JP5272356B2 - Vinyl chloride resin for paste processing, method for producing the same, and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paste vinyl chloride having high whiteness in the foam processing of the paste vinyl chloride, excellent foaming property and sol viscosity characteristics and suppressed change over time so as to obtain a foamed body constantly having stable whiteness, and to provide a method of producing the same and a paste vinyl chloride sol and a foamed molding using the same. <P>SOLUTION: The vinyl chloride based resin for paste processing is provided which contains at least one of a compound expressed by following general formula (1) and a compound expressed by following general formula (2) and the method of producing the same is also provided, wherein general formula (1) is M<SB>2</SB>SO<SB>3</SB>(where, M expresses one or more kinds selected from alkali metals) and general formula (2) is M<SB>2</SB>S<SB>2</SB>O<SB>3</SB>(where, M expresses one or more kinds selected from alkali metals). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a vinyl chloride resin for paste processing and a method for producing the same.

  A vinyl chloride resin for paste processing (hereinafter abbreviated as “paste vinyl chloride”) is kneaded with compounding agents such as a plasticizer, a stabilizer, a filler, and a foaming agent to form a vinyl chloride sol for paste processing. The composition (hereinafter abbreviated as a paste vinyl chloride sol) is used for processing, and various molded products such as foamed molded articles are obtained by various processing methods. Among them, the molded foam is toned and used for building materials such as wallpaper and flooring. For the foamed molded product before toning, a paste PVC capable of obtaining a foamed molded product with a high whiteness is desired because the toned product is easy to color or the foamed molded product user prefers many white products. ing.

  Paste vinyl chloride is a polymer of vinyl chloride monomer alone or a mixture of vinyl monomer and vinyl chloride monomer copolymerizable with vinyl chloride monomer (hereinafter referred to as vinyl chloride monomer). In general, an emulsion polymerization method using an emulsifier and a water-soluble initiator, or a homogenization treatment in the presence of a dispersion aid such as an emulsifier and a higher alcohol and an oil-soluble initiator, followed by a gentle It is obtained by producing a paste PVC latex by a fine suspension polymerization method in which polymerization is carried out under stirring, and drying this.

  Paste vinyl chloride is produced by the method as described above. Therefore, paste vinyl chloride contains many additives such as emulsifiers and modifiers used for polymerization in addition to the vinyl chloride resin component. Contains many impurities such as by-products. Additives and the like contained in these paste PVCs have a great influence on the sol physical properties of paste PVC typified by viscosity, the physical properties of finished products, and the finish.

  For example, alkylbenzenesulfonic acid or a salt thereof used as an emulsifier in the emulsion polymerization or fine suspension polymerization process includes a sulfonic acid of alkyltetralins and alkylindanes or a salt thereof as a by-product. These undergo a radical attack in the polymerization process to produce a colored precursor, which deteriorates the color stability of the resin product. Thus, as a method for obtaining a good resin, it has been proposed to use an emulsifier in which the by-product contained in the emulsifier is 5% by weight or less (Patent Document 1).

  However, in this method, the sulfonic acid or salt of alkyltetralins and alkylindanes contained as a by-product in the emulsifier to be used must be 5% by weight or less, and a substance capable of forming a colored precursor and its concentration In addition to the problem of always having to manage, it is necessary to purify and remove the colored precursors from the raw materials, which increases the cost and uses emulsifiers with low precursor content. The paste PVC obtained in this way had problems such as an increase in sol viscosity.

JP-A-8-169910

  The present invention solves the above-described conventional problems, and when foaming paste PVC, a foam having high whiteness, excellent foamability and sol viscosity characteristics, and always having stable whiteness is obtained. It is an object of the present invention to provide a paste PVC whose change with time is suppressed, a method for producing the same, a paste PVC sol using the same, and a foamed molded article.

  When foaming, the inventors have improved the temporal stability of the resin during storage so that a foam having high whiteness, excellent foamability and sol viscosity characteristics, and always having a stable whiteness can be obtained. As a result of diligent investigation on excellent paste PVC, even paste paste containing colored precursors is specified so that it does not generate color-causing substances due to oxidation reaction of colored precursors during long-term storage after paste PVC production The present inventors have found that the above-mentioned problems can be solved by uniformly presenting the reducing substance in the resin. That is, the present invention contains 100 to 3000 ppm of at least one compound represented by the following general formula (1) and the following general formula (2), and a vinyl chloride resin for paste processing, and its production Is the method.

