrer and a reflux condenser, ion-exchanged water 2 was added.
80 parts, potassium alkenyl succinate 1.5 parts, ammonium persulfate 2 parts, methyl methacrylate 92 parts, n
8 parts of butyl acrylate and 0.03 part of n-octyl mercaptan were charged. Next, after replacing the inside of the container with nitrogen, the temperature was raised to 65 ° C. with stirring, the mixture was heated with stirring for 4 hours, and polymerized to obtain a copolymer particle dispersion (P-1). This copolymer particle dispersion (P-1) has a reduced viscosity (η
_sp / C) was 8.0. Next, in a reactor equipped with a stirrer, 600 parts of ion-exchanged water and 3 parts of sulfuric acid were charged, and 50
The temperature was raised to 0 ° C., and the copolymer particle dispersion liquid (P-1) was added over 5 minutes while stirring. After charging, raise the temperature to 95 ° C and
After holding for minutes, it was filtered, washed and dried to obtain an acrylic high molecular weight polymer (C).

Reference Example 4 Production of Diene Rubber Graft Copolymer (D) In a pressure resistant autoclave, 150 parts of deionized water, 1,3
-Butadiene 85 parts, styrene 15 parts, t-dodecyl mercaptan 0.5 parts, diisopropylbenzene hydrido peroxide 0.4 parts, sodium pyrophosphate 1.5 parts, ferrous sulfate 0.02 parts, dextrose 1.0 part , And 1.0 part of potassium oleate were charged. Then, the mixture was reacted with stirring at 50 ° C. for 15 hours to produce a butadiene rubber copolymer latex. After charging 65 parts (as solid content) of the above butadiene rubber copolymer latex into a flask and substituting with nitrogen, 1.2 parts of NaHCO ₃ was added to 10 parts.
% Aqueous solution and added and stirred for 30 minutes. Then
After adding 1 part of potassium oleate as a 7% aqueous solution and stabilizing it, 0.6 part of Rongalit was added and the internal temperature was adjusted to 7
Hold at 0 ° C. Then, 35 parts of the monomer mixture was graft-polymerized as follows. First, in the first stage of grafting, a monomer mixture containing 40 parts of methyl methacrylate, 5 parts of ethyl acrylate and 0.1 part of tertiary butyl hydroperoxide (t-BH) was dropped into the flask over 1 hour. Polymerization was carried out for 2 hours while stirring. Then, in the second stage of grafting, styrene 40
And 0.1 part of t-BH were added dropwise over 1 hour and polymerized for 2 hours with stirring. Then the graft 3
In the second stage, 15 parts of methyl methacrylate and t-B
A monomer mixture containing 0.05 part of H was added dropwise over 1 hour and polymerized for 2 hours with stirring to obtain a diene rubber-based graft copolymer (D) latex. The total amount of the monomers used in the above graft polymerization is 100 parts by mass. B was added to the obtained diene rubber graft copolymer (D) latex.
After adding 0.5 parts of HT, a 0.2 mass% sulfuric acid aqueous solution was added to cause coagulation, and heat treatment solidified at 90 ° C. to obtain a coagulated product. Next, the coagulated product was washed with warm water and further dried to obtain a diene rubber-based graft copolymer (D) powder.

Reference Example-5 Production of Acrylic Rubber Graft Copolymer (E) To a separable flask equipped with a stirrer, 195 parts of distilled water and 0.1 part of sodium dodecylbenzenesulfonate were added, and the atmosphere was replaced with nitrogen. Then, the temperature was raised to 50 ° C. Then, ferrous sulfate 0.002 was added to the separable flask.
Parts, ethylenediaminetetraacetic acid disodium salt 0.006
Part, 0.26 parts of Rongalit and 5 parts of distilled water were charged, and then 70 parts of nitrogen-substituted n-butyl acrylate, 0.75 part of allyl methacrylate and te.
A mixture of 0.4 parts of rt-butyl hydroperoxide was charged to initiate radical polymerization, and then the internal temperature was 70 ° C.
It was held for 2 hours and polymerized to obtain an acrylic rubber copolymer latex. Part of this acrylic rubber copolymer latex was sampled and the average particle size was measured to be 0.22μ.
It was m. A mixed solution of 0.06 parts of tert-butyl hydroperoxide and 30 parts of methyl methacrylate was added to this acrylic rubber copolymer latex at 70 ° C. for 1 hour.
The mixture was added dropwise over 5 minutes, then kept at 70 ° C. for 4 hours, and graft-polymerized to obtain an acrylic rubber graft copolymer (E) latex. The final polymerization rate of methyl methacrylate was 98.2%, and the average particle size was 0.2.
It was 4 μm. The obtained acrylic rubber graft copolymer latex was treated with 20% hot water of calcium chloride 1.5%.
After dropping into 0 part, coagulating, separating and washing, 1 at 75 ° C
Acrylic rubber graft copolymer (E) after drying for 6 hours
A powder was obtained.

