JP2002317004A - Vinyl chloride-based paste resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride-based paste resin capable of giving a product excellent in heat resistance, also improving the crushing efficiency of the vinyl chloride-based paste resin and increasing the recovery rate of the resin in its production processes, and its paste sol composition and gelled composition. SOLUTION: This vinyl chloride-based paste resin is prepared from latex obtained by polymerizing a vinyl chloride-based monomer by using an ammonium salt-based emulsifying agent, and containing 100 pts.wt. vinyl chloride-based monomer, 0.1-5.0 pt.wt. ammonium salt-based emulsifying agent and 0.005-1.0 pt.wt. polymer-based suspension-stabilizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride paste resin, and a paste sol composition and a gelling composition using the same. More specifically, a vinyl chloride-based paste resin in which a product excellent in heat resistance is provided, the pulverization efficiency of the vinyl chloride-based paste resin is improved in a production process, and a resin recovery rate is increased, and a paste sol composition using the same. And gelled compositions.

[0002]

2. Description of the Related Art A paste processing of a vinyl chloride paste resin is performed by mixing a vinyl chloride paste resin with a plasticizer and, if necessary, a stabilizer and other components to form a paste sol. This is a method of shaping, then heating and gelling to form.

Examples of the forming method include a coating (coating) method, a dipping (dipping) method, a spray (spray) coating method, a casting method, a slush molding method, a rotational molding method, and a foam molding method.

Various products such as wallpaper, flooring cushion floor, flooring carpet tile, ceiling material, leather, canvas, steel plate, sealant, automobile interior material, automobile underbody coat, marking film, insulating coating material by paste processing Is manufactured. Of these, steel sheets, insulating coatings, top layers in floor cushion floors,
In particular, heat resistance is required for marking films, wallpaper, ceiling materials, canvas, and the like.

[0005] Japanese Patent No. 2853387 discloses a polyvinyl chloride resin for paste processing, which provides a soft vinyl chloride resin molded product having excellent transparency and capable of maintaining transparency and water resistance before immersion even when immersed in warm water. In order to efficiently produce the union, a method has been proposed in which an alkali metal alkylsulfosuccinate and an ammonium alkylsulfosuccinate are used in combination and homogenized together with an oil-soluble initiator to carry out polymerization.

According to this method, transparency and water resistance are improved, but problems such as deterioration of heat resistance of the product arise due to the presence of the alkali metal salt.

Japanese Patent Application Laid-Open No. 6-306234 discloses that a latex obtained by emulsion polymerization or fine suspension polymerization using a higher fatty acid ammonium salt contains an alkali metal hydroxide for the higher fatty acid ammonium salt used. A method has been proposed in which 0.4 to 0.8 equivalents of a product are added and mixed, followed by spray drying. By the addition of the alkali metal hydroxide, a part of the ammonium group of the higher fatty acid ammonium salt is replaced by the alkali metal, which contributes to the improvement of the viscosity of the plastisol. When a plastisol whose viscosity is improved by this method is used, the effect of eliminating flow, dripping, and the like can be obtained when rotary screen coating is performed, but problems such as deterioration of heat resistance of the product due to the alkali metal occur.

Further, Japanese Patent Publication No. 5-9446 (JP-A-61-206) discloses that the mechanical stability of latex is good, the amount of lumps is small, and In order to prevent whitening and deterioration in transparency of the molded product caused by the effect of the emulsifier contained therein or the moisture absorbed by the emulsifier, (1) sulfonates, ether sulfates and carbons are used as emulsifiers. Number 8-
At least one selected from 22 higher fatty acid salts;
(2) Mixture with maleic acid copolymer salt ((1) /
(2) weight ratio of 1/30 or more) is used in an amount of 0.05 to 2.0% by weight (hereinafter referred to as%) with respect to the vinyl chloride monomer, and the pH of the aqueous medium is 6 As described above, a method of seeding emulsion polymerization has been proposed.

In this case, the problems of prevention of whitening and transparency of the molded article are improved, but the maleic acid copolymer salt (2) has the effect of improving the mechanical stability of the latex, but (1) ), There is a problem that the polymerization stability is poor as compared with the general emulsifier for vinyl chloride. Further, there is a problem that the heat resistance of the product deteriorates due to the alkali metal salt contained in the maleic acid copolymer salt and a general emulsifier for vinyl chloride.

[0010] In Japanese Patent Publication No. 5-9446,
"If (1) exceeds 1.0% by weight, the water resistance of the polymer is reduced. If (2) is more than 1.5% by weight, the polymerization reaction rate is greatly reduced, and Decreases the water resistance ". When the maleic acid copolymer salt is added before the start of the polymerization or during the polymerization, the polymerization rate is reduced, the coalesced aggregation of the produced particles occurs, and the desired particle size distribution cannot be obtained, or It is not preferable because a scale may be generated.

JP-B-57-48568 discloses that in order to improve the mechanical stability of a latex of a vinyl chloride paste resin, an emulsifier contains a monobasic or dibasic carboxylic acid and / or a salt thereof. Polymer 0.01 to
A method of fine suspension polymerization using 0.5%, and JP-A-61-205, discloses that the latex of vinyl chloride paste resin has good mechanical stability and degassing property, Uses maleic acid copolymer salt as an emulsifier to prevent blooming that occurs on the surface of the molded product due to the emulsifier contained in the vinyl paste resin, or whitening of the molded product due to moisture absorption and decrease in transparency A way to do that has been proposed.

These methods also have the effect of preventing the whitening and transparency of the intended molded product, but they are disclosed in
It is not preferred because it has the same disadvantages as in JP-A-9446.

[0013]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and provides a product having excellent heat resistance, and has a pulverizing efficiency of a vinyl chloride paste resin in a production process. It is an object of the present invention to provide a vinyl chloride paste resin having improved resin recovery rate, and a paste sol composition and a gelling composition using the vinyl chloride paste resin.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, polymerizing a vinyl chloride paste resin with an ammonium salt emulsifier; Paste resin latex,
By adding 0.005 to 1.0 part of the polymer suspension stabilizer to 100 parts by weight of the vinyl chloride monomer (hereinafter referred to as "parts"), a product excellent in heat resistance is provided, and In the production process, it was found that the pulverization efficiency of the vinyl chloride-based paste resin was improved and the recovery rate of the resin was increased, and the present invention was completed.