M ₂ SO ₃ (1)
(However, M represents one or more selected from alkali metals.)
M ₂ S ₂ O ₃ (2)
(However, M represents one or more selected from alkali metals.)
The present invention is described in detail below.

  The vinyl chloride resin for paste processing of the present invention contains 100 to 3000 ppm of at least one compound represented by the following general formula (1) and the following general formula (2).

M ₂ SO ₃ (1)
(However, M represents one or more selected from alkali metals.)
M ₂ S ₂ O ₃ (2)
(However, M represents one or more selected from alkali metals.)
Here, examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium.

  The content of at least one of the compounds represented by the general formula (1) and the general formula (2) needs to be 100 to 3000 ppm. When the content is less than 100 ppm, the aging stability of the resin during storage is not improved. On the other hand, when it exceeds 3000 ppm, the aging stability of the resin during storage is improved, but the foaming property is deteriorated. In order to obtain a paste PVC with high whiteness, excellent foamability and sol viscosity characteristics, and excellent stability over time of the resin during storage so that a foam having always stable whiteness can be obtained. Is preferably 300 to 1500 ppm.

  As a method for producing the paste PVC of the present invention, at least one compound represented by the following general formula (1) and the following general formula (2) is added to a vinyl chloride resin latex obtained by polymerization. Addition of 0.01 to 0.3 parts by weight with respect to 100 parts by weight, followed by spray drying and pulverization. When the addition amount is less than 0.01 parts by weight, the aging stability of the resin during storage is not improved, while when it exceeds 0.3 parts by weight, the aging stability of the resin during storage is improved. However, the foaming property deteriorates. In order to obtain a paste PVC with high whiteness, excellent foamability and sol viscosity characteristics, and excellent stability over time of the resin during storage so that a foam having always stable whiteness can be obtained. Is preferably 0.03 to 0.15 parts by weight.

M ₂ SO ₃ (1)
(However, M represents one or more selected from alkali metals.)
M ₂ S ₂ O ₃ (2)
(However, M represents one or more selected from alkali metals.)
The above general formula (1) and general formula (2) may be added directly to the latex or added as an aqueous solution, and any method can be used as long as it is uniformly added to the latex.

  As a polymerization method for obtaining a vinyl chloride resin latex, any polymerization method can be used. As the most general method, a vinyl chloride monomer is aqueous in the presence of an emulsifier and a water-soluble polymerization initiator. Emulsion polymerization method that performs polymerization in a medium under mild stirring conditions, seed emulsion polymerization method that performs emulsion polymerization using particles obtained by emulsion polymerization method as seeds, vinyl chloride monomer as emulsifier, oil-soluble polymerization It is obtained by microsuspension polymerization method or microsuspension polymerization method in which polymerization is carried out under mild stirring conditions after mixing and dispersing in an aqueous medium in the presence of an initiator and, if necessary, an emulsification aid, with a homogenizer. Polymerization is carried out at a polymerization temperature of 30 to 80 ° C. by a seed micro-suspension polymerization method in which a seed containing an oil-soluble polymerization initiator is used to obtain a vinyl chloride resin latex. It is.

  At least one of the compounds represented by the above general formula (1) and the above general formula (2) is added to the latex obtained after the polymerization, sufficiently stirred, and dried to be adsorbed on the surface of the paste vinyl chloride resin. When the paste PVC sol made of the paste PVC is foamed, it has high whiteness, excellent foamability and sol viscosity characteristics, and even after long-term storage of the paste PVC. It is possible to obtain a paste PVC that gives a foamed molded article having a stable quality.

  The vinyl chloride monomer used when producing the paste vinyl chloride of the present invention is a vinyl chloride monomer alone or a vinyl monomer copolymerizable with a vinyl chloride monomer and a vinyl chloride monomer. And a mixture. Examples of vinyl monomers that can be copolymerized with vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl benzoate; acrylic acid, methacrylic acid, maleic acid, fumarate Unsaturated carboxylic acids such as acids or their anhydrides; esters of acrylic acid such as methyl, ethyl, and butyl; esters of methyl methacrylate such as methyl, ethyl, and butyl; maleic acid esters, fumaric acid esters, and cinnamic acid esters Unsaturated carboxylic acid esters; vinyl ethers such as vinyl methyl ether, vinyl amyl ether, vinyl phenyl ether; monoolefins such as ethylene, propylene, butene, pentene; vinylidene chloride, styrene and its derivatives, acrylonitrile, methacrylonitrile Vinyl chloride and radicals such as Can be mentioned ordinary vinyl compound may be polymerized, they may be used even more.

