JP4529430B2 - Vinyl chloride resin for paste, method for producing the same, and vinyl chloride resin composition for paste - Google Patents

Description

  The present invention relates to a vinyl chloride resin for paste, a method for producing the same, and a vinyl chloride resin composition for paste. More specifically, the present invention has a low-viscosity characteristic, exhibits a high yield value, has excellent processability without sagging during immersion molding, a method for producing the same, and a vinyl chloride resin composition for pastes It is about.

  Since vinyl chloride resin for paste has high adaptability to various processing, it is related to interiors such as wallpaper and flooring, automobiles such as underbody coat and sealant, steel sheet coating and pan cloth coating, medical treatment Disposable gloves such as disposable gloves such as industrial gloves and industrial gloves, cooking gloves, and toys such as dolls are used in a very wide range of fields.

  Among them, for molding processing of gloves and the like, an immersion processing method using a vinyl chloride resin for paste is generally used. This processing method involves dipping a ceramic, porcelain, or metal glove mold into a plastisol made of vinyl chloride resin for paste, plasticizer, stabilizer, etc., and depositing the required amount of plastisol on the mold surface. Then, it is heated to be gelled, and after cooling, it is peeled off from the mold to obtain a product.

In such a dipping process, the film thickness of the processed product is governed by the basis weight of the plastisol adhered to the mold surface. It is generally known that the basis weight of plastisol deposited on the surface of this mold correlates with the flow characteristics of the plastisol itself. On the other hand, in the dip processing method, it is an important processing technique to suppress uneven thickness due to sagging of plastisol adhered to the mold surface and crack formation due to local uneven thickness. The basis weight of plastisol adhering to the surface of these molds and the ease of sagging of plastisol are contradictory phenomena. Conventionally, since plastisol, which is easy to dripping, has the above-mentioned problems in processing, a method of adding a thixotropic agent (thickening agent) typified by SiO ₂ to the plastisol to improve the yield value and make it difficult to dripping is used. It is done.

  In addition, a production method has been proposed in which a polymer dispersant is added to a polymerization system and drying is performed at a high temperature of 60 ° C. or more to improve the yield value of the vinyl chloride resin for paste itself (see Patent Document 1). ).

  Furthermore, a vinyl chloride resin composition for paste containing a sulfate which is an inorganic salt has been proposed (see Patent Document 2).

JP-A-6-25316

However, the plastisol prepared by these methods has an improved yield value and has an effect of suppressing the plastisol sagging during the dipping process, but the viscosity of the plastisol itself is high, and the surface of the mold Since the basis weight of plastisol adhering to the substrate increases, there is a processing problem that only a processed product having a large film thickness can be obtained.

  Therefore, in order to produce a thin processed product with a film thickness of about 80 to 250 μm, such as disposable gloves and cooking gloves, by adding a large amount of plasticizer and solvent, the viscosity of the plastisol is lowered and a desired basis weight is obtained. There is a need.

  However, in this case, it is very difficult to maintain a yield value that can suppress the sagging property of plastisol. In addition, the addition of a large amount of plasticizer slows the gelation rate, which causes a problem of uneven thickness accompanied by plastisol sagging during the heating process, and it is difficult to obtain a processed product having high strength characteristics. It was. Regarding the addition of solvent, not only will the cost increase, but the solvent will volatilize during gelation, which may cause pinholes in the processed product, and the volatilized solvent may cause environmental deterioration and fire. Had many problems.

  From the above, even when the thixotropic agent is reduced or not added at the time of plastisol preparation, it exhibits high yield value and low viscosity characteristics, and does not have problems such as product strength reduction and environmental deterioration, especially film thickness It is to provide a vinyl chloride resin for paste that provides a plastisol suitable for dipping processing of a thin disposable glove, a method for producing the same, and a vinyl chloride resin composition for paste using the same.

  As a result of intensive studies on the above problems, the inventors of the present invention added a sodium compound having a specific structure to a vinyl chloride polymer latex obtained by polymerizing a vinyl chloride monomer in the presence of a reactive surfactant. The vinyl chloride resin for paste obtained by adding it gives a plastisol that has low viscosity characteristics and a high yield value, and is suitable for immersion processing in the molding processing of disposable gloves, cooking gloves, etc. The headline and the present invention were completed.

