JP2001031826A - Processing aid, vinyl, chloride-based resin composition using the same and production of molded article using the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing aid enabling occurrence of both matter not gelled and flow marks on a sheet to be reduced and enabling releasability of the sheet from the metal surface of a roll to be improved. SOLUTION: This processing aid comprises (A) a copolymer obtained by copolymerizing a monomer mixture consisting of 70-90 wt.% methyl methacrylate, 30-10 wt.% acrylate (or methacrylate except methyl methacrylate) and the rest of at least one comonomer and having a weight average molecular weight(Mw) measured by gel permeation chromatography and a molecular weight distribution (Mw/Mn) of 700,000-2,000,000 and <=3.0 respectively and (B) a copolymer obtained by copolymerizing a monomer mixture consisting of at least >=30 wt.% methyl methacrylate and the rest of at least one monomer having at least one kind selected from the group consisting of a methacrylate except only methyl methacrylate, an acrylate, an aromatic alkenyl compound and other comonomer as its structural unit and having a weight average molecular weight (Mw) of 10,000-500,000 when measured by gel permeation chromatography.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing aid for a vinyl chloride resin and a vinyl chloride resin composition using the same, and more particularly, to a vinyl chloride resin without impairing various properties inherent in the vinyl chloride resin. It provides a gelation accelerating effect at the time of calendering of vinyl chloride resin, and eliminates the non-gelled material of the calender sheet, which is a problem in calendering, and the occurrence of flow marks, which were difficult with conventional processing aids. In addition, a processing aid for calendering, which also improves the releasability from the roll metal surface of the sheet during calendering, a vinyl chloride resin composition for calendering using the same, and molding using the same It relates to a method of manufacturing a product.

[0002]

2. Description of the Related Art Vinyl chloride resins are excellent in various physical and chemical properties, and are therefore used in films, sheets,
It is widely used for various products such as bottles, building materials, floor materials, wire covering materials, and the like. However, since the molding temperature is close to the thermal decomposition temperature, vinyl chloride resin has a narrow molding area, and has a low gelation rate. The surface condition is often poor. Many techniques are known for overcoming these drawbacks. For example, addition of a plasticizer, copolymerization of a vinyl chloride resin with another monomer, and the like can be mentioned.
However, the addition of the plasticizer may cause problems such as volatilization and escape of the plasticizer, and may also cause a decrease in physical properties of the final molded article. Even in a method based on copolymerization of a vinyl chloride resin and another monomer, the amount of the monomer to be copolymerized is limited in order to perform copolymerization without impairing the intrinsic properties of the vinyl chloride resin, If the amount is too large, the physical properties of the final molded article may be reduced as in the case of adding a plasticizer.

[0003] On the other hand, the so-called processing such as accelerating the gelling of the resin at the time of molding processing of the vinyl chloride resin, keeping the surface of the molded article smooth even during long-time molding processing, and imparting the same surface gloss. For the purpose of improving
Some of the copolymers having compatibility with the vinyl chloride resin have been studied as processing aids, and a method of blending the copolymer as the processing aid has been proposed. These are all copolymers containing methyl methacrylate as a main component. The vinyl chloride resin mixed with these copolymers has a high gelation rate and the secondary processability is greatly improved, for example,
It has the drawback of lowering the commercial value of the final molded product, such as the generation of an ungelled product due to the poor dispersion.

[0004] Therefore, as a method of accelerating the gelation rate of the vinyl chloride resin and at the same time suppressing the generation of ungelled substances due to poor dispersion of the added processing aid, polymethyl methacrylate, acrylate and A multi-stage copolymer consisting of a copolymer of a superior amount of monomer selected from the group consisting of methacrylic acid esters excluding methyl methacrylate and an inferior amount of methyl methacrylate, or a polymer mixture obtained by mixing these in a latex state Or
A copolymer obtained from a superior amount of methyl methacrylate and an inferior amount of monomer selected from the group consisting of acrylates and methacrylic esters except methyl methacrylate, and an inferior amount of methyl methacrylate and acrylate and As a processing aid, a multi-stage copolymer consisting of a copolymer obtained from a predominant amount of monomers selected from the group consisting of methacrylic esters except methyl methacrylate, or a polymer mixture obtained by mixing these in a latex state A blended vinyl chloride resin composition has been proposed (JP-B-52-49020, JP-B-53-289).
No. 8).

Further, it has been proposed to use a multi-stage polymer in which the particle size of latex is specified when preparing a processing aid by an emulsion polymerization method (see Japanese Patent No. 2515014).

[0006] The vinyl chloride-based resin composition containing the processing aid comprising the specific copolymer described in the above-mentioned publication has the property of generating an ungelled substance and improving the secondary workability. .

However, in order to promote the gelation and to improve the secondary workability, it is necessary that the processing aid has a large molecular weight. For this reason, since the melt viscosity of the resin composition at the time of the molding process is increased, a flow mark is generated on the surface of the calender sheet at the time of the calendering process, which also has a disadvantage that the commercial value of the molded product is reduced.

For the purpose of remedying the above problems, a vinyl chloride resin composition has been proposed in which a copolymer comprising methyl methacrylate and a specific methacrylate ester is blended as a processing aid (Japanese Patent No. 281248). Gazette).

On the other hand, a copolymer containing methyl methacrylate as a main component has essentially high adhesion to a metal surface, and
Also, there is a disadvantage that the releasability from the roll metal surface is poor.

For the purpose of improving the releasability of the sheet from the roll metal surface in the calendering process, the use of various lubricants has been studied, but from the viewpoint of maintaining the physical properties of the vinyl chloride resin composition. There is an upper limit to the use amount of these lubricants, and even within the proper use amount range, lack of long-term persistence of the release property of the sheet, bloom on the surface of the final molded product, or roll metal during calender molding processing It cannot be a general solution because of the adhesion of lubricant to the surface.

[0011]

In recent years, in calender molding of vinyl chloride resin, high-speed production has been attempted to increase the size of molding machines and shorten molding time in order to improve productivity. . With the increase in the speed of the calendering process, a number of ungelled materials and flow marks are generated on the calendered sheet, causing a problem that the appearance and quality of the final molded product are greatly impaired,
There is a need for a technology that can greatly improve this. Further, there is a strong demand for a technique for improving the releasability of the sheet from the roll metal surface more than ever.