Reference Example 6 Production of Silicone / Acrylic Rubber Graft Copolymer (F) 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 octamethylcyclotetrasiloxane. The parts were mixed to obtain 100 parts of a siloxane mixture. Next, 100 parts of the above-mentioned mixed siloxane was added to 200 parts of distilled water in which 0.67 parts of sodium dodecylbenzenesulfonate and 0.67 parts of dodecylbenzenesulfonic acid were dissolved respectively, and after preliminarily stirring at 10,000 rpm with a homomixer, 200 kgf / with a homogenizer. It was emulsified and dispersed under a pressure of cm ² to obtain an organosiloxane latex. Next, the obtained organosiloxane latex was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then left at 20 ° C. Then, after 48 hours, the pH of this latex was neutralized to 7.0 with an aqueous sodium hydroxide solution and polymerized to obtain a polyorganosiloxane latex (PDMS-1). The final polyorganosiloxane polymerization rate was 89.1%,
The average particle size of the polyorganosiloxane was 0.19 μm. In addition, polyorganosiloxane latex (P
DMS-1) was coagulated and dried with isopropanol to obtain a solid, toluene was added to the solid, and the sol was extracted at 90 ° C. for 12 hours, and the gel content was measured to be 91.4.
%Met.

Next, 35 parts of polyorganosiloxane latex (PDMS-1) and 175 parts of distilled water were placed in a separable flask equipped with a stirrer, the atmosphere was replaced with nitrogen, and the temperature was raised to 50 ° C. Then, a mixed solution of 78.4 parts of n-butyl acrylate, 1.6 parts of allyl methacrylate and 0.3 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and this mixed solution was permeated into the polyorganosiloxane particles. Then ferrous sulfate 0.0
02 parts, ethylenediaminetetraacetic acid disodium salt 0.0
A mixed solution of 06 parts, 0.3 parts of Rongalit and 10 parts of distilled water was charged to initiate radical polymerization, and then the internal temperature was kept at 70 ° C. for 2 hours to obtain a silicone / acrylic rubber copolymer latex. The average particle diameter of the silicone / acrylic rubber copolymer latex was measured and found to be 0.22 μm. Further, this latex is dried to obtain a solid matter, and toluene is added to this solid matter.
The sol was extracted in 4 hours and the gel content was measured to be 9
It was 5%.

10 parts of methyl methacrylate and tert were added to this silicone / acrylic rubber copolymer latex.
-Butyl hydroperoxide 0.024 parts by mixture was added dropwise at 60 ° C over 15 minutes and then at 60 ° C for 2 minutes.
After holding for a period of time, graft polymerization was performed to obtain a silicone / acrylic rubber graft copolymer (F) latex. The final polymerization rate of methyl methacrylate was 97.1%. The average particle size of the obtained silicone / acrylic rubber graft copolymer (F) latex was 0.23 μm. Then, the obtained graft copolymer latex,
At 40 ° C., a silicone / acrylic rubber graft copolymer (F) latex: calcium chloride aqueous solution = 1: 2 was added to a 5 mass% calcium chloride aqueous solution, and then the temperature was raised to 90 ° C. After coagulation and repeated washing with water, solids were separated and dried at 80 ° C. for 24 hours to obtain a silicone / acrylic rubber graft copolymer (F) powder.

In Examples and Comparative Examples described later, PVC
10.0 parts by mass (TK1300 manufactured by Shin-Etsu Chemical Co., PVC
Average degree of polymerization: 1300) and a calcium zinc stabilizer (Stabilox CZ3122GN manufactured by Cognis).
3.0 parts by mass and internal lubricant (Loxiol manufactured by Cognis)
G15) 0.5 parts by mass, polyethylene wax (HiWax 220MP manufactured by Mitsui Chemicals, Inc.) 1.0 parts by mass, and an acrylic lubricant (Metablene L1000 manufactured by Mitsubishi Rayon Co., Ltd.)
1.0 parts by mass and calcium carbonate (CC manufactured by Shiraishi Industry Co., Ltd.
R) 5.0 parts by mass and titanium oxide (R83 manufactured by Ishihara Sangyo Co., Ltd.
0) The compounding with 3.5 parts by mass was a common compounding.