  That is, the present invention contains 0.01% to 0.5% by weight of a reactive surfactant represented by the following general formula [I] and 0.01% by weight of sodium sulfate and / or sodium sulfite. A vinyl chloride resin for paste containing ˜1.0% by weight, wherein 90 parts by weight of di-2-ethylhexyl phthalate is blended with 100 parts by weight of the resin, using a dissolver type mixer, at a rotational speed of 2000 rpm, The plastisol obtained by kneading for 90 seconds is allowed to stand at 25 ° C. for 2 hours, and the corrected viscosity obtained by the following formula (1) from the viscosity measured with a BM type viscometer is 100 mPa · s or more and less than 1000 mPa · s, and The yield value calculated | required by following formula (2) is 10 mPa or more, The vinyl chloride resin for pastes characterized by the above-mentioned, The manufacturing method, and the vinyl chloride for pastes It relates resin composition.

Corrected viscosity V ₉ = 2V ′ ₁₂ −V ′ ₆ (1)
Yield value Y = 12 (V ′ ₆ −V ′ ₁₂ ) (2)
(Wherein, V _'6 is a BM type viscometer, using a No.2 rotor viscosity at a rotational speed 6rpm (mPa · s), V ' 12 is a BM type viscometer, the No.2 rotor Used and shows viscosity (mPa · s) at 12 rpm.)

（式中、Ｒは炭素数６から１８のアルキル基、アルケニル基又はアラルキル基、Ａは炭素数２から４のアルキレン基、ｎは１から２００の整数、Ｍは水素、スルホン酸アルカリ金属塩又はスルホン酸アンモニウム塩である。）
以下に、本発明を詳細に説明する。

Wherein R is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 200, M is hydrogen, an alkali metal sulfonate or (Sulphonic acid ammonium salt.)
The present invention is described in detail below.

  The vinyl chloride resin for paste of the present invention is not particularly limited as long as it falls within the scope of the present invention, and a vinyl monomer homopolymer or a vinyl monomer copolymerizable with a vinyl chloride monomer and Either of these copolymers may be used.

  Examples of the reactive surfactant represented by the following general formula [I] contained in the vinyl chloride resin for paste of the present invention include nonylpropenylphenol ethylene oxide 10 mol adduct, nonylpropenylphenol ethylene oxide 20 mol adduct, nonyl. Propenylphenol ethylenoxide 100 mol adduct, octylpropenylphenol ethylene oxide 10 mol adduct, octylpropenylphenol ethylene oxide 20 mol adduct, dodecylpropenylphenol ethylene oxide 10 mol adduct, nonylpropenylphenol ethylene oxide 10 mol adduct, propylene oxide 10 mol random addition , Nonylpropenylphenol butylene oxide 4 mol, ethylene oxide 30 mol block adduct, and sulfonic acid Potassium salts, sulfonic acid ammonium salts.

（式中、Ｒは炭素数６から１８のアルキル基、アルケニル基又はアラルキル基、Ａは炭素数２から４のアルキレン基、ｎは１から２００の整数、Ｍは水素、スルホン酸アルカリ金属塩又はスルホン酸アンモニウム塩である。）
本発明のペースト用塩化ビニル樹脂において、上記一般式［Ｉ］で示される反応性界面活性剤の含有量としては、０．０１重量％〜０．５重量％であることが必要である。含有量が０．０１重量％未満の場合は充分な低粘度を有するプラスチゾルが得られず、また、プラスチゾル貯蔵による粘度の経時変化が大きくなる。一方、０．５重量％を超えた場合は、良好な粘度特性が得られるものの、重合時間が長くなったり、重合が不安定化したりと却って生産性の悪化を招く。なお、浸漬加工に適した流動特性の向上と安定した生産の確保のために０．０３重量％〜０．３重量％であることが好ましく、浸漬槽中におけるプラスチゾルの粘度の経時安定化を向上するために０．０５重量％から０．３重量％であることが特に好ましい。