An object of the present invention is to satisfy the above requirements. In other words, under the conditions of high-speed calendering of vinyl chloride resin, it reduces the occurrence of ungelled materials and flow marks on the sheet, which reduces the commercial value of the final molded product, and releases the sheet from the roll metal surface. Another object of the present invention is to provide a processing aid for calendering and a vinyl chloride resin composition for calendering using the same.

[0013]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that two kinds of polymers having different functions, namely, a copolymer (A) and a copolymer (B). ) Is mixed with a vinyl chloride resin to reduce ungelled materials and flow marks on the sheet during calendering, and to improve the releasability of the sheet from the roll metal surface. It has been found that the present invention can be performed, and the present invention has been completed.

That is, the gist of the present invention is as follows.
(1) A monomer mixture composed of 70 to 90% by weight of methyl methacrylate, 30 to 10% by weight of methacrylate except acrylate or methyl methacrylate, and another monomer copolymerizable therewith. The weight average molecular weight (Mw) measured by gel permeation chromatography, obtained by copolymerization, is 700,0.
Excluding copolymer (A) having a molecular weight distribution (Mw / Mn) of 3.0 or less, methyl methacrylate of at least 30% by weight or more, and methyl methacrylate in the range of 00 to 2,000,000. Gel particles obtained by copolymerizing a monomer mixture comprising a monomer having at least one structural unit selected from methacrylic acid esters, acrylic acid esters, aromatic alkenyl compounds, and other monomers. Weight average molecular weight (Mw) measured by migration chromatography is 10,000 to 500,
(2) 100 parts by weight of a vinyl chloride resin and 0.1 to 20 parts by weight of the processing aid described in the above item (1). (3) A method for producing a molded article from the vinyl chloride resin composition according to the above item (2) by calender molding.

By blending the processing aid of the present invention with a vinyl chloride resin, it is possible to reduce ungelled materials and flow marks on the sheet during calendering and to improve the releasability of the sheet from the roll metal surface. And its industrial value is extremely large.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The processing aid of the present invention comprises 70 to 90% by weight of methyl methacrylate, 30 to 10% by weight of acrylate or methacrylate other than methyl methacrylate, and other methacrylates copolymerizable therewith. And a weight average molecular weight (Mw) measured by gel permeation chromatography, obtained by copolymerizing a monomer mixture consisting of
Molecular weight distribution (Mw / Mn).
0 or less, and at least 30% by weight of the copolymer (A)
Methyl methacrylate and a monomer mixture comprising a monomer having at least one selected from the group consisting of methacrylates other than methyl methacrylate, acrylates, aromatic alkenyl compounds, and other monomers And a copolymer (B) having a weight average molecular weight (Mw) measured by gel permeation chromatography in the range of 10,000 to 500,000, obtained by copolymerizing

Hereinafter, the processing aid will be described in detail.

The copolymer (A) constituting the processing aid of the present invention comprises 70 to 90% by weight of methyl methacrylate, 30 to 10% by weight of methacrylic acid ester excluding acrylate or methyl methacrylate. And a weight average molecular weight (Mw) measured by gel permeation chromatography, which is obtained by copolymerizing a monomer mixture composed of a monomer mixture composed of a monomer component of at least 700,000 and It is a copolymer having a molecular weight distribution (Mw / Mn) of 3.0 or less in the range of 2,000,000.

The acrylate ester has 1 carbon atom.
The alkyl group of the acrylate ester 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, stearyl 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. If the alkyl group has more than 18 carbon atoms, the polymerizability of the monomer may be reduced, and copolymerization may be difficult. Furthermore, the gelation-promoting effect of the vinyl chloride resin during the calendering process may be impaired, and an ungelled product may be formed on the sheet.

The methacrylates other than methyl methacrylate include those having an alkyl group having 2 to 18 carbon atoms. The alkyl group of the methacrylate may be linear or branched, and may be cyclic. May be used. Specifically, those having a linear alkyl group include ethyl methacrylate and n-methacrylic acid.
-Butyl, lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate and the like. Also,
Examples of those having a branched alkyl group include i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Furthermore, examples of those having a cyclic alkyl group include cyclohexyl methacrylate and the like. If the alkyl group has more than 18 carbon atoms, the polymerizability of the monomer is reduced, and copolymerization becomes difficult, which is not preferable. Furthermore, the gelation-promoting effect of the vinyl chloride resin during the calendering process may be impaired, and an ungelled product may be formed on the sheet.

The ratio of the methyl methacrylate component to the methacrylate component other than the acrylate or methyl methacrylate component in the monomer component constituting the copolymer (A) is such that the methyl methacrylate component is 70 to 90% by weight. And preferably 80 to 90% by weight. The content of the methacrylate component other than the acrylate or methyl methacrylate is 30 to 10% by weight, preferably 20 to 10% by weight.

If the proportion of the methyl methacrylate component in the monomer component exceeds 90% by weight, the dispersibility of the copolymer (A) in the vinyl chloride resin at the time of calendering is reduced, and There is a possibility that a gel is formed. When the proportion of the methacrylate component other than the acrylate or methyl methacrylate exceeds 30% by weight, the compatibility with the vinyl chloride resin decreases,
The gelation promoting effect of the vinyl chloride resin may be impaired during the calendering process, and an ungelled product may be formed on the sheet.

Further, other types of monomers copolymerizable therewith include aromatic alkenyl compounds such as styrene, α-methylstyrene, chlorostyrene and vinyltoluene;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate; dicarboxylic anhydrides such as maleic anhydride; and polyfunctional monomers such as divinylbenzene and allyl methacrylate. In the present invention, these may be used alone or in combination of two or more depending on the purpose, but so as not to impair the gelation promotion of the vinyl chloride resin which is the original function of the processing aid of the present invention. The proportion of these monomer components in the monomer components constituting the copolymer (A) is preferably 3% by weight or less, more preferably 2% by weight or less.

The weight average molecular weight of the copolymer (A) measured by gel permeation chromatography
(Mw) and molecular weight distribution (Mw / Mn) have a great effect on the properties as a processing aid for calendering,
Weight average molecular weight (Mw) of 700,000 to 2,000,000
It is preferable that the molecular weight distribution (Mw / Mn) be in the range of 00 and 3.0 or less.