That is, the present invention relates to (1) a latex of a vinyl chloride-based paste resin obtained by polymerizing a vinyl chloride-based monomer using an ammonium salt-based emulsifier, and based on 100 parts by weight of the vinyl chloride-based monomer. And a vinyl chloride paste resin from a latex containing 0.1 to 5.0 parts by weight of an ammonium salt-based emulsifier and 0.005 to 1.0 parts by weight of a polymer suspension stabilizer (Claim 1) , (2)
The vinyl chloride paste resin according to claim 1, wherein the polymer suspension stabilizer is contained in an amount of 0.005 to 0.3 parts by weight based on 100 parts by weight of the vinyl chloride monomer.
(3) The vinyl chloride paste resin according to claim 1, wherein the polymer suspension stabilizer is contained in an amount of 0.01 to 0.2 parts by weight based on 100 parts by weight of the vinyl chloride monomer. 3), (4) a polymer suspension stabilizer added to a latex of a vinyl chloride paste resin after polymerization,
2. The vinyl chloride paste resin according to claim 2 or 3, wherein the ammonium salt emulsifier is selected from the group consisting of ammonium carboxylate emulsifier, ammonium sulfate emulsifier and ammonium sulfonate emulsifier. The polyvinyl chloride paste resin according to claim 1, which is at least one kind (claim 5),
(6) The vinyl chloride paste resin according to claim 1, 2, 3, 4, or 5, wherein the ammonium salt emulsifier is a fatty acid ammonium having 10 to 20 carbon atoms.
(7) The ammonium salt-based emulsifier is represented by the general formula (I): R ¹ O (CH ₂ CH ₂ O) _n R ² COONH ₄ (I) (wherein, R ¹ is a monovalent carbon having 8 to 30 carbon atoms) Hydrogen group, R ²
Is a divalent hydrocarbon group having 1 to 30 carbon atoms, and n is 1 to 30)
And a compound represented by the general formula (II):

[0016]

Embedded image

(Wherein R ³ , R ⁴ and R ⁵ are a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 30 carbon atoms, n is at least one selected from the group consisting of compounds represented by 1 to 30), the vinyl chloride paste resin according to claim 1, 2, 3, 4 or 5 (claim 7), and (8) ammonium. The salt emulsifier is represented by the general formula (III): R ¹ O (CH ₂ CH ₂ O) _n SO ₃ NH ₄ (III) (wherein, R ¹ is a monovalent hydrocarbon group having 8 to 30 carbon atoms, n
Is a compound represented by 1 to 30) and a general formula (IV):

[0018]

Embedded image

(Wherein R ³ , R ⁴ and R ⁵ are a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and n is 1 to 30)
6. The vinyl chloride paste resin according to claim 1, which is at least one member selected from the group consisting of compounds represented by the formula (8), (9): a polymer suspension stabilizer. Is at least one selected from the group consisting of vinyl polymers, vinyl copolymers, and ammonium salts thereof.
The vinyl chloride paste resin according to claim 1,2,3,4,5,6,7 or 8 which is a seed (claim 9), (10)
The polyvinyl chloride paste resin according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the polymer suspension stabilizer is polyvinyl alcohol. Claims 1, 2, 3, wherein the stabilizer is a cellulose derivative.
The vinyl chloride paste resin described in 4, 5, 6, 7 or 8 (Claim 11), wherein the polymer suspension stabilizer is a carboxylic acid polymer, a carboxylic acid copolymer, or an ammonium thereof. 9. The vinyl chloride paste resin according to claim 1, which is at least one member selected from the group consisting of salts (claim 12), (13) a polymer suspension. The turbidity stabilizer is at least one selected from the group consisting of a maleic anhydride-based polymer, a maleic anhydride-based copolymer, and an ammonium salt thereof.
The vinyl chloride paste resin described in 3, 4, 5, 6, 7 or 8 (Claim 13); (14) the polymer suspension stabilizer is a copolymer of maleic anhydride and styrene; The vinyl chloride paste resin according to claim 1, which is at least one member selected from the group consisting of salts (claim 14), (15).
The polymer suspension stabilizer is a vinyl polymer, a vinyl copolymer, a carboxylic acid polymer, a carboxylic acid copolymer, a maleic anhydride polymer, a maleic anhydride copolymer, or maleic anhydride. Natonium salt of a copolymer of acid and styrene,
The vinyl chloride paste resin according to claim 2, which is at least one selected from the group consisting of potassium salts, (claim 15), (16). , 3, 4, 5, 7, 8, 9, 10, 11, 12,
A paste sol composition using the vinyl chloride paste resin according to claim 13, 14 or 15 (claim 16), and (17) claims 1, 2, 3, 4, 5, 7, 8, 9, 1
A gel composition using the vinyl chloride paste resin described in 0, 11, 12, 13, 14, or 15 (claim 17).
About.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride paste resin suitable for the paste processing of the present invention is a vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith. Also referred to as vinyl chloride monomer)
In an aqueous medium, using an emulsifier, a dispersing aid such as a higher alcohol or a higher fatty acid as needed, and further performing emulsion polymerization or seed emulsion polymerization using a water-soluble initiator, a vinyl chloride monomer alone. Alternatively, a mixture of a vinyl chloride monomer and a copolymerizable monomer with the same, in an aqueous medium, using an emulsifier and, if necessary, a dispersing aid such as a higher alcohol or a higher fatty acid, and further starting oil-soluble polymerization. The mixture is homogenized by adding an agent and then subjected to fine suspension polymerization, and then the vinyl chloride paste resin latex (aqueous homogeneous dispersion) after polymerization is spray-dried. The latex obtained in each polymerization may be mixed and spray-dried. If necessary, the resin after spray drying may be pulverized. When drying, generally dehydration,
Raw materials such as emulsifiers remain in the resin because filtration is not performed. In the polymerization of the vinyl chloride paste resin, the vinyl chloride monomer used is generally 80 to 95%
Becomes a resin, and the remaining unreacted monomers are removed. In the vinyl chloride paste resin, a part of the basic particles are aggregated and aggregated during spray drying to form secondary aggregated particles. In the pulverizing step, these secondary aggregated particles are crushed to improve the releasability of the resin at the time of forming the paste sol, and to prevent the occurrence of bumps (fish eyes) in the gelled product. In addition, 6-5
As described in JP-A-5831 and JP-B-6-72169, it may be produced by a method for producing a granular resin which is used without being pulverized.

The above-mentioned vinyl chloride paste resin has a basic particle diameter of generally 0.001 to 10 μm and a finer particle diameter than a general-purpose vinyl chloride resin, so that it has good dispersibility in a plasticizer and has good paste processing properties. Suitable for.