  Examples of the emulsifier used in producing the paste vinyl chloride of the present invention include alkyl sulfates such as sodium lauryl sulfate and myristyl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate. Anionic surfactants such as sodium succinates such as sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate, fatty acid salts such as ammonium laurate and potassium stearate, polyoxyethylene alkyl sulfates and polyoxyethylene alkylaryl sulfates Agents, sorbitan esters such as sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene alkyl pheny Ethers, those conventionally known, such as nonionic surfactants such as polyoxyethylene alkyl esters can be used one or more kinds.

  If the polymerization initiator used in producing the paste vinyl chloride of the present invention is an emulsion polymerization system, it is usually a water-soluble initiator such as potassium persulfate or ammonium persulfate used in these polymerizations, a micro suspension polymerization method. Or if it is a seed polymerization method, an azo compound represented by azobisisobutyronitrile, lauroyl peroxide, t-butylperoxypivalate, an oil-soluble initiator such as diacyl peroxide, peroxyester, peroxydicarbonate, etc. Can be mentioned.

  Specific examples of the emulsification aid used as necessary when producing the paste PVC of the present invention include higher alcohols such as cetyl alcohol and lauryl alcohol, higher fatty acids such as lauric acid, palmitic acid and stearic acid. Or the ester, aromatic hydrocarbon, higher fatty acid hydrocarbon, halogenated hydrocarbon like a chlorinated paraffin, etc. are mentioned.

  The aqueous medium used in the present invention is water, a surfactant, or other water-soluble polymerization aid (buffering agent, etc.), which is a medium in which an organic layer such as a vinyl chloride monomer is dispersed. .

  As a method for obtaining paste vinyl chloride from the vinyl chloride resin latex, any method may be used, but a method by spray drying is preferable because water can be efficiently removed from the latex. The dryer used for spray drying may be a commonly used one. For example, “SPRAY DAYING HANDBOOK” (K. Masters, 3rd edition, 1979, published by George Godwin Limited), page 121, item 4. There are various spray dryers described in FIG. The drying temperature is generally 80 to 200 ° C. at the inlet of the dryer and 40 to 70 ° C., preferably 45 to 65 ° C. at the outlet. After drying, the obtained paste vinyl chloride is an aggregate of particles constituting the vinyl chloride resin latex and is usually in the form of granules of 10 to 150 μm. When the drying outlet temperature exceeds 52 ° C, it is preferable to pulverize the obtained granular paste PVC from the viewpoint of dispersibility in a plasticizer. If the drying outlet temperature is 52 ° C or lower, it remains granular. However, it may be used after being crushed.

  Paste PVC obtained by the above method has excellent long-term storage stability, and paste PVC sols containing plasticizers, stabilizers, fillers, foaming agents, etc. have excellent sol viscosity characteristics. The foam made from is high in whiteness and excellent in foamability.

  The plasticizer, stabilizer, filler, and foaming agent blended to form such a paste vinyl chloride sol are not particularly limited as long as they are used in conventional paste foaming blending. Preferably, 30 to 300 parts by weight of a plasticizer, 1 to 5 parts by weight of a stabilizer, 10 to 500 parts by weight of a filler, and 20 parts by weight or less of a foaming agent are blended with 100 parts by weight of a paste vinyl chloride.

  As for the plasticizer used, phthalate plasticizers such as dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, di-2-adipate Fatty acid ester plasticizers such as ethylhexyl, di-n-octyl adipate, diisononyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate, tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, Phosphate ester plasticizers such as octyl diphenyl phosphate, trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitic acid, triisodecyl trimellitic acid, other polyester-based, epoxy-based plasticizers and mixtures thereof Can be used. For the stabilizer, barium-zinc, barium-zinc-tin, zinc, tin, calcium-zinc and mixtures thereof can be used. As the filler, calcium carbonate, lithium carbonate, calcium silicate, clay, talc, silica, and mixtures thereof can be used. As the foaming agent, an azo-based, sulfonyl hydrazide-based or nitroso-based foaming agent typified by azodicarbonamide can be suitably used.