The weight average molecular weight (Mw) of the copolymer (A) is 7
If it is less than 000, the flow marks on the sheet will be good during the calendering process, but air marks will easily occur. Also, the weight average molecular weight (Mw) is 2,000
If it exceeds 000, the melt viscosity is increased during calendering, so that flow marks tend to be generated on the sheet.

If the molecular weight distribution (Mw / Mn) of the copolymer (A) exceeds 3.0, low molecular weight components increase and plate-out tends to occur, which is not preferable. In addition, there is a possibility that the flow mark may be adversely affected.

Examples of the polymerization method for obtaining the copolymer (A) 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.

Here, the emulsifier that can be used in the emulsion polymerization 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 sulfonate salts, alkyl phosphate ester salts, dialkyl sulfosuccinate salts; polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, glycerin Nonionic surfactants such as 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, an appropriate pH adjuster may be used to prevent the hydrolysis of the alkyl methacrylate and the alkyl acrylate. it can. Examples of the pH adjuster used include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, and dihydrogen phosphate. Potassium hydrogen-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 a redox type. Examples of the water-soluble initiator include ordinary inorganic initiators such as persulfates. Can be used alone or in combination with a sulfite, a hydrogen sulfite, a thiosulfate or the like as a redox initiator.

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

Further, the weight average molecular weight (M
w) and the molecular weight distribution (Mw / Mn) can be arbitrarily adjusted by a chain transfer agent such as n-octyl mercaptan, t-dodecyl mercaptan, polymerization conditions, and the like.

The copolymer (B) comprising the processing aid of the present invention together with the copolymer (A) is at least 30% by weight or more of methyl methacrylate, methacrylic acid ester excluding methyl methacrylate, and acrylic acid ester. , Obtained by copolymerizing a monomer mixture consisting of a monomer having at least one structural unit selected from aromatic alkenyl compounds and other monomers, measured by gel permeation chromatography Is a copolymer having a weight-average molecular weight (Mw) in the range of 10,000 to 500,000, and imparts releasability from a roll metal surface to a vinyl chloride resin during calendering. .

The amount of methyl methacrylate used is 30 to 55
%, Preferably 40 to 50% by weight. If the amount of methyl methacrylate used is less than 30% by weight, the promotion of gelation of the vinyl chloride resin may be hindered. Further, secondary agglomeration is likely to occur in a post-process such as coagulation, dehydration, and drying, which may cause a problem in productivity. If it exceeds 55% by weight, the effect of imparting releasability to the vinyl chloride resin is impaired.

The methacrylic acid ester other than methyl methacrylate has an alkyl group having 2 to 18 carbon atoms, and the alkyl group of the methacrylic acid ester may be linear or branched. It may be a cyclic alkyl group. Specifically, those having a linear alkyl group include ethyl methacrylate and n-methacrylic acid.
-Butyl, lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate and the like. Also,
Examples of a compound having a branched alkyl group include i-butyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate. Furthermore, examples of those having a cyclic alkyl group include cyclohexyl methacrylate and the like.

When the alkyl group has more than 18 carbon atoms, the polymerization rate is lowered, so that the polymerizability is poor and there is a possibility that a problem may occur in terms of productivity.

The acrylate ester has 1 carbon atom.
To 18 alkyl groups, and the alkyl group of the acrylate ester 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, stearyl 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.

When the number of carbon atoms in the alkyl group exceeds 18, the polymerization rate is reduced, so that the polymerizability is poor and there is a possibility that a problem may occur in terms of productivity.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, chlorostyrene, vinyltoluene and the like.

Other monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl acetate, and dicarboxylic anhydrides such as maleic anhydride.

The use amount of these monomers is 70 to 45% by weight, preferably 60 to 50% by weight. If the amount of these monomers is less than 45% by weight, the effect of imparting releasability to the vinyl chloride resin is impaired. Also, 70
If the amount is more than 10% by weight, the effect of accelerating the gelation of the vinyl chloride resin may be impaired during calendering.

Further, polyfunctional monomers such as divinylbenzene and allyl methacrylate can be used,
In this case, the amount of these polyfunctional monomers used is 2% by weight.
The following is preferred.

Further, the weight average molecular weight (Mw) of the copolymer (B) used in the present invention as measured by gel permeation chromatography is 10,000.
It is preferably from 0 to 500,000.

The weight average molecular weight of the copolymer (B) is 50
If it exceeds 000, the effect of imparting releasability during calendering processing will be significantly impaired. Also, 1
Even when it is less than 000, the effect of imparting releasability at the time of calendering is significantly impaired.

Examples of the polymerization method for obtaining the copolymer (B) of the present invention include an emulsion polymerization method, a suspension polymerization method, and a solution polymerization method, and the emulsion polymerization method is most preferable.

Here, the emulsifier that can be used in the emulsion polymerization 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, an appropriate pH adjuster may be used to prevent hydrolysis of the alkyl methacrylate and the alkyl acrylate. it can. Examples of the pH adjuster used include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, and dihydrogen phosphate. Potassium hydrogen-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 a redox type. Examples of the water-soluble initiator include ordinary inorganic initiators such as persulfates. Can be used alone or in combination with a sulfite, a hydrogen sulfite, a thiosulfate or the like as a redox initiator.

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

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

The processing aid of the present invention is a blend of the copolymer (A) and the copolymer (B) obtained as described above,
The mixing ratio is 0.5 to 100 parts by weight of the copolymer (B) with respect to 100 parts by weight of the copolymer (A). When the blending amount of the copolymer (B) is less than 0.5 part by weight, there is a possibility that a good roll releasability of the sheet during calendering, which is a major feature of the present invention, cannot be obtained. If the blending amount of the copolymer (B) exceeds 100 parts by weight, the promotion of gelation of the vinyl chloride resin may be hindered. Also, air marks are likely to be generated on the sheet during calendering processing, and the secondary workability may be further reduced.