For the purpose of improving the fluidity of the paste sol, a polyvinyl chloride blending resin can be used in combination.

The vinyl chloride blending resin is
The particle size is generally in the range of 10 to 100 μm, and is generally blended in the range of 50% or less with respect to the vinyl chloride paste resin. The vinyl chloride blending resin is, for example, a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith in an aqueous medium containing a polymer suspension stabilizer and the like. , A suspension polymerization is performed by adding an oil-soluble polymerization initiator, the slurry after the polymerization is dehydrated by a centrifugal dehydrator or the like, and further subjected to flash drying, fluid drying and the like.

Examples of the monomers copolymerizable with the vinyl chloride include olefins such as ethylene, propylene and butene; vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate and vinyl stearate; Vinyl ethers having an alkyl group such as vinyl ether, ethyl vinyl ether, octyl vinyl ether and lauryl vinyl ether; vinylidene halides such as vinylidene chloride; acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride Unsaturated carboxylic acids, such as their anhydrides, methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, unsaturated carboxylic esters such as butyl benzyl maleate, styrene, α-methyl Styrene, aromatic vinyl compounds such as divinylbenzene, unsaturated nitriles such as acrylonitrile, further including cross-linking monomer such as diallyl phthalate. These may be used alone or in combination of two or more.

The vinyl chloride paste resin is generally made of an alkali metal such as a fatty acid compound, a sulfuric acid compound, a sulfonic acid compound, a sulfosuccinic acid compound, or the like.
Although it is manufactured using an emulsifier consisting of a salt such as potassium), the alkali metal salt contained in the emulsifier lowers the heat resistance of the product. On the other hand, in the case of an emulsifier comprising an ammonium salt of the above compound (ammonium salt-based emulsifier), a decrease in heat resistance due to an emulsifier comprising an alkali metal salt does not occur. Therefore, in the present invention, an ammonium salt-based emulsifier is used.

Specific examples of the ammonium salt emulsifier include, for example, ammonium carboxylate emulsifier, ammonium sulfate emulsifier, and ammonium sulfonate emulsifier. These may be used alone or in combination of two or more. These ammonium salt-based emulsifiers are preferred from the viewpoint of polymerization stability and heat resistance.

The ammonium salt emulsifier is used in an amount of 0.1 to 5 parts, preferably 0.2 to 2 parts, particularly preferably 0.3 to 1 part, per 100 parts of the vinyl chloride monomer. When the addition amount of the ammonium salt-based emulsifier is less than 0.1 part, the polymerization becomes unstable, which is not preferable. Even when added in an amount of more than 5 parts, the production cost is high. Is not practical.

The ammonium emulsifier may be added to the aqueous medium before polymerization of the vinyl chloride paste resin, or may be continuously added during the polymerization. Furthermore, in order to improve the mechanical stability of the polymerized latex, it may be added to the polymerized latex as needed.

As described above, the vinyl chloride monomer used in the polymerization of the vinyl chloride paste resin is generally 8
0-95% becomes resin, and the remaining unreacted monomers are removed. Therefore, polymerization is carried out using 1 part of an ammonium salt-based emulsifier with respect to 100 parts of a vinyl chloride-based monomer, and when the polymerization addition ratio is 80%, the content of the ammonium salt-based emulsifier with respect to 100 parts of a vinyl chloride-based paste resin Is 1.25 parts.

Specific examples of the ammonium salt emulsifier include an ammonium carboxylate emulsifier, an ammonium sulfate emulsifier and an ammonium sulfonate emulsifier.

Specific examples of the carboxylic acid ammonium salt-based emulsifier include, for example, caprylic acid, perlagonic acid,
Ammonium salts of saturated fatty acids having 10 to 20 carbon atoms such as capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid and arachinic acid; undecylenic acid, olein 10 carbon atoms such as acid, elaidic acid, linoleic acid, linolenic acid, stearic acid
Ammonium salts of unsaturated fatty acids having 20 to 20 carbon atoms; ammonium salts of fatty acids having 10 to 20 carbon atoms having a substituent such as hydroxylauric acid, dihydroxylauric acid, hydroxystearic acid, dihydroxystearic acid; adipic acid, pimelic acid, suberin Ammonium salts of dicarboxylic acids such as acid, azelaic acid and sebacic acid; benzoic acid,
Examples thereof include ammonium salts of aromatic carboxylic acids having 7 to 30 carbon atoms such as toluic acid, phenylacetic acid, phenylpropionic acid, and phenyllauric acid. In addition, general formula (I): R ¹ O (CH ₂ CH ₂ O) _n R ² COONH ₄ (I) (wherein, R ¹ is a monovalent hydrocarbon group having 8 to 30 carbon atoms, preferably a carbon number of 1 to 30) An alkyl group of 8 to 20, R ² has 1 carbon atom
To 30 divalent hydrocarbon groups, preferably 1 to 20 carbon atoms
Alkylene group or polymethylene group, n is 1 to 30)
And a compound represented by the general formula (II):

[0032]

Embedded image

(Wherein R ³ , R ⁴ and R ⁵ are a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² is A divalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms
20 alkylene groups or polymethylene groups, n is 1 to 3
0). These may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (I) include ammonium polyoxyethylene lauryl ether acetate, ammonium polyoxyethylene lauryl ether propionate, ammonium polyoxyethylene lauryl ether laurate, and polyoxyethylene nonyl. Examples thereof include ammonium ether acetate and polyoxyethylene oleyl ether ammonium acetate.

Specific examples of the compounds represented by the general formula (II) include, for example, ammonium polyoxyethylene phenyl ether acetate, ammonium polyoxyethylene phenyl ether propionate, ammonium polyoxyethylene octyl phenyl ether acetate, and polyoxyethylene octyl phenyl ether acetate. Ammonium ethylene dioctyl phenyl ether acetate, ammonium polyoxyethylene trioctyl phenyl ether acetate, ammonium polyoxyethylene nonyl phenyl ether acetate, ammonium polyoxyethylene dinonyl phenyl ether acetate, ammonium polyoxyethylene trinonyl phenyl ether acetate, polyoxyethylene octyl Carboxylic acids containing polyoxyethylene groups such as ammonium phenyl ether propionate Bromide, and the like.