  A foam-molded article can be obtained by coating the above paste vinyl chloride sol on a flame-retardant paper and heating. This foam molded article can be used for applications such as wallpaper.

  When the vinyl chloride resin composition for paste processing is foamed, the paste PVC of the present invention provides a foam having high whiteness, excellent foamability and sol viscosity characteristics, and always having stable whiteness. Thus, since the time-dependent change of paste PVC is suppressed, its industrial value is extremely high.

  Examples The present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Synthesis Example 1 (Production Example of Sodium Alkylbenzenesulfonate)
101 g of sulfuric anhydride was added to 300 g of alkylbenzene containing alkylbenzene (dodecylbenzene) having an alkyl chain length of 12 as a main component, and sulfonation was performed while stirring at 30 ° C. in a flask. Thereafter, 46 g of sodium hydroxide and 405 g of deionized water were added and neutralized to obtain sodium alkylbenzenesulfonate (ABS1).

The phosphoric acid decomposition method (Kitahara et al.) Which analyzes the content of the sulfonic acid or its salt of alkyltetralins and alkylindanes in the obtained ABS1 by pyrolysis with phosphoric acid and then gas chromatography analysis Based on “surfactant analysis and test method” (Kodansha) P225), measurement was performed under the conditions of column temperature: 180 ° C., inlet, detector temperature: 270 ° C., carrier gas: nitrogen 1.8 kg / cm ² . However, it was 11.4% by weight.

Synthesis Example 2 (Production example of purified sodium alkylbenzene sulfonate)
Into a 1 L Claisen flask equipped with a fractionating tube, 500 g of alkylbenzene mainly composed of alkylbenzene having an alkyl chain length of 12 (dodecylbenzene) was added, and the pressure was reduced to 1 mmHg with a vacuum pump. Next, the Claisen flask was heated in an oil bath at about 80 ° C., and 60 to 65 ° C. was recovered as a fraction, and alkylbenzene was purified by distillation under reduced pressure.

  The alkylbenzene obtained by distillation purification was sulfonated and neutralized in the same manner as in Synthesis Example 1 to obtain purified sodium alkylbenzenesulfonate (ABS2).

  The content of the sulfonic acid or salt of alkyltetralins and alkylindanes in the obtained ABS2 was measured by the same method as in Synthesis Example 1 and found to be 1.8% by weight.

Synthesis example 3 (production example of seed containing initiator, etc.)
A 2.5 L autoclave was charged with 900 g of deionized water, 750 g of vinyl chloride monomer, 15 g of lauroyl peroxide and 75 g of 15 wt% ABS1 aqueous solution, and the polymerization solution was circulated for 2 hours using a homogenizer. The temperature was raised to 45 ° C. to proceed the polymerization. After the pressure of 0.2 MPa decreased from the saturated vapor pressure of vinyl chloride at 45 ° C., unreacted vinyl chloride monomer was recovered. The obtained initiator-containing seed latex (hereinafter abbreviated as seed 1) had an average particle size of 0.60 μm and a solid content concentration of 32%.

Synthesis Example 4 (Production example of initiator-containing seed)
An initiator-containing seed latex (hereinafter abbreviated as seed 2) was obtained in the same manner as in Synthesis Example 3 except that ABS1 was changed to ABS2.

Synthesis Example 5 (Example of production of seed not containing monomer-soluble polymerization initiator)
In a 2.5 L autoclave, 800 g of deionized water, 700 g of vinyl chloride monomer, 4 g of 16 wt% potassium laurate aqueous solution and 10 g of 16 wt% ABS 1 aqueous solution were charged, and the temperature was raised to 54 ° C. to proceed the polymerization. After the pressure of 0.3 MPa was lowered from the saturated vapor pressure of vinyl chloride at 54 ° C., unreacted vinyl chloride monomer was recovered. The obtained seed latex containing no monomer-soluble polymerization initiator (hereinafter abbreviated as seed 3) had an average particle size of 0.15 μm and a solid content concentration of 35%.