The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the processing aid for calendering of the present invention measured by gel permeation chromatography.
Has a large effect on the properties as a processing aid, so that the weight average molecular weight of the blend of the copolymer (A) and the copolymer (B) measured by gel permeation chromatography is also 700. 2,000-2,000,
000, the molecular weight distribution is also preferably 3.0 or less, and the weight average molecular weight and the molecular weight distribution of the blend are preferably within the above-mentioned ranges even at the aforementioned mixing ratio.

In practicing the present invention, the copolymer (A) and the copolymer (B) are blended by mixing each latex at the above-mentioned mixing ratio in terms of solid content.

The method of recovering the copolymer (A) and the copolymer (B) from the blend latex may be, for example, an acid such as sulfuric acid, hydrochloric acid or phosphoric acid, or an aluminum chloride, Calcium, magnesium sulfate,
The polymer may be precipitated by acid coagulation or salting out with an electrolyte of a salt such as aluminum sulfate or calcium acetate, followed by filtration, washing, and drying to collect the powder.

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.

Further, a known recovery method such as a spray drying method or a freeze drying method can also be used.

Further, the copolymer (A) and the copolymer (B)
There is also a method of obtaining the processing aid of the present invention by blending individual powders of the following later, but the method of obtaining the above-mentioned latex blend is particularly preferred.

The processing aid of the present invention can be used for various purposes, for example, calendering, extrusion molding, injection molding, foam molding, etc., and is particularly preferably used for calendering. .

The vinyl chloride resin used in the vinyl chloride resin composition of the present invention is not particularly limited. For example, vinyl chloride homopolymer, post-chlorinated vinyl chloride polymer, partially crosslinked vinyl chloride polymer Alternatively, there may be mentioned copolymers of vinyl chloride and other vinyl compounds containing not more than 30% by weight of other vinyl compounds copolymerizable with vinyl chloride, and mixtures thereof.

Other vinyl compounds copolymerizable with the vinyl chloride component are not particularly limited, but specific examples thereof include fatty acid vinyl esters such as vinyl acetate and vinyl propionate; methyl methacrylate and methacrylic acid. Alkyl methacrylates such as ethyl and butyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; α-olefins such as ethylene, propylene and styrene; alkyls such as vinyl methyl ether and vinyl butyl ether Vinyl ether; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride; and acid anhydrides thereof. 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, it is not preferable because the inherent characteristics of the vinyl chloride resin are greatly impaired. Further, these vinyl chloride resins may be used alone or in combination of two or more.

The vinyl chloride resin used in the vinyl chloride resin composition of the present invention has an average degree of polymerization of 300.
~ 5,000, more preferably 500
~ 3,000. When the average degree of polymerization is less than 300, a calendered product has sufficient strength to be obtained and has warpage. On the other hand, if the average degree of polymerization exceeds 5,000, it is difficult to sufficiently knead the mixture during calendering, and the processability may be reduced.

The method for producing the vinyl chloride resin used in the vinyl chloride resin composition of the present invention is not particularly limited, and various known methods such as an emulsion polymerization method, a suspension polymerization method and a bulk polymerization method can be used. Technology can be used.

The vinyl chloride resin composition of the present invention preferably contains 0.1 to 20 parts by weight of a processing aid with respect to 100 parts by weight of the vinyl chloride resin, and more preferably 0.2 to 20 parts by weight. 10 parts by weight were blended. If the mixing ratio of the processing aid is less than 0.1 part by weight, air marks are generated on the sheet during calendering, and the releasability of the sheet from the roll metal surface may be reduced. If the compounding ratio is more than 20 parts by weight, the releasability of the sheet from the roll metal surface is improved, but the effect of improving the flow mark may be significantly reduced.

The method of blending and adding the processing aid to the vinyl chloride resin is not particularly limited, and any known kneading and mixing method may be used. For example, a predetermined amount of the vinyl chloride resin and the processing aid may be added. The vinyl chloride resin composition of the present invention is mixed with a Henschel mixer, a Banbury mixer, a ribbon blender, a V-type mixer, or the like, using a kneader such as a single screw extruder, a twin screw extruder, a pressure kneader, or a mixing roll. Can be obtained. Further, the vinyl chloride resin composition of the present invention can be used in any form of powder or pellet.

In the case where the vinyl chloride resin composition of the present invention is obtained by blending the vinyl chloride resin and a processing aid, known heat stabilization may be carried out according to the purpose, as long as the effects of the present invention are not impaired. Agents, lubricants, processing aids, impact modifiers, plasticizers, heat resistance improvers, fillers, foaming agents, pigments, UV stabilizers, antifogging agents, antibacterial agents, antistatic agents, surfactants,
Various additives such as a flame retardant can be used together.

Examples of the heat stabilizer include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite and lead silicate; potassium, magnesium, barium, zinc, cadmium and lead. Metal soap derived from metals such as 2ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid, etc. Organic tin-based stabilizer derived from an alkyl group, an ester group and a fatty acid salt, a maleate, or a sulfide-containing agent; 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, alicyclic acids such as naphthenic acid, and aromatic acids such as phenolic acid, benzoic acid, salicylic acid, and substituted derivatives thereof, and metals usually derived from two or more organic acids. Salt stabilizers; these stabilizers can be used as petroleum hydrocarbons, alcohols,
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 the like. Non-metallic stabilizers such as organic phosphites having an aromatic compound such as the above can be used, and these can 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.

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, and 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 impact modifiers, 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 thereof include propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / acrylic composite rubber-based graft copolymer, and silicone-based rubber.

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

Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate and colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, talc, wollastonite,
Inorganic fibers such as zeolite, silica, zinc oxide, magnesium oxide, carbon black, graphite, glass beads, glass fibers, carbon fibers, and metal fibers, as well as organic fibers such as polyamides can be used. These may be used alone or in combination. Can be used in combination. Others
Flame retardants such as chlorinated paraffin, aluminum hydroxide, antimony trioxide, and halogen compounds, flow improvers, colorants, antistatic agents, surfactants, antifoggants, antibacterial agents, etc. As long as the effect of the resin composition is not impaired, it can be arbitrarily added according to the purpose.

While the description has been given of the compound which can be added together with the vinyl chloride resin composition of the present invention, the present invention is not limited to the specific examples.

The vinyl chloride resin composition of the present invention can be applied to known molding methods, for example, calender molding, extrusion molding, injection molding and the like to obtain various molded products. The effect of the present invention is great in molding.