Wherein R is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 200, M is hydrogen, an alkali metal sulfonate or (Sulphonic acid ammonium salt.)
In the vinyl chloride resin for paste of the present invention, the content of the reactive surfactant represented by the above general formula [I] needs to be 0.01% by weight to 0.5% by weight. When the content is less than 0.01% by weight, a plastisol having a sufficiently low viscosity cannot be obtained, and the change with time in viscosity due to plastisol storage becomes large. On the other hand, if it exceeds 0.5% by weight, good viscosity characteristics can be obtained, but the polymerization time becomes longer or the polymerization becomes unstable, leading to deterioration of productivity. In addition, in order to improve flow characteristics suitable for immersion processing and to ensure stable production, it is preferably 0.03% to 0.3% by weight, and improves the plastisol viscosity stabilization in the immersion tank over time. Therefore, the content is particularly preferably 0.05 to 0.3% by weight.

  In addition, the amount of sodium sulfate and / or sodium sulfite contained in the vinyl chloride resin for paste of the present invention needs to be 0.01% by weight to 1.0% by weight. When the content is less than 0.01% by weight, in the plastisol prepared from the obtained vinyl chloride resin for paste, a high yield value cannot be obtained, and it is difficult to suppress sagging of the plastisol during the dipping process. On the other hand, when the content exceeds 1.0% by weight, a plastisol having a high yield value can be obtained, but the viscosity of the plastisol itself increases, resulting in flow characteristics unsuitable for dipping. In addition, it is preferable that it is 0.025 wt% to 0.5 wt% in order to improve the workability for the dip processing due to the improvement of the yield value and the low viscosity property, and the sagging during heating in the gelation step In order to suppress and facilitate film thickness control of the processed product, the content is particularly preferably 0.05% by weight to 0.5% by weight.

  The vinyl chloride resin for paste of the present invention is obtained by blending 90 parts by weight of di-2-ethylhexyl phthalate with 100 parts by weight of the resin and kneading for 90 seconds at a rotation speed of 2000 rpm using a dissolver mixer. The plastisol was allowed to stand at 25 ° C. for 2 hours, and the corrected viscosity obtained from the following formula (1) from the viscosity measured with a BM viscometer was 100 mPa · s or more and less than 1000 mPa · s, and was obtained from the following formula (2). The yield value obtained is 10 mPa or more.

Corrected viscosity V ₉ = 2V ′ ₁₂ −V ′ ₆ (1)
Yield value Y = 12 (V ′ ₆ −V ′ ₁₂ ) (2)
(In the formula, V ′ ₆ is a BM type viscometer, using a No. 2 rotor, viscosity (mPa · s) at a rotation speed of 6 rpm, V ′ ₁₂ is a BM type viscometer, No. 2 rotor Used and shows viscosity (mPa · s) at 12 rpm.)
Here, when the corrected viscosity is less than 100 mPa · s, when a plastisol is prepared from the obtained vinyl chloride resin for paste, a uniform film formation can be obtained with a low basis weight of the plastisol adhering to the mold surface. It becomes difficult. On the other hand, when the corrected viscosity is 1000 mPa · s or more and the plastisol is prepared from the obtained vinyl chloride resin for paste, the amount of plastisol adhering to the mold surface increases, and only a thick processed product can be obtained. It has a processing problem that cannot be performed. In addition, when the yield value is less than 10 mPa, the yield value is low, so processing problems such as uneven thickness due to sagging of plastisol adhered to the mold surface and formation of cracks due to local uneven thickness. Produce.

  As the dissolver mixer used here, any commercially available dissolver mixer can be used. As the BM type viscometer used for measuring the viscosity of plastisol, any commercially available BM type viscometer can be used.

  The method for producing the vinyl chloride resin for paste of the present invention will be described below.