Among the above-mentioned ammonium carboxylate emulsifiers, ammonium salts of fatty acids having 10 to 20 carbon atoms, especially ammonium salts of capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, and palmitic acid are exemplified. It is preferable from the viewpoint of providing a product having excellent polymerization stability and heat resistance. Further, the compound represented by the general formula (I) and the compound represented by the general formula (II) are also preferable from the viewpoint of giving a product excellent in polymerization stability and heat resistance. These may be used alone or in combination of two or more.

[0037] Examples of the ammonium salt emulsifier, for example, the general formula ^{(III): R 1 O (} CH 2 CH 2 O) n SO 3 NH 4 (III) ( In the formula, R ¹ 8 carbon atoms 30 monovalent hydrocarbon group, preferably an alkyl group having 8 to 20 carbon atoms, n is 1 to 30)
A compound represented by the general formula (IV):

[0038]

Embedded image

Wherein R ³ , R ⁴ and R ⁵ are a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n is 1 ~ 3
0). These may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (III) include ammonium polyoxyethylene decyl ether sulfate, polyoxyethylene lauryl ether ammonium sulfate, and polyoxyethylene oleyl ether ammonium sulfate.

Specific examples of the compound represented by the general formula (IV) include, for example, ammonium polyoxyethylene phenyl ether sulfate, ammonium polyoxyethylene octyl phenyl ether sulfate, ammonium polyoxyethylene dioctyl phenyl ether sulfate, and polyoxyethylene trioctyl. Examples include ammonium sulfate-based emulsifiers containing a polyoxyethylene group, such as ammonium phenyl ether sulfate, polyoxyethylene nonyl phenyl ether sulfate, ammonium polyoxyethylene dinonyl phenyl ether sulfate, and ammonium polyoxyethylene trinonyl phenyl ether sulfate. Examples of ammonium sulfate-based emulsifiers containing no polyoxyethylene group include ammonium alkyl sulfates having 8 to 20 carbon atoms such as ammonium decyl sulfate, ammonium lauryl sulfate, and ammonium myristyl sulfate; castor oil sulfate (rotating oil); And ammonium salts of natural oils and fats such as sulfates.

Specific examples of the above-mentioned ammonium sulfonate-based emulsifier include ammonium salts of alkylbenzenesulfonic acid having 8 to 30 carbon atoms, α-olefinsulfonic acid and alkanesulfonic acid. These are preferred from the viewpoint of providing a product having excellent polymerization stability and heat resistance. These may be used alone or in combination of two or more.

In the present invention, together with the ammonium salt-based emulsifier, a known nonionic emulsifier, an alkali metal emulsifier, or the like is used for mechanical stabilization of polymerization and polymerization latex, or for lowering the viscosity of plastisol with a vinyl chloride paste resin. A salt-based anionic emulsifier, polyethylene glycol or the like may be used. These may be added to the aqueous medium before the polymerization of the vinyl chloride paste resin, may be continuously added during the polymerization, or may be added to the latex after the polymerization.

Since the nonionic emulsifier generally does not contain a metal salt, it has little effect on heat resistance.

Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkenyl ether, polyoxyethylene derivative, glycerin fatty acid ester, sorbitan fatty acid ester, and the like.
Examples include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, silicone-based emulsifier, polyethylene glycol / polypropylene glycol copolymer, and polyethylene glycol derivative.
These may be used alone or in combination of two or more.

The amount of the nonionic emulsifier used is not particularly limited, but is preferably 0.3 parts or less, more preferably 0.1 part or less, per 100 parts of the vinyl chloride paste resin.
It is preferable from the viewpoint of heat resistance.

Examples of the alkali metal salt-based anionic emulsifier include fatty acid compounds, sulfuric acid compounds,
Anionic emulsifiers composed of alkali metal (sodium, potassium, etc.) salts such as sulfonic acid compounds, sulfosuccinic acid compounds, and phosphoric acid compounds can be mentioned. These may be used alone or in combination of two or more.

When the alkali metal salt-based anionic emulsifier is used, the amount used is preferably 0.3 parts or less, more preferably 0.1 parts or less, per 100 parts of the vinyl chloride paste resin. It is preferable because the influence on the property is small.

In the present invention, a dispersing aid may be used together with the emulsifier and the like for polymerization and mechanical stabilization of the polymerized latex.

In general, the dispersing aid is often added continuously before or during the polymerization of the vinyl chloride paste resin, but may be added to the latex after the polymerization.

Examples of the dispersing aid include higher alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol;
Examples include higher fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid. These may be used alone or in combination of two or more.

The vinyl chloride-based paste resin latex in the present invention uses the above-mentioned vinyl chloride-based monomer and the above-mentioned ammonium salt-based emulsifier, if necessary, other emulsifiers and dispersion aids used. It is manufactured by emulsion polymerization, seed emulsion polymerization, fine suspension polymerization, and the like.

Examples of the water-soluble initiator used in the emulsion polymerization and the seed emulsion polymerization include ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and the like. If necessary, sodium sulfite, sodium thiosulfate, etc. , Sodium formaldehyde sulfoxylate (Rongalit), ascorbic acid, sodium ascorbate and the like.

The oil-soluble initiator used in the fine suspension polymerization includes dilauroyl peroxide and di-
Diacyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate and di-2-ethylhexylperoxydicarbonate;
organic peroxide-based initiators such as peroxyesters such as t-butyl peroxypivalate and t-butyl peroxy neodecanoate; 2,2′-azobisisobutyronitrile, 2,2′- Azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-
Azo initiators such as 2,4-dimethylvaleronitrile).

The initiators may be used alone or in combination of two or more.

In the present invention, a polymer suspension stabilizer is further added to the vinyl chloride paste resin latex in order to improve the pulverization efficiency of the produced vinyl chloride paste resin. For example, a vinyl chloride paste resin obtained by spray-drying a latex of a vinyl chloride paste resin is pulverized as necessary,
By adding the polymer suspension stabilizer, effects such as an increase in the resin recovery rate in the pulverizing step can be obtained. As a result, the pulverized product can be efficiently produced, like the unpulverized granular product.

In the prior art, for example, Japanese Patent Application Laid-Open No. 6-3062
As described in JP-A No. 34, when an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide of about 0.4 to 0.8 equivalent of the ammonium emulsifier used is added to the latex after polymerization, The effect of improving the grinding efficiency is small. In addition, the heat resistance of the product deteriorates.