[0076]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Note that “parts”,
"%" Means "parts by weight" and "% by weight", respectively.
Is shown.

In order to demonstrate the remarkable effects of the processing aid of the present invention and the vinyl chloride resin composition using the same, evaluation tests of roll release properties, flow marks, air marks, gelling properties, and ungelled products were conducted. Carried out.

(Example 1) After the inside of a reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 230
Parts, sodium dioctyl sulfosuccinate 1.0 part, potassium persulfate 0.15 part, methyl methacrylate 85 parts,
A mixture of 15 parts of n-butyl acrylate and 0.0175 part of n-octyl mercaptan was charged, and the inside of the vessel was replaced again with nitrogen. Thereafter, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 2 hours. Then, the polymerization reaction was completed, and the mixture was cooled to obtain a latex of the copolymer (A). A part of the obtained latex was added to an aqueous solution of aluminum chloride for salting out and coagulation, followed by washing and drying to obtain a copolymer (A). 0.05 g of the obtained copolymer (A) was added to 10
After dissolving in chloroform, the solution was subjected to gel permeation chromatography (LC-1 manufactured by Shimadzu Corporation).
0A system), a weight average molecular weight (M) measured using a column (K-806L manufactured by Showa Denko KK).
w) is 1,100,000 and the molecular weight distribution (Mw / Mn)
Was 2.0.

After the inside of the reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 260 parts of ion-exchanged water, 1.5 parts of sodium dioctylsulfosuccinate, 0.2 parts of potassium persulfate, 30 parts of methyl methacrylate, n-octyl After a mixture of 0.03 parts of mercaptan was charged and the inside of the vessel was replaced again with nitrogen, the temperature of the reaction vessel was raised to 65 ° C. with stirring, followed by heating and stirring for 2 hours. Subsequently, methacrylic acid n-
20 parts of butyl, 30 parts of n-butyl acrylate and n-butyl
A mixture of 0.5 parts of octyl mercaptan was added over 1 hour, and after the addition was completed, the mixture was further stirred for 2 hours. Thereafter, 20 parts of methyl methacrylate and n
-A mixture of 0.05 parts of octyl mercaptan was added over 30 minutes, and the mixture was further heated and stirred for 2 hours. Then, the polymerization reaction was terminated and cooled to obtain a latex of copolymer (B).

A part of the obtained latex was added to an aluminum chloride aqueous solution and subjected to salting out and coagulation, followed by washing and drying to obtain a copolymer (B). The weight average molecular weight (Mw) of the obtained copolymer (B) was 220,000.

Next, 100 parts of a latex of the copolymer (A) as a solid content is put into a reaction vessel equipped with a stirrer and stirred. Thereto, 10 parts of a latex of the copolymer (B) as a solid content was added over 10 seconds, followed by stirring for 20 minutes. The obtained latex mixture was added to an aqueous solution of aluminum chloride, subjected to salting out and coagulation, then washed, dehydrated, and dried to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the copolymer mixture is 1,040,00.
0, molecular weight distribution (Mw / Mn) was 2.4.

This copolymer mixture was subjected to the following evaluation tests.

(1) Roll releasability evaluation: A 6-inch roll (manufactured by Kansai Roll Co., Ltd.) was used at a kneading temperature of 200 ° C.
A sample was kneaded with 100 g of the sample at a roll interval of 0.25 mm, and the time until the sheet was hardly peeled was measured. The longer the time, the better the releasability of the sheet from the roll metal surface.

The resin composition used for evaluation of the roll release property was as follows:
The following formulation was used.

100 parts of a vinyl chloride homopolymer (TK-800, manufactured by Shin-Etsu Chemical Co., Ltd.) having an average degree of polymerization of 800 was added to dibutyltin mercaptide (T-Made, manufactured by Katsuta Kako Co., Ltd.).
17MJ) 1.7 parts, polyhydric alcohol fatty acid ester (Loxiol G-16 manufactured by Henkel Japan K.K.)
1.0 part, 6.0 parts of Metablen C-201A (manufactured by Mitsubishi Rayon Co., Ltd.) and the copolymer mixture obtained in Examples or Comparative Examples were blended, and the internal temperature was adjusted to 120 ° C. using a Henschel mixer. And then cooled to room temperature to obtain a vinyl chloride resin composition.

(2) Flow mark evaluation: Using a 6-inch roll (manufactured by Kansai Roll Co., Ltd.) at a kneading temperature of 200 ° C.
A sheet having a thickness of 0.5 mm was prepared by kneading with a roll interval of 0.25 mm and a sample of 100 g for 3 minutes, and the flow mark amount on the sheet was visually determined.
Δ, × was evaluated. Here, ○ indicates that there is almost no flow mark, Δ indicates that the flow mark is conspicuous and may pose a practical problem, and x indicates that the flow mark is generated and is very conspicuous and impractical.

This evaluation was performed using the same vinyl chloride resin composition as used in the evaluation of roll release property.

(3) Air mark evaluation: Using a 6-inch roll (manufactured by Kansai Roll Co., Ltd.) at a kneading temperature of 200 ° C.
A sheet having a thickness of 2 mm is prepared by kneading with a roll interval of 0.25 mm and a sample of 100 g for 3 minutes, and the size and amount of the air mark on the sheet are visually determined. did. Here, ○ indicates that there is almost no air mark, Δ indicates that the air mark is conspicuous and may cause a practical problem, and x indicates that the air mark is generated and conspicuous and is not practical.

This evaluation was performed using the same vinyl chloride resin composition as used in the evaluation of roll release property.

(4) Evaluation of gelling properties: Maximum torque and maximum torque when kneaded using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) at a temperature of 160 ° C., a rotation speed of 30 rpm, and a filling amount of 53 g. (Gelation time) was measured. The shorter the gelation time, the faster the gelation.

The following composition was used for the resin composition used for the evaluation of the gelation characteristics.