  When the vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith is seeded in an aqueous medium and subjected to fine suspension polymerization, the general formula [I ] 0.01% by weight to 0.5% by weight of a reactive surfactant represented by the formula:

  Here, in the case of a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith, the vinyl chloride monomer is preferably 80% by weight or more, and preferably 90% by weight or more. More preferred. The monomer that can be copolymerized with vinyl chloride may be any monomer that can be copolymerized with vinyl chloride, such as monoolefins such as ethylene, propylene, and butene; Vinyl esters such as vinyl, vinyl propionate, vinyl myristate, vinyl benzoate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid or anhydrides thereof; methyl acrylate, ethyl acrylate, acrylic Acrylic acid esters such as acid-n-butyl and acrylic acid-2-hydroxyethyl; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, methacrylic acid-N, N-dimethylaminoethyl; Maleic acid ester, fumarate Unsaturated carboxylic acid esters such as acid esters and cinnamic acid esters; vinyl methyl ester Ether, vinyl amyl ether, vinyl ethers such as vinyl phenyl ether; can be mentioned acrylonitrile, methacrylonitrile and the like; vinylidene chloride, styrene and its derivatives.

  In addition, seeding fine suspension polymerization here means vinyl chloride monomer (vinyl chloride monomer alone or a mixture of vinyl chloride monomer and monomer copolymerizable therewith), initiator, etc. Seed particles containing surfactants, or surfactants, if necessary, free of monomer-soluble initiators, in the presence of a polymerization degree modifier, aliphatic higher alcohol, buffer, In this method, polymerization is carried out in an aqueous medium at 40 to 70 ° C. with stirring.

  Seed particles containing an initiator and the like can be prepared, for example, by the following fine suspension polymerization method. First, vinyl chloride monomer, polymerization initiator soluble in vinyl chloride monomer, surfactant, pure water, buffer, higher alcohol, higher fatty acid, higher fatty acid ester, chlorinated paraffin and other dispersants If necessary, a polymerization degree regulator is added and premixed, and homogenization is performed by a homogenizer to adjust oil droplets. As a homogenizer at this time, for example, a colloid mill, a vibration stirrer, a two-stage high-pressure pump, or the like can be used. Then, the homogenized liquid is sent to the polymerization vessel and the polymerization reaction is started by gradually raising the temperature in the polymerization vessel while stirring gently. The polymerization is carried out until a predetermined conversion rate is reached, and an initiator and the like are contained. It is possible to prepare seed particles. The polymerization temperature at this time is preferably 30 to 50 ° C. As a polymerization initiator soluble in a vinyl chloride monomer, a diacyl peroxide having a 10-hour half-life temperature of 30 to 70 ° C. is preferable. Examples of such a polymerization initiator include isobutyryl peroxide, 3, Examples include 3,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and succinic acid peroxide. As the surfactant, surfactants used for a general paste vinyl chloride polymerization system described later can be used alone or in combination of two or more. As the polymerization degree modifier used as necessary, those described later can be used.

  In addition, seed particles that do not contain an initiator or the like can be prepared, for example, by the following emulsion polymerization method. Charged with pure water, surfactant, water-soluble polymerization initiator, etc., degassed in the polymerization vessel or replaced with inert gas such as nitrogen as necessary, charged with vinyl chloride monomer, stirred While forming the surfactant micelle phase solubilized with the vinyl chloride monomer, the temperature in the polymerization vessel is increased to advance the polymerization. In that case, an initiator, a reducing agent, a surfactant, a particle size controlling agent and the like may be added before or during the polymerization reaction in order to control the reaction rate and particle size. The polymerization temperature is preferably in the range of 40 to 70 ° C. Examples of the water-soluble polymerization initiator include water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide; these peroxides, or hydrous such as cumene hydroperoxide and t-butyl hydroperoxide. Redox initiators in which peroxide is combined with reducing agents such as acidic sodium sulfite, ammonium sulfite, ascorbic acid, ethylene diamine tetraacetate sodium complex of ferrous ion, ferrous pyrophosphate; 2,2'-azobis And water-soluble azo compounds such as (2-methylpropionamidine) dihydrochloride. As the surfactant, surfactants used in the general vinyl chloride polymerization system for paste described later can be used alone or in combination of two or more. Examples of the particle size control agent include a combination of an alkali metal sulfate such as sodium sulfate or potassium sulfate with a surfactant used for the above-described general vinyl chloride polymerization system for paste.