Synthesis Example 6 (Example of producing seed not containing monomer-soluble polymerization initiator)
A seed latex containing no monomer-soluble polymerization initiator (hereinafter abbreviated as seed 4) was obtained in the same manner as in Synthesis Example 5 except that ABS1 was changed to ABS2.

Example 1
In a 2.5 L autoclave, 650 g of deionized water, 750 g of vinyl chloride monomer, 4 g of 20 wt% ABS1 aqueous solution, 29.3 g of seed 1 (3.9 wt% with respect to the vinyl chloride monomer), and seed 3 27.0 g (3.6% by weight based on the vinyl chloride monomer) was charged, and the temperature of the reaction mixture was raised to 64 ° C. to initiate polymerization. From the start of polymerization to the end of polymerization, 26.3 g of 20 wt% ABS1 aqueous solution (0.7 wt% with respect to vinyl chloride monomer) was continuously added to the vinyl chloride monomer. The polymerization was stopped when the polymerization pressure dropped 0.6 MPa from the saturated vapor pressure of the vinyl chloride monomer at 64 ° C. Thereafter, unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin latex having a solid content concentration of 43%. 0.015 parts by weight of Na ₂ SO ₃ is added to 100 parts by weight of the solid content of the obtained vinyl chloride resin latex, and after sufficiently stirring so that Na ₂ SO ₃ is uniform in the vinyl chloride latex, a spray dryer Then, spray drying was performed at a hot air inlet of 190 ° C and an outlet temperature of 63 ° C. Thereafter, pulverization was performed to obtain paste vinyl chloride (Na ₂ SO ₃ content: 150 ppm).

The obtained paste PVC was evaluated for sol viscosity by the following measurement method. Further, the obtained paste vinyl chloride is 55 parts by weight of di-2-ethylhexyl phthalate (manufactured by J-Plus) as a plasticizer and 55 parts by weight of CaCO ₃ (manufactured by Shiroishi Kogyo, Whiten H), 3 parts by weight of a stabilizer (manufactured by Kyodo Yakuhin, trade name KF65-J2), 5 parts by weight of a foaming agent (manufactured by Eiwa Chemical Co., Ltd., trade name AC1C), 12 parts by weight of a pigment (manufactured by Teika, JR-600A), A sol was prepared by adding 5 parts by weight of a diluent (Exxon Mobil, Exol D40), and the prepared paste vinyl chloride sol was coated on a flame retardant paper to a thickness of 0.25 mm, and heated in an oven heated to 140 ° C. A semi-gel sheet was prepared by heating at 40 ° C., and the sheet was cooled to room temperature and then heated in an oven heated to 210 ° C. for 60 seconds to obtain a foam. The obtained foam was evaluated for sol viscosity, foam hue, and foam cell structure by the following measurement method. The evaluation results are shown in Table 1.

＜ゾル粘度＞
ペースト塩ビ１５０重量部に対し、可塑剤としてジオクチルフタレート９０重量部をＴ．Ｋ．ホモディスパー（プライミクス製）を用い、２５℃、８００ｒｐｍで１．５分混練しペースト塩ビゾルを調製した。該ゾルを２５℃で３時間放置した後、Ｂ８Ｈ型粘度計（ローターＮｏ．５、２０ｒｐｍ、東京計器製）を用い、測定した。ゾル粘度値が低いほどゾル粘度特性が優れることを示す。

<Sol viscosity>
90 parts by weight of dioctyl phthalate as a plasticizer is added to 150 parts by weight of paste PVC. K. Using a homodisper (manufactured by Primemics), a paste vinyl chloride sol was prepared by kneading at 25 ° C. and 800 rpm for 1.5 minutes. The sol was allowed to stand at 25 ° C. for 3 hours, and then measured using a B8H type viscometer (rotor No. 5, 20 rpm, manufactured by Tokyo Keiki Co., Ltd.). A lower sol viscosity value indicates better sol viscosity characteristics.

<Measurement of foaming hue>
The yellow index value (YI) was measured with a color difference meter (manufactured by Nippon Denshoku, trade name MODEL-9463). YI is an index representing yellowness, and the smaller the value of YI, the more white the foamed molded product. If the difference in YI values is 0.5 or more, it is possible to determine the difference in foam hue change by observation with the naked eye.