Examples 1 to 20 Table 1
Alternatively, as shown in Table 2, a carboxylic acid-containing copolymer (B-1) and a carboxylic acid-containing copolymer (B-2) are blended as a gelation accelerator, and as a impact strength modifier, Diene rubber graft copolymer (D), acrylic rubber polymer (E), silicone / acrylic rubber polymer (F), chlorinated polyethylene (Showa Denko Erasulene 351A, chlorine content 35% by mass) Mix each,
A polyvinyl chloride resin composition was obtained by mixing using a Henschel mixer. This polyvinyl chloride resin composition is
A sheet having a thickness of about 3 mm was formed at a molding temperature of 210 ° C. by using an extrusion molding machine manufactured by KG (screw diameter: φ50 mm single screw extruder, rotation speed 50 rpm, die shape: width 80 mm). With respect to the polyvinyl chloride resin composition, kneadability, moldability, impact resistance, and surface appearance of the molded product were evaluated by the following methods. The evaluation results are shown in Tables 1 and 2.

[0055]

[Table 1]

[0056]

[Table 2]

[Kneading properties]: A Labo Plastomill manufactured by Toyo Seiki Co., Ltd. was equipped with a mixer type head: R-60 / 3 zone,
The gelation time of the polyvinyl chloride resin composition was measured at a container temperature of 200 ° C., a filling amount of 55 g, a holding time of 4 minutes, and a mixer rotation speed of 30 rpm. In the time-torque curve,
The point at which the torque showed the maximum value was taken as the gelling time, and the kneading property was evaluated by this gelling time. That is, the faster the gelation time, the better the kneading property. [Moldability]: Toyo Seiki Co., Ltd. Labo Plastomill equipped with a mixer type head: R-60 / 3 zone, container temperature 200 ° C., filling amount 55 g, holding time 4 minutes, mixer rotation speed 30 rpm. Then, the equilibrium torque of the vinyl chloride resin composition was measured. In the time-torque curve,
The point where the torque shows a constant value for 2 minutes or more is defined as the equilibrium torque,
The moldability was evaluated using this balance torque. That is, the lower the equilibrium torque, the better the workability. [Impact resistance test]: using a sheet of a polyvinyl chloride resin composition, at 23 ° C. according to JIS K-7111,
The impact strength at 10 ° C was measured. [Surface appearance of molded product]: The sheet of the polyvinyl chloride resin composition was visually evaluated as follows. ◯: Good (with surface gloss). Δ: Surface gloss is present, but some surface roughness is confirmed. X: There is no surface gloss and the entire surface is rough.

(Comparative Examples 1-28) In Comparative Examples 1-4, the substitutes for the carboxylic acid-containing copolymer (B-1) and the carboxylic acid-containing copolymer (B-2) in the examples were used. A polyvinyl chloride resin composition was produced in the same manner as in the example except that it was not compounded. And it evaluated similarly to the Example. The evaluation results are shown in Table 3. Comparative Example 5
In Nos. 20 to 20, in place of the carboxylic acid-containing copolymer (B-1) and the carboxylic acid-containing copolymer (B-2) in the examples, the common composition was high, as shown in Table 3 or Table 4. A polyvinyl chloride resin composition was produced in the same manner as in Example except that the density-oxidized polyethylene (A-C316A manufactured by Allied Signal, acid value: 16 mgKOH / g) was blended. And it evaluated similarly to the Example. The evaluation results are shown in Table 3 or Table 4. Comparative Examples 21-24
Then, the carboxylic acid-containing copolymer (B-
1) and the carboxylic acid-containing copolymer (B-2), instead of the carboxylic acid-containing copolymer (B-2), as shown in Table 5, a carboxylic acid-containing copolymer containing a carboxylic acid-containing monomer in an amount of more than 40% by mass. A polyvinyl chloride resin composition was produced in the same manner as in Example except that the compound (B-3) was blended. And it evaluated similarly to the Example. The evaluation results are shown in Table 5. In Comparative Examples 24-28, as shown in Table 5, instead of the carboxylic acid-containing copolymer (B-1) and the carboxylic acid-containing copolymer (B-2) in the Examples, the acrylic resin was used as shown in Table 5. A polyvinyl chloride resin composition was produced in the same manner as in Example except that the high molecular weight polymer (C) was blended. And it evaluated similarly to the Example. The evaluation results are shown in Table 5.