100 parts of vinyl chloride homopolymer (TK-800, manufactured by Shin-Etsu Chemical Co., Ltd.) having an average degree of polymerization of 800 was added to dibutyltin mercaptide (Tatsuda Kako Co., Ltd.
-17MJ), 1.1 parts of polyhydric alcohol fatty acid ester (Loxiol G-1 manufactured by Henkel Japan Ltd.)
5. 6) 0.8 parts, polymer ester (Loxiol G-70S, manufactured by Henkel Japan KK) 0.15 parts, Metablen C-201A (manufactured by Mitsubishi Rayon Co., Ltd.)
0 parts and the copolymer mixture obtained in Examples or Comparative Examples were blended, and the internal temperature was 120 ° C. using a Henschel mixer.
And then cooled to room temperature to obtain a vinyl chloride resin composition.

(5) Ungelled product: Using a 20 mm single screw extruder equipped with a T-die, the screw rotation speed was 40 r.
A film having a thickness of 0.1 mm was extruded at pm and a cylinder temperature of 180 ° C., and the number of ungelled substances in a fixed area of the film surface was visually determined, and evaluated in good order by 良好, Δ, and ×. Here, ○ means very good, 未 means that the ungelled matter is conspicuous and may have a practical problem, and × means that the ungelled matter is too many to be practical.

The following composition was used for the resin composition used for the evaluation of the ungelled product.

A vinyl chloride homopolymer having an average degree of polymerization of 700 (TK-700 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to dibutyltin mercaptide (T-17MJ manufactured by Katsuta Kako Co., Ltd.).
2.0 parts, 0.9 part of polyhydric alcohol fatty acid ester (Loxiol G-16, manufactured by Henkel Japan K.K.),
Polymer ester (Lox, manufactured by Henkel Japan Ltd.)
iolG-72) 0.6 parts, Metablen C-201A
(Mitsubishi Rayon Co., Ltd.) 5.0 parts and the copolymer mixture obtained in Examples or Comparative Examples were blended, mixed using a Henschel mixer until the internal temperature reached 120 ° C., and then cooled to room temperature. Thus, a vinyl chloride resin composition was obtained.

Example 2 After replacing the inside of a reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, 150 parts of ion-exchanged water, 1.0 part of sodium dioctylsulfosuccinate, 0.15 part of potassium persulfate, and 80 parts of methyl methacrylate were used. , A mixture of 4 parts of n-butyl acrylate and 0.018 part of n-octylmercaptan was charged, and the inside of the vessel was replaced with nitrogen again. After heating and stirring for a period of time, a mixture of 10 parts of methyl methacrylate and 6 parts of n-butyl acrylate was added to the reaction vessel in 5 minutes. After the addition was completed, the mixture was further heated and stirred for 3 hours. As a result, a latex of the copolymer (A) was obtained. Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The weight average molecular weight of the obtained copolymer (A) was 1,120,000, and the molecular weight distribution was 2.3.

After the inside of the reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, a mixture of 150 parts of ion-exchanged water, 1.5 parts of sodium dioctylsulfosuccinate, 0.2 parts of potassium persulfate and 30 parts of methyl methacrylate was charged. After the inside of the vessel was replaced with nitrogen again, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 3 hours. continue,
33 parts of styrene, 22 parts of n-butyl acrylate and n
-A mixture of 0.5 parts of octyl mercaptan was added over 90 minutes, and after the addition was completed, the mixture was further heated and stirred for 2 hours. Thereafter, 15 parts of methyl methacrylate was added to the reaction system in 30 minutes, and after the addition was completed, the mixture was heated and stirred for 1.5 hours, and then the polymerization reaction was terminated, and the mixture was cooled to obtain a latex of the copolymer (B). I got Hereinafter, a dried product of the copolymer (B) was obtained for a part of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (B) was 400,000.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was prepared. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture is 1,100,00
0, molecular weight distribution (Mw / Mn) was 2.8.

Example 3 After the inside of a reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 150 parts of ion-exchanged water was removed.
Parts and sodium dioctyl sulfosuccinate 1.5 parts,
0.2 parts of potassium persulfate, 70 parts of methyl methacrylate,
1. A mixture of 4 parts of n-butyl acrylate and 0.025 part of n-octyl mercaptan was charged, the atmosphere in the vessel was replaced with nitrogen, and the temperature of the reaction vessel was raised to 65 ° C. with stirring.
After heating and stirring for 5 hours, a mixture of 8 parts of methyl methacrylate, 8 parts of n-butyl acrylate and 0.5 part of n-octyl mercaptan was added to the reaction vessel over 15 minutes. The mixture was heated and stirred for hours.
Subsequently, 10 parts of methyl methacrylate were added over 10 minutes, and after completion of the addition, the mixture was heated and stirred for 2 hours to terminate the polymerization reaction and cooled to obtain a latex of the copolymer (A).
Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (A) was 730,000, and the molecular weight distribution was 2.7.

After the inside of the reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 150 parts of ion-exchanged water, 1.5 parts of sodium dioctylsulfosuccinate and 0.3 parts of potassium persulfate, 10 parts of methyl methacrylate, n-octyl After a mixture of 0.1 part of mercaptan was charged and the inside of the vessel was replaced again with nitrogen, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 1.5 hours. Then, styrene 36
, A mixture of 24 parts of n-butyl acrylate and 1.0 part of n-octylmercaptan was added over 90 minutes, and after the addition was completed, the mixture was further heated and stirred for 2 hours. Thereafter, 30 parts of methyl methacrylate and 0.1 part of n-octyl mercaptan were added to this reaction system over 45 minutes, and after the addition was completed, the mixture was heated and stirred for 2 hours, and then the polymerization reaction was terminated. A latex of the polymer (B) was obtained. Hereinafter, a dried product of the copolymer (B) was obtained for a part of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (B) was 70,000.

A latex blend of copolymer (A) and copolymer (B) was prepared in the same manner as in Example 1. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture was 700,000, and the molecular weight distribution (Mw / Mn) was 2.9.

(Example 4) After the inside of a reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 150 parts of ion-exchanged water was removed.
Parts, 1.5 parts of sodium dioctyl sulfosuccinate and 0.15 part of potassium persulfate, 40 parts of methyl methacrylate,
A mixture of 6 parts of n-butyl acrylate and 0.0035 parts of n-octyl mercaptan was charged, and after the inside of the vessel was replaced with nitrogen again, the temperature of the reaction vessel was increased to 65 ° C. with stirring, followed by heating and stirring for 2 hours. Thereafter, a mixture of 40 parts of methyl methacrylate and 14 parts of n-butyl acrylate was added to the reaction vessel over 60 minutes. After the addition was completed, the mixture was further heated and stirred for 3 hours. Coalescing (A)
Latex was obtained. Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The weight average molecular weight of the obtained copolymer (A) was 1,600,000, and the molecular weight distribution was 2.8.