<Foamed cell structure>
The foamed cell structure was evaluated visually with the following contents. The denser the foam cell structure, the better the foamability.

(◎): Cell is very dense (O): Cell is dense (x): Cell is rough <Stability with time of storage of paste PVC>
Immediately after production of the paste PVC produced by the above method, after 1 month, 3 months, and 6 months after production, a foamed molded article was prepared by the above method, and the YI value obtained by the above method was measured. The change 6 months after the production was calculated, and the value (ΔYI) was used to evaluate the temporal stability of the paste PVC during storage. That is, the smaller the value of ΔYI, the better the stability over time when the paste PVC is stored.

Example 2
Except that the amount of Na ₂ SO ₃ added was 0.04 parts by weight, paste vinyl chloride was obtained in the same manner as in Example 1 (Na ₂ SO ₃ content: 400 ppm) and evaluated. The evaluation results are shown in Table 1.

Example 3
Except that the amount of Na ₂ SO ₃ added was 0.13 parts by weight, paste vinyl chloride was obtained in the same manner as in Example 1 (Na ₂ SO ₃ content: 1300 ppm) and evaluated. The evaluation results are shown in Table 1.

Example 4
Except that the amount of Na ₂ SO ₃ added was 0.28 parts by weight, paste vinyl chloride was obtained in the same manner as in Example 1 (Na ₂ SO ₃ content: 2800 ppm) and evaluated. The evaluation results are shown in Table 1.

Example 5
Except that Na ₂ SO ₃ of Example 1 was changed to K ₂ SO ₃ , paste vinyl chloride was obtained by the same method as in Example 1 (K ₂ SO ₃ content: 150 ppm) and evaluated. The evaluation results are shown in Table 1.

Example 6
Except that the amount of K ₂ SO ₃ added was 0.28 parts by weight, paste vinyl chloride was obtained in the same manner as in Example 5 (K ₂ SO ₃ content: 2800 ppm) and evaluated. The evaluation results are shown in Table 1.

Example 7
Except that Na ₂ SO ₃ in Example 1 was changed to Na ₂ S ₂ O ₃ , paste vinyl chloride was obtained by the same method as in Example 1 (Na ₂ S ₂ O ₃ content: 150 ppm) and evaluated. . The evaluation results are shown in Table 1.

Example 8
Except that the amount of Na ₂ S ₂ O ₃ added was 0.28 parts by weight, paste vinyl chloride was obtained by the same method as in Example 7 (Na ₂ S ₂ O ₃ content: 2800 ppm) and evaluated. . The evaluation results are shown in Table 1.

Example 9
Except that Na ₂ SO ₃ of Example 1 was changed to K ₂ S ₂ O ₃ , paste vinyl chloride was obtained by the same method as in Example 1 (K ₂ S ₂ O ₃ content: 150 ppm) and evaluated. . The evaluation results are shown in Table 1.

Example 10
Except that the amount of K ₂ S ₂ O ₃ added was 0.28 parts by weight, paste vinyl chloride was obtained by the same method as in Example 9 (K ₂ S ₂ O ₃ content: 2800 ppm) and evaluated. . The evaluation results are shown in Table 1.

Example 11
_Na 2 _SO 3 0.0075 parts by weight of _Na 2 SO ₃ in Example _1, except that the Na ₂ S ₂ O 3 0.0075 parts by weight to obtain a paste PVC in the same manner as in Example 1 (Na ₂ SO ₃ content: 75 ppm, Na ₂ S ₂ O ₃ content: 75 ppm) was evaluated. The results are shown in Table 2.

実施例１２
実施例１のＮａ_２ＳＯ_３をＮａ_２ＳＯ_３０．１４重量部、Ｎａ_２Ｓ_２Ｏ_３０．１４重量部とした以外は実施例１と同様の方法によりペースト塩ビを得て（Ｎａ_２ＳＯ_３含有量：１４００ｐｐｍ，Ｎａ_２Ｓ_２Ｏ_３含有量：１４００ｐｐｍ）、評価を行った。その結果を表２に示す。

Example 12
_Na 2 _SO 3 0.14 parts by weight of _Na 2 SO ₃ in Example _1, except that the Na ₂ S ₂ O 3 0.14 parts by weight to obtain a paste PVC in the same manner as in Example 1 (Na ₂ SO ₃ content: 1400 ppm, Na ₂ S ₂ O ₃ content: 1400 ppm), and evaluation was performed. The results are shown in Table 2.