As described in Japanese Patent No. 2853387, an alkali metal (such as sodium and potassium) such as a sulfosuccinic compound, a fatty acid compound, a sulfuric acid compound and a sulfonic acid compound is added to the latex after polymerization. By incorporating a salt emulsifier, the pulverization efficiency may be improved, but these alkali metal salt-based emulsifiers are generally used unless 0.3 parts or more are added to 100 parts of the vinyl chloride-based monomer. No effect is observed. On the other hand, if the alkali metal salt-based emulsifier is added in an amount exceeding 0.3 parts, the heat resistance of the product will deteriorate.

When an antistatic agent such as a quaternary ammonium salt or imidazolinium betaine other than the above-mentioned alkali metal salt-based emulsifier is added, the heat resistance is often remarkably lowered, which is not preferable.

The content ratio of the polymer suspension stabilizer is 0.005 to 1.0 with respect to 100 parts of the vinyl chloride monomer.
Parts, more preferably 0.005 to 0.3 parts, especially 0.01
In the case of 0.2 parts, the pulverization efficiency can be improved while maintaining the heat resistance of the vinyl chloride-based paste resin product. When the polymer suspension stabilizer is a sodium salt or potassium salt compound, its content is 0.005 to 0.3 parts based on 100 parts of the vinyl chloride monomer.

As described above, in the polymerization of the vinyl chloride paste resin, the vinyl chloride monomer used generally accounts for 80 to 95% of the resin, and the remaining unreacted monomer is removed. Therefore, for example, vinyl chloride monomer 1
When 0.3 part of the polymer suspension stabilizer is contained with respect to 00 parts, when the polymerization addition rate is 80%, the content of the polymer suspension stabilizer with respect to 100 parts of the vinyl chloride paste resin is as follows: 0.375 parts.

When the content is less than 0.005 part, the above-mentioned improvement effect cannot be sufficiently obtained, and when the content is more than 1.0 part, there is a concern that the heat resistance may be adversely affected. The polymer suspension stabilizer often improves the pulverization efficiency with a smaller content than the alkali metal salt emulsifier and the antistatic agent. In general, a sufficient effect can be obtained by adding 0.2 parts by weight. .

The polymer suspension stabilizer may be added to the aqueous medium before the polymerization of the polyvinyl chloride paste resin, may be added continuously during the polymerization, or may be added to the latex after the polymerization. Although it may be added, it is most preferable to add it to the latex after polymerization. By adding the polymer suspension stabilizer after the polymerization, these are present in large amounts on the surface of the resin particles, and exhibit a great effect by improving the pulverization efficiency.
If the polymer suspension stabilizer is added before or during the polymerization, it will be taken into the inside of the product particles, so that to obtain the same effect as when it is added after the polymerization, it is necessary to increase the addition amount. In addition, when the polymer suspension stabilizer is present in the polymerization system, there is a fear that coalescence and aggregation of the produced particles may occur and scale may be generated.

Examples of the polymer suspension stabilizer include, for example, cellulose derivatives, proteins, vinyl polymers, vinyl copolymers, ammonium salts, sodium salts, potassium salts, polyvinyl alcohol and carboxylic acid-based polymers. Copolymers, carboxylic acid-based copolymers, ammonium salts, sodium salts, and potassium salts thereof, maleic anhydride-based polymers, maleic anhydride-based copolymers, and ammonium salts, sodium salts, and potassium salts thereof are used. These may be used alone or in combination of two or more.

Examples of the cellulose derivative include methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and the like.

As the above proteins, for example, casein, gelatin and the like are used.

Examples of the vinyl polymer and vinyl copolymer include polymers such as polyvinyl acetal, polyvinyl alcohol, polyvinyl isobutyl ether, polyvinyl ether, polyvinyl pyrrolidone, polyvinyl butyral, and styrene, and copolymers thereof. Can be These vinyl polymers and vinyl copolymers may be any one or more selected from the group consisting of ammonium salts, sodium salts and potassium salts. Of these, polyvinyl alcohol is preferred. As the polyvinyl alcohol, any of a completely saponified type, an intermediate saponified type, a partially saponified type, and a low saponified type may be used, but a partially saponified type easily soluble in water is preferable.

Examples of the carboxylic acid-based polymer and carboxylic acid-based copolymer include polymers such as maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, vinylbenzoic acid and vinylacetic acid, and copolymers of these. Is raised.
These carboxylic acid polymers, carboxylic acid copolymers,
At least one selected from the group consisting of ammonium salts, sodium salts, and potassium salts may be used. Among these, a maleic anhydride copolymer is preferred.

Examples of the maleic anhydride copolymer include:
For example, copolymers of maleic anhydride and vinyl compounds such as styrene, divinylbenzene, vinylanisole, vinylcyclohexane, and methylvinylether; maleic anhydride and ethylene such as isobutylene, diisobutylene, isoprene, hexene, octene, and butadiene. And a copolymer with a base compound. These maleic anhydride copolymers may be at least one selected from the group consisting of ammonium salts, sodium salts and potassium salts. Among these, a copolymer of maleic anhydride and styrene is particularly preferred. The copolymer of maleic anhydride and styrene is an ammonium salt,
At least one selected from the group consisting of sodium salts and potassium salts may be used.

The vinyl chloride paste resin thus obtained is used in an amount of 30 to 200 parts, more preferably 40 to 100 parts of a plasticizer per 100 parts of the vinyl chloride paste resin, and, if necessary, a stabilizer and a filler. , Reinforcing agents, diluents, thickeners, antioxidants, ultraviolet absorbers, foaming agents, flame retardants, antistatic agents, lubricants, pigments, surface treatment agents, thixotropic agents, adhesion promoters, fungicides, etc. In addition, the mixture is kneaded to form a paste sol, shaped by utilizing its fluidity, and then formed into a gel by heating.

The plasticizer is not particularly limited.
Examples of the primary plasticizer include phthalate plasticizers such as di-2-ethylhexyl phthalate, dinormal octyl phthalate, dibutyl phthalate, diisononyl phthalate, and butyl benzyl phthalate, tricresyl phosphate, and tri-2-ethylhexyl phosphate. Phosphate plasticizers, adipate plasticizers such as di-2-ethylhexyl adipate, di-2-
Sebacic ester plasticizers such as ethylhexyl sebacate, azelaic ester plasticizers such as di-2-ethylhexyl azelate, trimellitic ester plasticizers such as tri-2-ethylhexyl trimellitate, and polyester plasticizers , Di-2-ethylhexyl benzoate, diethylene glycol dibenzoate,
A benzoate plasticizer such as 2,2,4-trimethyl-1,3-pentanediol isobutyrate benzoate and a citrate plasticizer such as acetyltributyl citrate can be used. These may be used alone or in combination of two or more.
Further, a secondary plasticizer such as a glycolic acid ester plasticizer, a chlorinated paraffin plasticizer, a chlorinated fatty acid ester plasticizer, an epoxy plasticizer, or texanol isobutyrate may be used in combination. These secondary plasticizers may be used alone or in combination of two or more.