After replacing the inside of the reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, 150 parts of ion-exchanged water, 1.2 parts of sodium dioctylsulfosuccinate and 0.15 parts of potassium persulfate, 40 parts of styrene and n-acrylic acid were used. Butyl 3
A mixture of 0 part and 0.9 part of n-octyl mercaptan was charged, and the inside of the vessel was replaced with nitrogen again. Then, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 2 hours. A mixture of 30 parts of methyl methacrylate and 0.03 part of n-octylmercaptan was added to the mixture over 35 minutes. After the addition was completed, the mixture was heated and stirred for 3 hours, and then the polymerization reaction was terminated and cooled to obtain a copolymer (B). Latex was obtained. Hereinafter, a dried product of the copolymer (B) was obtained for a part of the obtained latex in the same manner as in Example 1.

The weight average molecular weight of the obtained copolymer (B) was 90,000.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was prepared. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture is 1,480,00
0, molecular weight distribution (Mw / Mn) was 2.8.

(Example 5) After the inside of a reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, ion-exchanged water 230
Parts, 1.0 part of sodium dioctyl sulfosuccinate, 0.15 part of potassium persulfate, 80 parts of methyl methacrylate,
18 parts of n-butyl acrylate, 2 parts of styrene and n-butyl
After charging a mixture of 0.0185 parts of octyl mercaptan and replacing the inside of the vessel again with nitrogen, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 2 hours. A latex of the copolymer (A) was obtained.
Hereinafter, a dried product of the copolymer (A) was obtained for a part of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (A) was 900,000, and the molecular weight distribution (Mw / Mn)
Was 2.1.

After the inside of the reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 260 parts of ion-exchanged water, 1.5 parts of sodium dioctylsulfosuccinate, 0.2 parts of potassium persulfate, 30 parts of methyl methacrylate, n-octyl After a mixture of 0.03 parts of mercaptan was charged and the inside of the vessel was replaced again with nitrogen, the temperature of the reaction vessel was raised to 65 ° C. with stirring, followed by heating and stirring for 2 hours. Subsequently, a mixture of 20 parts of styrene, 30 parts of n-butyl acrylate and 0.5 part of n-octyl mercaptan was added over 1 hour, and after the addition was completed, the mixture was further stirred for 2 hours. Thereafter, a mixture of 20 parts of methyl methacrylate and 0.05 part of n-octyl mercaptan was added to the reaction system over 30 minutes,
After further heating and stirring for 2 hours, the polymerization reaction was terminated and cooled to obtain a latex of the copolymer (B). Hereinafter, a dried product of the copolymer (B) was obtained for a part of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (B) was 190,000.

A latex blend of the copolymer (A) and the copolymer (B) was prepared in the same manner as in Example 1. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture was 830,000, and the molecular weight distribution (Mw / Mn) was 2.8.

(Comparative Example 1) Molding was evaluated without adding the copolymer mixture to the vinyl chloride resin composition.

Comparative Example 2 The copolymer (A) was prepared in the same manner as in Example 1 except that n-octyl mercaptan was not used.
A latex was prepared in the same manner as in Example 1. Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The weight average molecular weight of the obtained copolymer (A) was 3,000,000, and the molecular weight distribution was 3.7.

As the copolymer (B), a latex was prepared in the same manner as in Example 1.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was prepared. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture is 2,910,00
0, molecular weight distribution (Mw / Mn) was 3.4.

Comparative Example 3 After the inside of a reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 150 parts of ion-exchanged water was removed.
Parts and sodium dioctyl sulfosuccinate 1.5 parts,
0.2 parts of potassium persulfate, 85 parts of methyl methacrylate,
After a mixture of 0.025 parts of n-octyl mercaptan was charged and the inside of the vessel was replaced with nitrogen, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 3 hours, and then methyl methacrylate 2 was added to the reaction vessel. A mixture of 0.5 part, 2.5 parts of n-butyl acrylate and 0.5 part of n-octyl mercaptan was added over 15 minutes, and after the addition was completed, the mixture was further heated and stirred for 1.5 hours. Subsequently, 10 parts of methyl methacrylate were added over 10 minutes, and after completion of the addition, the mixture was heated and stirred for 2 hours to terminate the polymerization reaction and cooled to obtain a latex of the copolymer (A). Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (A) was 790,000, and the molecular weight distribution was 2.7.

As the copolymer (B), a latex was prepared in the same manner as in Example 1.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was prepared. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture was 760,000, and the molecular weight distribution (Mw / Mn) was 2.9.

(Comparative Example 4) After the inside of a reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 150 parts of ion-exchanged water was replaced.
Parts and sodium dioctyl sulfosuccinate 1.5 parts,
0.2 parts of potassium persulfate, 50 parts of methyl methacrylate,
A mixture of 30 parts of n-butyl acrylate and 0.009 parts of n-octyl mercaptan was charged, and the inside of the vessel was replaced with nitrogen. Then, the temperature of the reaction vessel was increased to 65 ° C. with stirring, and the mixture was heated and stirred for 3 hours. Methyl methacrylate 2 in the reaction vessel
A mixture of 0 part and 0.06 part of n-octyl mercaptan was added over 30 minutes, and after completion of the addition, the mixture was heated and stirred for 2 hours to terminate the polymerization reaction and cooled to obtain a latex of the copolymer (A). . Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (A) was 270,000, and the molecular weight distribution was 2.6.

As the copolymer (B), a latex was prepared in the same manner as in Example 1.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was performed. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture was 220,000, and the molecular weight distribution (Mw / Mn) was 2.8.

Comparative Example 5 80 parts of methyl methacrylate of the copolymer (A) in Example 1
A latex was prepared in the same manner as in Example 1 except that butyl was used in 20 parts. Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The weight average molecular weight of the obtained copolymer (A) was 1,060,000, and the molecular weight distribution (Mw / Mn) was 2.3.
Met.