  Examples of the polymerization degree regulator used as necessary include halogenated hydrocarbons such as trichloroethylene and carbon tetrachloride, mercaptans such as 2-mercaptoethanol, octyl 3-mercaptopropionate, and dodecyl mercaptan, acetone, n -Aldehydes, such as butyraldehyde, etc. are mentioned, What kind of thing may be used if a polymerization degree can be adjusted. Although there is no restriction | limiting in particular as an aliphatic higher alcohol used as needed, Usually, a C8-C18 aliphatic higher alcohol is used. This can be used alone or in a mixture of aliphatic higher alcohols having different carbon numbers. Examples of the buffering agent used as necessary include monobasic or dihydrogen alkali metal salts, potassium hydrogen carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, and the like.

  When the addition amount of the reactive surfactant is less than 0.01% by weight, it is difficult to obtain a plastisol having a sufficiently low viscosity characteristic, while when the addition amount exceeds 0.5% by weight. Has problems of productivity, such as a long polymerization time and unstable polymerization. The reactive surfactant may be added as it is or may be added as an aqueous solution. In this case, it is preferable to add it as an aqueous solution in order to disperse it efficiently and uniformly in the polymerization aqueous medium.

  As a method of adding the reactive surfactant, a method of batch charging, a method of charging continuously or batch-wise during a polymerization reaction with a polymerization conversion rate of 85% or less after reaching a predetermined polymerization temperature, and polymerization before starting polymerization Examples include a method in which the reaction is divided into two during the reaction, and any method may be used, but the reactive surfactant may be continuously added during the polymerization reaction with a polymerization conversion of 85% or less after reaching the predetermined polymerization temperature. It is preferable from the viewpoint of polymerization stability. Here, examples of the predetermined polymerization temperature include 40 ° C to 70 ° C.

  In addition, when the reactive surfactant is used alone, the reactive surfactant / in order to achieve both the stability of polymerization and the physical properties of the plastisol prepared with the vinyl chloride resin for paste obtained. It is preferable that the surfactant used in other general vinyl chloride polymerization systems for pastes is added in the range of 1/20 to 2/1 (weight ratio), and the reactive surfactant / It is particularly preferable to add the surfactant used in other general vinyl chloride polymerization systems for paste in the range of 1/20 to 1/1 (weight ratio).

  Here, examples of the surfactant used in other general vinyl chloride polymerization systems for paste include an anionic surfactant and a nonionic surfactant. Here, examples of the anionic surfactant include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate esters such as sodium lauryl sulfate and sodium tetradecyl sulfate; sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate. Sulfosuccinates such as: fatty acid salts such as sodium laurate and semi-cured tallow fatty acid potassium; ethoxy sulfate salts such as polyoxyethylene lauryl ether sulfate sodium salt and polyoxyethylene nonylphenyl ether sulfate sodium salt; alkane sulfonates; Examples thereof include ether phosphate sodium salt. Nonionic surfactants include, for example, polyoxyethylene fatty alcohol ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether and other polyoxyethylene fatty alcohol ethers. Ethylene alkyl allyl ethers; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan tristearate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleate; Glycerin fatty acid esters such as stearic acid monoglyceride and oleic acid monodiglyceride; sorbitan monoparimidate, sorbitan trio It can be given over sorbitan fatty acid esters such as bets like.

  In addition, when the amount of sodium sulfate and / or sodium sulfite added is less than 0.01% by weight, it is difficult to obtain a sufficiently high yield value necessary to suppress plastisol sagging in the immersion processing method. On the other hand, when the added amount exceeds 1.0% by weight, the viscosity of the plastisol itself increases, which is a flow characteristic unsuitable for obtaining a thin processed product such as a disposable glove. Sodium sulfate and / or sodium sulfite may be added as it is, or may be added as an aqueous solution. In this case, it is preferable to add the compound as an aqueous solution in order to efficiently disperse the compound in the latex.