Example 13
Paste vinyl chloride was obtained in the same manner as in Example 1 except that Na ₂ SO ₃ of Example 1 was changed to 0.0075 parts by weight of K ₂ SO _{3 and} 0.0075 parts by weight of K ₂ S ₂ O ₃ (K ₂ SO ₃ content: 75 ppm, K ₂ S ₂ O ₃ content: 75 ppm) was evaluated. The results are shown in Table 2.

Example 14
Paste vinyl chloride was obtained in the same manner as in Example 1 except that Na ₂ SO ₃ of Example 1 was changed to 0.14 parts by weight of K ₂ SO _{3 and} 0.14 parts by weight of K ₂ S ₂ O ₃ (K ₂ SO ₃ content: 1400 ppm, K ₂ S ₂ O ₃ content: 1400 ppm), and evaluation was performed. The results are shown in Table 2.

Example 15
_Na 2 _SO 3 0.0075 parts by weight of _Na 2 SO ₃ in Example _1, except that the K ₂ SO 3 0.0075 parts by weight to obtain a paste PVC in the same manner as in Example 1 _(K 2 SO ₃ Evaluation: content: 75 ppm, K ₂ S ₂ O ₃ content: 75 ppm). The results are shown in Table 2.

Example 16
_Na 2 _SO 3 0.14 parts by weight of _Na 2 SO ₃ in Example _1, except that the K ₂ SO 3 0.14 parts by weight to obtain a paste PVC in the same manner as in Example 1 _(K 2 SO ₃ Evaluation: content: 1400 ppm, K ₂ S ₂ O ₃ content: 1400 ppm). The results are shown in Table 2.

Comparative Example 1
A paste PVC was obtained and evaluated by the same method as in Example 1 except that Na ₂ SO ₃ was not charged. The evaluation results are shown in Table 3. ΔYI = 3.3, and the temporal stability of the resin deteriorated during storage.

比較例２
シード１をシード２に、シード３をシード４に、ＡＢＳ１をＡＢＳ２に変更し、Ｎａ_２ＳＯ_３の仕込みを行わなかったこと以外は、実施例１と同様の方法によりペースト塩ビを得て、評価を行った。その評価結果を表３に示す。ΔＹＩ＝０．６となり、貯蔵時に樹脂の経時安定性は改善したが、ゾル粘度＝６０００ｍＰａ・ｓとなり、ゾル粘度特性が悪化した。

Comparative Example 2
Except that seed 1 was changed to seed 2, seed 3 was changed to seed 4, ABS1 was changed to ABS2, and Na ₂ SO ₃ was not charged, paste PVC was obtained and evaluated in the same manner as in Example 1. Went. The evaluation results are shown in Table 3. ΔYI = 0.6 and the temporal stability of the resin was improved during storage, but the sol viscosity was 6000 mPa · s, and the sol viscosity characteristics were deteriorated.

Comparative Example 3
Except that the amount of Na ₂ SO ₃ added was 0.005 parts by weight, paste vinyl chloride was obtained in the same manner as in Example 1 (Na ₂ SO ₃ content: 50 ppm) and evaluated. The evaluation results are shown in Table 3. ΔYI = 3.3, and the temporal stability of the resin deteriorated during storage.

Comparative Example 4
Except that the amount of Na ₂ SO ₃ added was 0.5 parts by weight, paste vinyl chloride was obtained by the same method as in Example 1 (Na ₂ SO ₃ content: 5000 ppm) and evaluated. The evaluation results are shown in Table 3. ΔYI = 0.2, and the stability with time of the resin was improved during storage, but the foamed cell structure was deteriorated.

Comparative Example 5
Except that Na ₂ SO ₃ was changed to Na ₂ S ₂ O ₃ , paste vinyl chloride was obtained by the same method as in Comparative Example 3 (Na ₂ S ₂ O ₃ content: 50 ppm) and evaluated. The evaluation results are shown in Table 3. ΔYI = 3.2, and the stability over time of the resin deteriorated during storage.