The gelled composition thus obtained can be used, for example, for wallpaper, floor cushion floor, floor carpet tile, ceiling, leather, canvas, steel plate, sealant, automobile interior material, automobile underbody coat, marking film, table It is used to provide products suitable for cloths, dolls, gloves, waterproof covering materials, insulating covering materials, medical supplies, cap seals, food models, and various other uses. In particular, the vinyl chloride paste resin of the present invention is suitably used for applications such as steel plates, insulating covering materials, top layers in floor cushion floors, marking films, wallpaper, ceiling materials, canvas and the like.

[0073]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

(Pulverization Efficiency) Using a spray drier (manufactured by Mitsubishi Kakoki Co., Ltd.), 1 kg of resin spray-dried at 135 ° C. at the inlet and 52 ° C. at the outlet was added to a bantam mill (AP-B).
Using a mold (manufactured by Hosokawa Micron Co., Ltd.) to determine the resin recovery.

Resin recovery = weight of resin after grinding / weight of resin before grinding (1 kg) × 100

(Viscosity of Paste Sol) To 100 parts of the crushed vinyl chloride resin, 57 parts of DINP (diisononyl phthalate), 3 parts of a Ba-Zn-based stabilizer, and 3 parts of epoxidized soybean oil were added and mixed until uniform. After that, the mixture was kneaded and defoamed at room temperature for 20 minutes using an Ishikawa crusher to prepare a paste sol.

The obtained paste sol was stored in a thermostat at 30 ° C. for 1 hour, and measured by a BM type viscometer (manufactured by TOKIMEC) with a rotor at 4 and 6 rpm.

(Heat resistance) The paste sol prepared for viscosity measurement was coated on a glass plate to a thickness of 250 μm, and was heated in a gear oven at 215 ° C. × 3 minutes or 215 ° C. × 8.
After heating for a minute, a gelled sheet was prepared.

The color tone of the obtained gelled sheet was
R AND COLOR DIFFERENCE ME
It was measured with TER MODEL Z-1001DP (manufactured by Nippon Denshoku Co., Ltd.).

Further, the heating time was increased at 215 ° C., and the time until the sheet turned black was measured.

The determination of heat resistance was such that the b value at 215 ° C. × 3 minutes was 2.0 or less, the b value at 215 ° C. × 8 minutes was 5.0 or less, and the blackening time was 20 minutes or more. Those that did not satisfy any one of these criteria were rejected.

Production Example 1 In a pressure vessel equipped with a stainless steel stirrer, 15
0 parts, 0.5 parts of ammonium laurate, 0.3 parts of lauryl alcohol and 0.05 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were charged and degassed, and then 100 parts of vinyl chloride monomer was added. , And homogenized. Then, the temperature was raised to 50 ° C. to carry out polymerization, and when the polymerization pressure dropped, unreacted monomers were removed to terminate the polymerization. The polymerization addition rate was 90%.

Production Example 2 In Production Example 1, instead of ammonium laurate,
Polymerization was carried out in the same manner using 0.5 part of sodium lauryl sulfate. The polymerization addition rate was 92%.

Production Example 3 150 ion-exchanged water was placed in a pressure vessel with a stainless steel stirrer.
Parts, ammonium polyoxyethylene dinonylphenyl ether sulfate 0.03 part, sodium formaldehyde sulfoxylate (Rongalit) 0.03 part, ferrous sulfate 0.0003 part, and hydrochloric acid 0.003 part were charged and degassed. Thereafter, 100 parts of a vinyl chloride monomer was fed. With stirring, the temperature was raised to 50 ° C., and 0.01 parts of hydrogen peroxide equivalent to pure hydrogen peroxide and 0.27 parts of ammonium polyoxyethylene dinonylphenyl ether sulfate were continuously added to lower the polymerization pressure. At this point, unreacted monomer was removed to terminate the polymerization. The polymerization addition rate was 90%.

Production Example 4 In Production Example 3, the initial addition amount of polyoxyethylene dinonyl phenyl ether ammonium sulfate was 0.01
The polymerization was carried out in the same manner with the addition of 0.29 parts by weight. The polymerization addition rate was 90%.

Production Example 5 In Production Example 3, the initial addition amount of ammonium polyoxyethylene dinonylphenyl ether sulfate was 0.003.
The polymerization was carried out in the same manner with the addition of 0.297 parts by weight. The polymerization addition rate was 91%.

Production Example 6 150 ion-exchanged water was placed in a pressure vessel with a stainless steel stirrer.
Parts, an amount containing 3 parts of the seed latex obtained in Production Example 4 as a solid content, 0.02 part of ammonium myristate,
After 0.03 parts of sodium sulfite and 0.0003 parts of copper sulfate were charged and deaerated, 100 parts of a vinyl chloride monomer was fed. While stirring, the temperature was raised to 50 ° C., 0.01 parts of ammonium persulfate and 0.48 parts of ammonium myristate were continuously added, and when the polymerization pressure was lowered, unreacted monomers were removed to terminate the polymerization. . The polymerization addition rate was 90%.

Production Example 7 150 ion-exchanged water was placed in a pressure vessel with a stainless steel stirrer.
And 2 parts by weight of the seed latex obtained in Production Example 3 as solids, 0.02 part of ammonium polyoxyethylene dinonylphenyl ether sulfate, 0.03 part of sodium sulfite, and 0.0003 part of copper sulfate. After that, 100 parts of a vinyl chloride monomer were fed. While stirring, the temperature was raised to 50 ° C.
One part and 0.48 parts of polyoxyethylene dinonylphenyl ether ammonium sulfate were continuously added, and when the polymerization pressure was lowered, unreacted monomers were removed to terminate the polymerization. The polymerization addition rate was 92%.

Production Example 8 Polymerization was carried out in the same manner as in Production Example 7, except that ammonium polyoxyethylene lauryl ether sulfate was used instead of ammonium polyoxyethylene dinonylphenyl ether sulfate as the initially charged and continuously added emulsifier. The polymerization addition rate was 89%.