  The timing of adding sodium sulfate and / or sodium sulfite is, for example, before the start of polymerization and / or polymerization reaction of a vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith. The method of adding to the aqueous medium in the inside, the method of adding to the latex after the completion of the polymerization reaction, etc. are mentioned, but among these, the method of adding to the latex after the completion of the polymerization reaction is intended to further stabilize the polymerization system Most preferable in terms of production and characteristics of the plastisol prepared with the obtained vinyl chloride resin for paste. These compounds can be added individually or in combination at any ratio. Here, the arbitrary ratio is a ratio in which two kinds of the compounds of sodium sulfate and sodium sulfite are mixed at a weight ratio, for example, sodium sulfate / sodium sulfite (50/50 wt%).

  As a method of adding sodium sulfate and / or sodium sulfite, a method of directly adding a predetermined amount of the compound, an aqueous solution in which the compound is dissolved in deionized water, the compound becomes a predetermined amount with respect to the vinyl chloride resin for paste. And the like.

  The vinyl chloride resin for paste of the present invention can be recovered by drying a latex of vinyl chloride resin for paste obtained by polymerization by the seeding fine suspension polymerization method as described above. The drying method is not particularly limited, but drying with a spray dryer is preferable because the obtained vinyl chloride resin for paste is obtained as desired secondary particles. Examples of the drying with a spray dryer include various spray dryers such as “SPRAY DRYING HANDBOOK” (K. Masters, 3rd edition, 1979, George Godwin Limited), page 121, FIG. 4.10. As drying conditions, for example, the drying outlet temperature is operated in the range of 40 ° C to 90 ° C, and the drying is usually performed at 40 ° C to 70 ° C, preferably 40 ° C to 65 ° C.

  A vinyl chloride resin composition for paste can be obtained by blending a plasticizer with the vinyl chloride resin for paste of the present invention. In this case, since the obtained vinyl chloride resin composition for paste has a low corrected viscosity value and a high yield value, the plasticizer is added in an amount of 30 to 300 parts by weight with respect to 100 parts by weight of the vinyl chloride resin for paste. However, in order to improve product physical properties such as tensile strength and tactile sensation of the processed product, it is particularly preferably 50 to 150 parts by weight. When the plasticizer to be blended is less than 30 parts by weight relative to 100 parts by weight of the vinyl chloride resin for paste, it is difficult to prepare a plastisol, while when the plasticizer to be blended exceeds 300 parts by weight, it is obtained. The resulting plastisol has a low viscosity, and it is difficult not only to maintain a yield value that can suppress sagging, but also causes a problem of stickiness in the processed product.

  Examples of the plasticizer when preparing the vinyl chloride resin composition for paste using the vinyl chloride resin for paste of the present invention include, for example, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, Phthalate ester plasticizers such as octyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate; Aliphatic monobasic ester plasticizers such as butyl oleate and glycerin monooleate: di-n-adipate Aliphatic dibasic acid ester plasticizers such as hexyl, di-2-ethylhexyl adipate, diisononyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate; tris-2-ethylhexyl trimellitic acid, Acetyl triethyl citrate, acetyl tributyl citrate, male Examples include plasticizers such as di-2-ethylhexyl acid, dibutyl fumarate, epoxidized oils and fats, epoxy fatty acid esters, and chlorinated paraffins. These plasticizers can be used alone or in combination of two or more. .

  When preparing a vinyl chloride resin composition for paste using the vinyl chloride resin for paste of the present invention, a stabilizer may be used in combination as necessary. Examples of the stabilizer include an epoxy stabilizer. , Barium stabilizers, calcium stabilizers, tin stabilizers, zinc stabilizers, and the like, and one or more of these may be used in combination. Moreover, commercially available composite stabilizers such as calcium-zinc (Ca-Zn) and barium-zinc (Ba-Zn) can also be used. And as addition amount of these stabilizers, it is preferable that they are 0.5 weight part-10 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

  The vinyl chloride resin for paste according to the present invention is a vinyl chloride resin for paste having excellent characteristics such as a low corrected viscosity and a high yield value when a vinyl chloride composition for paste is prepared in the case of molding. The composition has a very high industrial value, and particularly has high suitability for immersion processing in glove processing such as disposable gloves and cooking gloves.