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

In Examples 1 to 20, 0.01 to 20 parts by mass of the carboxylic acid-containing copolymer (B-1 or B-2) containing 40% by mass or less of the carboxylic acid-containing monomer was contained. Therefore, the moldability and surface appearance were excellent.
In Comparative Examples 1 to 4, the carboxylic acid-containing monomer was 40% by mass.
Since no additive was added to replace the carboxylic acid-containing copolymer contained below, both moldability and surface appearance were low. In Comparative Examples 5 to 20, high-density oxidized polyethylene was blended in place of the carboxylic acid-containing copolymer containing 40% by mass or less of the carboxylic acid-containing monomer, but the surface appearance was not improved. In Comparative Examples 21 to 24, methacrylic acid, which is a carboxylic acid-containing monomer, is contained in excess of 40 mass% instead of the carboxylic acid-containing copolymer containing 40 mass% or less of the carboxylic acid-containing monomer. The carboxylic acid-containing copolymer (B-3) was blended, but the surface appearance was not improved. In Comparative Examples 24-28,
An acrylic high molecular weight polymer (C) was blended in place of the carboxylic acid-containing copolymer, but the surface appearance was not improved.

[0063]

INDUSTRIAL APPLICABILITY In the present invention, the polyvinyl chloride resin (A) contains 0.1 to 40% by mass of a carboxylic acid-containing monomer.
And a carboxylic acid-containing copolymer (B) obtained by copolymerizing 99.9 to 60% by mass of a vinyl monomer that is copolymerizable with the carboxylic acid-containing monomer as a structural unit. ) Since 0.01 to 20 parts by mass is added to 100 parts by mass, the carboxylic acid of the carboxylic acid-containing copolymer reacts at an appropriate reaction rate during molding and promotes gelation of the polyvinyl chloride resin. Therefore, the molding processability is improved. Therefore, the kneadability and the surface appearance of the molded product are improved. In addition, the addition of the carboxylic acid-containing copolymer (B) does not lower productivity and mechanical properties. Such a polyvinyl chloride resin composition is a flat plate,
It can be used particularly suitably for pipes and other shaped extrusion products.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Koichi Ito             3816 Noborito, Tama-ku, Kawasaki-shi, Kanagawa Mitsubishi             Rayon Co., Ltd. Tokyo Technology and Information Center             Within F term (reference) 4J002 BB24X BC04Y BC09Y BC11Y                       BD03W BD04W BD06W BG04Y                       BG05Y BN12X BN16X BN22X                       CD19Y FD010 FD030 FD050                       FD170 FD320 GL00

Claims (7)

[Claims] 1. A polyvinyl chloride resin (A) having 0.1 to 40% by mass of a carboxylic acid-containing monomer and 99.9 to 60% of a vinyl monomer copolymerizable with the carboxylic acid-containing monomer. The carboxylic acid-containing copolymer (B) copolymerized with 1% by mass as a constituent unit is added in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin (A). A method for promoting gelation of vinyl chloride resin. 2. A polyvinyl chloride resin (A) and 0.01 to 100 parts by mass of the polyvinyl chloride resin (A).
20 parts by mass of the carboxylic acid-containing copolymer (B), wherein the carboxylic acid-containing copolymer (B) is 0.1 to 40% by mass of the carboxylic acid-containing monomer and the carboxylic acid-containing unit amount. A polyvinyl chloride resin composition characterized in that 99.9 to 60% by mass of a vinyl monomer copolymerizable with the polymer is copolymerized as a constitutional unit. 3. The polyvinyl chloride resin composition according to claim 2, wherein the polyvinyl chloride resin (A) contains 1 to 30 parts by mass of an impact strength modifier with respect to 100 parts by mass of the polyvinyl chloride resin (A). object. 4. The polyvinyl chloride resin composition according to claim 3, wherein the impact strength modifier is a diene rubber graft copolymer. 5. The polyvinyl chloride resin composition according to claim 3, wherein the impact strength modifier is an acrylic rubber graft copolymer. 6. The polyvinyl chloride resin composition according to claim 3, wherein the impact strength modifier is a silicone / acrylic rubber graft copolymer. 7. The polyvinyl chloride resin composition according to claim 3, wherein the impact strength modifier is a chlorinated polyolefin.