A latex was prepared in the same manner as in Example 2 except that the copolymer (B) was changed to 0.05 part of n-octyl mercaptan. Hereinafter, a dried product of the copolymer (B) was obtained for a part of the obtained latex in the same manner as in Example 1.

The weight average molecular weight (Mw) of the obtained copolymer (B) was 810,000.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was prepared. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture was 220,000, and the molecular weight distribution (Mw / Mn) was 2.5.

Comparative Example 6 In the same manner as in Example 1, latexes of the copolymer (A) and the copolymer (B) were produced.

A latex blend of the copolymer (A) and the copolymer (B) was carried out in the same manner as in Example 1 except that 200 parts of the copolymer (B) as a solid content was used for the latex blend. . Hereinafter, the obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. Weight average molecular weight (Mw) of the obtained copolymer mixture
Is the weight average molecular weight (Mw) of the copolymer mixture is 740,0
The molecular weight distribution (Mw / Mn) was 3.8.

(Comparative Example 7) In the same manner as in Example 1, a latex of the copolymer (A) was prepared. Latex blending of copolymer (A) and copolymer (B) was not performed.

Comparative Example 8 In the same manner as in Example 1, a latex of the copolymer (A) was prepared.

After replacing the inside of the reaction vessel equipped with a stirrer and a reflux condenser with nitrogen, 150 parts of ion-exchanged water, 1.0 part of sodium dioctylsulfosuccinate and 0.15 part of potassium persulfate, 20 parts of styrene, n-acrylic acid Butyl 6
A mixture of 0 parts and 0.09 parts of n-octyl mercaptan was charged, and the inside of the vessel was replaced again with nitrogen. Then, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 2 hours. Was added for 30 minutes, and after completion of the addition, the mixture was further heated and stirred for 3 hours, and then the polymerization reaction was terminated and cooled to obtain a latex of the copolymer (B). Hereinafter, a dried product of the copolymer (B) was obtained for a part of the obtained latex in the same manner as in Example 1.

The weight average molecular weight of the obtained copolymer (B) was 230,000.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was prepared. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture was 1,060,00
0, molecular weight distribution (Mw / Mn) was 2.4.

(Comparative Example 9) After the inside of a reaction vessel equipped with a stirrer and a reflux condenser was replaced with nitrogen, 150 parts of ion-exchanged water
Parts, 1.5 parts of sodium dioctyl sulfosuccinate and 0.15 part of potassium persulfate, 40 parts of methyl methacrylate,
A mixture of 6 parts of n-butyl acrylate and 0.0035 parts of n-octyl mercaptan was charged, and the inside of the vessel was replaced with nitrogen again. Then, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and the mixture was heated and stirred for 2 hours. Thereafter, a mixture of 40 parts of methyl methacrylate and 14 parts of n-butyl acrylate was added to the reaction vessel over a period of 30 minutes. After the addition was completed, the mixture was heated and stirred for another 3 hours. A latex of the combined (A) was obtained. Hereinafter, a dried product of the copolymer (A) was obtained for a portion of the obtained latex in the same manner as in Example 1.

The obtained copolymer (A) had a weight average molecular weight of 1,750,000 and a molecular weight distribution of 3.6.

A latex of the copolymer (B) was prepared in the same manner as in Example 1.

In the same manner as in Example 1, a latex blend of the copolymer (A) and the copolymer (B) was prepared. Less than,
The obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture. The weight average molecular weight (Mw) of the obtained copolymer mixture is 1,720,00
0, molecular weight distribution (Mw / Mn) was 3.4.

(Comparative Example 10) In the same manner as in Example 1, a latex of the copolymer (A) and the copolymer (B) was prepared.
Latex blending was performed in the same manner as in Example 1. Hereinafter, the obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture.

0.1 part of the obtained copolymer mixture was added to and blended with the chloride-based resin composition.

(Comparative Example 11) In the same manner as in Example 1, a latex of the copolymer (A) and the copolymer (B) was prepared.
Latex blending was performed in the same manner as in Example 1. Hereinafter, the obtained latex mixture was operated in the same manner as in Example 1 to obtain a powdery copolymer mixture.

30 parts of the obtained copolymer mixture was added to and mixed with the chlorinated vinyl resin composition.

[0149]

[Table 1]

[0150]

As described above, the processing aid for vinyl chloride-based resin and the vinyl chloride-based resin composition using the same according to the present invention improve the processability of vinyl chloride-based resin, and also provide a sheet or a sheet formed by calendering. Eliminates flow marks generated on films or extruded sheets or films, reduces plate-out, and exhibits excellent sheet release properties when calendered, and its industrial value is extremely large. is there.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 27/04 C08L 27/04 33/08 33/08 33/10 33/10 // (C08L 27/04 33:12) (72) Inventor Ken Ken Dobe 3816 Notobe, Tama-ku, Kawasaki-shi, Kanagawa Prefecture, Tokyo Mitsubishi Rayon Co., Ltd.

Claims (5)

[Claims] 1. 70 to 90% by weight of methyl methacrylate
And a gel obtained by copolymerizing a monomer mixture comprising 30 to 10% by weight of a methacrylate ester excluding an acrylate ester or methyl methacrylate and another monomer copolymerizable therewith. Copolymer (A) having a weight average molecular weight (Mw) measured by permeation chromatography in the range of 700,000 to 2,000,000 and a molecular weight distribution (Mw / Mn) of 3.0 or less.
And at least 30% by weight or more of methyl methacrylate and a monomer having at least one selected from the group consisting of methacrylic acid esters other than methyl methacrylate, acrylic acid esters, aromatic alkenyl compounds, and other monomers Weight average molecular weight (Mw) measured by gel permeation chromatography, obtained by copolymerizing a monomer mixture consisting of
A processing aid consisting of the copolymer (B) in the range of 0.000; 2. A vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin and 0.1 to 20 parts by weight of the processing aid according to claim 1. 3. The processing aid according to claim 1, which is used for calendering. 4. A vinyl chloride resin composition according to claim 2, which is used for calender molding. 5. A method for producing a molded article from the vinyl chloride resin composition according to claim 2 by calender molding.