Production Example 9 Polymerization was carried out in the same manner as in Production Example 7 except that ammonium polyoxyethylene lauryl ether acetate was used instead of ammonium polyoxyethylene dinonylphenyl ether sulfate as the initially charged and continuously added emulsifier. The polymerization addition rate was 90%.

Production Example 10 Polymerization was carried out in the same manner as in Production Example 7, except that sodium laurate was used instead of ammonium polyoxyethylene dinonyl phenyl ether sulfate as the initially charged and continuously added emulsifier. The polymerization addition rate was 91%.

Comparative Example 1 The latex obtained in Production Example 1 was spray-dried using a spray dryer (manufactured by Mitsubishi Kakoki Co., Ltd.) at 135 ° C. inlet and 52 ° C. outlet. 1 kg of the spray-dried resin was pulverized with a bantam mill (AP-B type, manufactured by Hosokawa Micron Corporation) to determine the resin recovery. In addition, the viscosity and heat resistance of this resin were evaluated and judged. Table 1 shows the results.

Example 1 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 1.
Sodium salt of styrene / anhydrous maleic 1/1 copolymer per 100 parts (trade name: SMA1000H, Elf
Spray drying was performed by adding 0.05 parts of Atochem (product of Elf Atochem) as a pure component, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 1 shows the results.

Comparative Example 2 The latex obtained in Production Example 2 was spray-dried.
The same evaluation and judgment as described above were performed. Table 1 shows the results.

Comparative Example 3 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 5.
The polyoxyalkylene / polydimethylsiloxane copolymer (trade name: FZ2105, manufactured by Nippon Unicar Co., Ltd.) was added in an amount of 0.05 part per 100 parts by weight and spray-dried. A decision was made. Table 1 shows the results.

Example 2 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 5.
Spray drying was carried out by adding 0.05 parts of FZ2105 as a pure component and 0.05 parts of SMA1000H as a pure component per 00 parts, and evaluated in the same manner as Comparative Example 1.
A decision was made. Table 1 shows the results.

[0097]

[Table 1]

Comparative Example 4 The latex obtained in Production Example 6 was spray-dried.
The same evaluation and judgment as described above were performed. Table 2 shows the results.

Comparative Example 5 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
Spray drying was performed by adding 0.05 parts of sodium hydroxide per 00 parts, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 2 shows the results.

Comparative Example 6 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
Per 100 parts of sodium di-2-ethylhexylsulfosuccinate (trade name: Lapisol A-80, NOF Corporation)
Was added as a pure component in an amount equivalent to 0.3 parts and spray-dried, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 2 shows the results.

Comparative Example 7 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
Spray drying was performed by adding 0.3 part of sodium lauryl sulfate per 00 parts, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 2 shows the results.

Comparative Example 8 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
A modified aliphatic dimethylethylammonium ethosulfate (trade name: Elegan 264-WAX, manufactured by NOF CORPORATION), which is effective as an antistatic agent per 00 parts, is added in an amount equivalent to 0.3 part as a pure component, and spray drying is performed. The same evaluation and judgment as in Comparative Example 1 were performed. Table 2 shows the results.

[0103]

[Table 2]

Examples 3 and 4 The latex obtained in Production Example 6 was added to the vinyl chloride monomer 1
Spray drying was carried out by adding 0.02 parts equivalent and 0.2 parts equivalent of SMA1000H as pure components per 00 parts, respectively, and the same evaluation and judgment as in Comparative Example 1 were performed.
Table 3 shows the results.

Examples 5 to 6 The latex obtained in Production Example 6 was added to a vinyl chloride monomer 1
An ester type ammonium salt of a styrene / anhydrous maleic 1/1 copolymer per 100 parts (trade name: SMA1
440H, manufactured by Elf Atochem Co., Ltd.) were spray-dried by adding 0.05 parts and 0.3 parts of pure components, respectively, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 3 shows the results.

Example 7 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
Sodium salt of styrene / anhydrous maleic 3/1 copolymer per 100 parts (trade name: SMA3000H, Elf
(Atochem Co., Ltd.) was added as a pure component in an amount of 0.05 part and spray-dried, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 3 shows the results.

[0107]

[Table 3]

Example 8 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
A sodium salt of a maleic anhydride / diisobutylene copolymer (trade name: POLYSTAR OM, manufactured by NOF CORPORATION) was added as a pure component in an amount of 0.05 part per 00 parts, and spray drying was performed. The same evaluation and judgment as in Example 1 were performed. Table 4 shows the results.

Example 9 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
A spray drying was carried out by adding an equivalent amount of 0.05 part of an ammonium salt of a maleic anhydride / diisobutylene copolymer (trade name: Polystar OMA, manufactured by NOF CORPORATION) per 00 parts as a pure component, and spray-drying. The same evaluation and judgment as in Example 1 were performed. Table 4 shows the results.

Example 10 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
A maleic anhydride / styrene copolymer having a polyoxylene alkylene group per 00 parts (trade name: Marialim HK)
M-50A, manufactured by NOF Corporation)
And spray drying was carried out with the addition of an equivalent amount, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 4 shows the results.

Example 11 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
Spray-drying was carried out by adding an equivalent of 0.05 part of a copolymer of methoxyethylene maleic anhydride (trade name: GANTREZ AN-139, manufactured by Gokyo Sangyo Co., Ltd.) per 100 parts as pure matter, and spray-drying. The same evaluation and judgment as described above were performed. Table 4 shows the results.

Example 12 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 6.
Hydroxypropyl methylcellulose (trade name: Metroose 60SH-50, manufactured by Shin-Etsu Chemical Co., Ltd.) was added in an amount of 0.05 part per 100 parts as a pure component, spray-dried, and evaluated and determined in the same manner as in Comparative Example 1. Was performed. Table 4 shows the results.

[0113]

[Table 4]

Examples 13 to 14 The latex obtained in Production Example 6 was added to a vinyl chloride monomer 1
Per 100 parts of partially saponified polyvinyl alcohol (trade name: Gohsenol GM-14, Nippon Synthetic Chemical Industry Co., Ltd.)
) As pure components, respectively.
One part equivalent was added and spray drying was performed, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 5 shows the results.

Examples 15 to 16 The latex obtained in Production Example 6 was added to a vinyl chloride monomer 1
Spray drying was performed by adding 0.05 parts and 0.1 parts of partially saponified polyvinyl alcohol (trade name: Kuraray Poval PVA-217, manufactured by Kuraray Co., Ltd.) per 00 parts, and evaluated in the same manner as Comparative Example 1. A decision was made. Table 5 shows the results.