Comparative Example 6
Except that Na ₂ SO ₃ was changed to Na ₂ S ₂ O ₃ , paste vinyl chloride was obtained by the same method as in Comparative Example 4 (Na ₂ S ₂ O ₃ content: 5000 ppm) and evaluated. The evaluation results are shown in Table 3. ΔYI = 0.3, and the stability with time of the resin was improved during storage, but the foamed cell structure was deteriorated.

Comparative Example 7
Except that Na ₂ SO ₃ was changed to Na ₂ SO ₄ , paste vinyl chloride was obtained in the same manner as in Example 2 (Na ₂ SO ₄ content: 400 ppm) and evaluated. The evaluation results are shown in Table 3. ΔYI = 3.3, and the temporal stability of the resin deteriorated during storage.

Comparative Example 8
Except that Na ₂ SO ₃ was changed to Na ₂ S ₂ O ₄ , paste vinyl chloride was obtained by the same method as in Example 2 (Na ₂ S ₂ O ₄ content: 400 ppm) and evaluated. The evaluation results are shown in Table 3. ΔYI = 3.3, and the temporal stability of the resin deteriorated during storage.

Comparative Example 9
Except that Na ₂ SO ₃ was changed to K ₂ S ₂ O ₈ , paste vinyl chloride was obtained by the same method as in Example 2 (K ₂ S ₂ O ₈ content: 400 ppm) and evaluated. The evaluation results are shown in Table 3. The foamed hue immediately after production was YI = 12.5, which deteriorated. Further, ΔYI = 3.3, and the stability with time of the resin deteriorated during storage.

Comparative Example 10
Except for using Na ₂ SO ₃ ascorbic acid, paste vinyl chloride was obtained by the same method as in Example 2 (ascorbic acid content: 400 ppm) and evaluated. The evaluation results are shown in Table 3. The foamed hue immediately after production was YI = 12.5, which deteriorated.

Comparative Example 11
The _Na 2 _SO 3 0.0025 part by weight _{Na 2 SO 3, K 2 SO} 3 except for using 0.0025 parts by weight, to obtain a paste PVC in the same manner as in Comparative Example _{3 (Na} 2 SO 3 content: 25 ppm, Na ₂ S ₂ O ₃ content: 25 ppm). The results are shown in Table 3. ΔYI = 3.3, and the temporal stability of the resin deteriorated during storage.

Comparative Example 12
The _Na 2 _SO 3 0.25 parts by weight _{Na 2 SO 3, K 2 SO} 3 except for using 0.25 parts by weight, to obtain a paste PVC in the same manner as in Comparative Example _{3 (Na} 2 SO 3 content: 2500 ppm, Na ₂ S ₂ O ₃ content: 2500 ppm), and the evaluation was performed. The results are shown in Table 3. ΔYI = 0.2, and the stability with time of the resin was improved during storage, but the foamed cell structure was deteriorated.

Claims (5)

A vinyl chloride resin composition for wallpaper or flooring paste processing, comprising 100 to 3000 ppm of at least one compound represented by the following general formula (1) and the following general formula (2).
M ₂ SO ₃ (1)
(However, M represents one or more selected from alkali metals.)
M ₂ S ₂ O ₃ (2)
(However, M represents one or more selected from alkali metals.) A vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and a vinyl monomer copolymerizable with a vinyl chloride monomer is polymerized in an aqueous medium in the presence of an emulsifier and a polymerization initiator. In the obtained vinyl chloride resin latex, at least one compound represented by the following general formula (1) and the following general formula (2) is added in an amount of 0.01 to 0.3 with respect to 100 parts by weight of the vinyl chloride resin. The method for producing a vinyl chloride resin composition for wallpaper or flooring paste processing according to claim 1, wherein parts by weight are added and dried.
M ₂ SO ₃ (1)
(However, M represents one or more selected from alkali metals.)
M ₂ S ₂ O ₃ (2)
(However, M represents one or more selected from alkali metals.) 3. The method for producing a vinyl chloride resin composition for wallpaper or flooring paste processing according to claim 2, wherein alkylbenzene sulfonate is used as an emulsifier. A vinyl chloride sol composition for wallpaper or flooring paste processing, comprising the vinyl chloride resin composition for wallpaper or flooring paste processing according to claim 1. A foamed molded article for wallpaper or flooring, comprising the vinyl chloride sol composition for wallpaper or flooring paste processing according to claim 4.