Example 17 A vinyl chloride monomer 1 was added to the latex obtained in Production Example 8.
Comparative Example 1 was spray-dried by adding an equivalent of 0.1 part of Kuraray Povar PVA-217 per 100 parts as a pure component.
The same evaluation and judgment as described above were performed. Table 5 shows the results.

[0117]

[Table 5]

Comparative Examples 9 to 12 The latexes obtained in Production Examples 7 to 10 were each spray-dried, and evaluated and evaluated in the same manner as in Comparative Example 1. Table 6 shows the results.

[0119]

[Table 6]

Examples 18 to 20 The latexes obtained in Production Examples 7 to 9 were added to SMA 1000H per 100 parts of vinyl chloride monomer, respectively.
Was added as a pure component in an amount equivalent to 0.05 part, spray drying was performed, and the same evaluation and judgment as in Comparative Example 1 were performed. Table 7 shows the results.

[0121]

[Table 7]

[0122]

By using an ammonium salt emulsifier and containing a polymer suspension stabilizer, a product having excellent heat resistance can be obtained, the pulverization efficiency is improved, and the resin recovery rate is increased. .

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinji Inoue 2-13-13-101 Mishima, Settsu-shi, Osaka Person Nobori Toba 40-7 Tamase-cho, Ibaraki-shi, Osaka F-term (reference) 4J011 AA05 DA01 EA07 KA03 KA15 KA16 NA01 NA04 4J100 AA02Q AA03Q AA04Q AB02Q AB03Q AB16Q AC03P AC04Q AE02Q AE03Q03 A04QAQAQQAE03 CA04 DA22 DA62 FA20 JA67

Claims (17)

[Claims] 1. A latex of a vinyl chloride paste resin obtained by polymerizing a vinyl chloride monomer using an ammonium salt emulsifier, wherein 100 parts by weight of the vinyl chloride monomer is mixed with an ammonium salt emulsifier. A vinyl chloride paste resin from a latex containing 0.1 to 5.0 parts by weight and 0.005 to 1.0 parts by weight of a polymer suspension stabilizer. 2. The vinyl chloride paste resin according to claim 1, wherein the polymer suspension stabilizer is contained in an amount of 0.005 to 0.3 parts by weight based on 100 parts by weight of the vinyl chloride monomer. 3. The vinyl chloride paste resin according to claim 1, wherein the polymer suspension stabilizer is contained in an amount of 0.01 to 0.2 part by weight based on 100 parts by weight of the vinyl chloride monomer. 4. The vinyl chloride paste resin according to claim 1, wherein a polymer suspension stabilizer is added to the latex of the vinyl chloride paste resin after polymerization. 5. The ammonium salt emulsifier is at least one selected from the group consisting of ammonium carboxylate emulsifier, ammonium sulfate emulsifier and ammonium sulfonate emulsifier. The vinyl chloride paste resin as described in the above. 6. An ammonium salt-based emulsifier comprising 10 carbon atoms.
Claims 1, 2, 3, which are ammonium fatty acids of up to 20.
6. The vinyl chloride paste resin according to 4 or 5. 7. An ammonium salt-based emulsifier having the general formula (I): R ¹ O (CH ₂ CH ₂ O) _n R ² COONH ₄ (I) (wherein, R ¹ is a monovalent having 8 to 30 carbon atoms) A hydrocarbon group of R ²
Is a divalent hydrocarbon group having 1 to 30 carbon atoms, and n is 1 to 30)
And a compound represented by the general formula (II): (Wherein, R ³ , R ⁴ , and R ⁵ represent a hydrogen atom or a carbon atom
A monovalent hydrocarbon group of 30; R ² is a monovalent hydrocarbon group having 1 to 30 carbon atoms;
A monovalent hydrocarbon group, wherein n is at least one member selected from the group consisting of compounds represented by 1 to 30).
A vinyl chloride paste resin according to 2, 3, 4 or 5. 8. An ammonium salt-based emulsifier having the general formula (II)
I): R ¹ O (CH ₂ CH ₂ O) _n SO ₃ NH ₄ (III) (wherein, R ¹ is a monovalent hydrocarbon group having 8 to 30 carbon atoms, n
Is a compound represented by 1 to 30) and a general formula (IV): (Wherein, R ³ , R ⁴ , and R ⁵ represent a hydrogen atom or a carbon atom
The vinyl chloride paste resin according to claim 1, 2, 3, 4, or 5, wherein 30 monovalent hydrocarbon groups and n is at least one selected from the group consisting of compounds represented by 1 to 30). 9. The polymer suspension stabilizer is at least one selected from the group consisting of vinyl polymers, vinyl copolymers, and ammonium salts thereof.
The vinyl chloride paste resin described in 3, 4, 5, 6, 7 or 8. 10. The vinyl chloride paste resin according to claim 1, wherein the polymer suspension stabilizer is polyvinyl alcohol. 11. The vinyl chloride paste resin according to claim 1, wherein the polymer suspension stabilizer is a cellulose derivative. 12. The polymer suspension stabilizer is at least one selected from the group consisting of carboxylic acid polymers, carboxylic acid copolymers, and ammonium salts thereof. The vinyl chloride paste resin described in 4, 5, 6, 7, or 8. 13. The polymer suspension stabilizer is at least one selected from the group consisting of a maleic anhydride polymer, a maleic anhydride copolymer, and an ammonium salt thereof. The vinyl chloride paste resin described in 3, 4, 5, 6, 7, or 8. 14. The polymer-based suspension stabilizer is at least one selected from the group consisting of a copolymer of maleic anhydride and styrene, and ammonium salts thereof.
The vinyl chloride paste resin described in 2, 3, 4, 5, 6, 7, or 8. 15. The polymer suspension stabilizer is a vinyl polymer, a vinyl copolymer, a carboxylic acid polymer, a carboxylic acid copolymer, a maleic anhydride polymer, or a maleic anhydride copolymer. 9. The vinyl chloride according to claim 2, which is at least one selected from the group consisting of a polymer, a sodium salt and a potassium salt of a copolymer of maleic anhydride and styrene. Based paste resin. 16. The method of claim 1, 2, 3, 4, 5, 7, 8,
A paste sol composition using the vinyl chloride paste resin described in 9, 10, 11, 12, 13, 14, or 15. 17. The method of claim 1, 2, 3, 4, 5, 7, 8,
A gel composition using the vinyl chloride paste resin according to 9, 10, 11, 12, 13, 14, or 15.