  The present invention will be described in more detail with reference to the following examples, but the contents thereof do not particularly limit the scope of the present invention.

  The seed particles used in the following examples were produced as follows.

<Production of oil-soluble polymerization initiator-containing seed particles>
A 1 m ³ autoclave was charged with 360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide, and 30 kg of a 15% by weight aqueous sodium dodecylbenzenesulfonate solution, and this polymerization solution was circulated for 3 hours using a homogenizer. After the homogenization treatment, the temperature was raised to 45 ° C. to proceed the polymerization. After the pressure drops, the unreacted vinyl chloride monomer is recovered, the solid content is 35% by weight, the particles have an average particle size of 0.55 μm, and the polymer is based on 2% by weight peroxidation. A latex containing lauroyl (hereinafter abbreviated as seed 1) was obtained.

<Production of seed particles containing no polymerization initiator>
A 1 m ³ autoclave was charged with 400 kg of deionized water, 350 kg of vinyl chloride monomer, 2 kg of 16 wt% potassium persulfate aqueous solution, and 5 kg of 16 wt% sodium dodecylbenzenesulfonate aqueous solution, and the temperature was raised to 54 ° C. to proceed the polymerization. It was. After the pressure dropped, unreacted vinyl chloride monomer was recovered to obtain a latex (hereinafter abbreviated as seed 2) having a solid content of 40% by weight and particles having an average particle size of 0.15 μm. .

Example 1
In a 2.5 L autoclave, 720 g of deionized water, 800 g of vinyl chloride monomer, 1.1% by weight of a 5% aqueous solution of sodium lauryl sulfate as a surfactant (sodium lauryl sulfate: 0.055% by weight), 90 g of seed 1 The temperature of the reaction mixture was raised to 48 ° C. and polymerization was started. After the internal temperature reaches 48 ° C., the polymerization conversion rate is up to 85%, and the nonylpropenylphenol ethylene oxide 10 mol adduct sulfonate ammonium salt (Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon HS-10, hereinafter HS-10) 5% aqueous solution (HS-10: 0.13% by weight) and 12.6% by weight of 5% aqueous solution of sodium lauryl sulfate (0.63% by weight sodium lauryl sulfate). ) Was added continuously. The polymerization reaction was stopped when the polymerization pressure dropped by 0.196 MPa from the saturated vapor pressure of vinyl chloride at 48 ° C. Thereafter, unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex. Then, 0.5% by weight of a 10% aqueous solution of sodium sulfite (sodium sulfite: 0.05% by weight) was added to the vinyl chloride polymer latex. Then, the obtained vinyl chloride polymer latex was dried at a drying inlet temperature of 158 ° C. and a drying outlet temperature of 55 ° C. using a rotary disk spray dryer to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

得られたペースト用塩化ビニル樹脂１００重量部に対し、フタル酸ジー２−エチルヘキシル９０重量部を配合し、ディゾルバー式ミキサーを用い、回転数２０００ｒｐｍで、９０秒間混練を行い、プラスチゾルを調製した。

A plastisol was prepared by blending 90 parts by weight of di-2-ethylhexyl phthalate with 100 parts by weight of the obtained vinyl chloride resin for paste, and kneading at a rotation speed of 2000 rpm for 90 seconds using a dissolver mixer.

  The obtained plastisol was allowed to stand for 2 hours in a thermostatic bath at 25 ° C. Measurements were taken at 6 and 12 rpm using 2 rotors.

By substituting the apparent viscosity V ′ ₆ (viscosity of 6 rpm) and V ′ ₁₂ (viscosity of ₁₂ rpm), which are the measurement results, into the following formulas (1) and (2), the corrected viscosity V ₉ and the yield value Y are obtained. Asked.

Corrected viscosity V ₉ = 2V ′ ₁₂ −V ′ ₆ (1)
Yield value Y = 12 (V ′ ₆ −V ′ ₁₂ ) (2)
The obtained results are shown in Table 2.

得られたペースト用塩化ビニル樹脂より調製されたプラスチゾルは、低い補正粘度値を有し、高い降伏値を有するものであった。

The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 2
A paste vinyl chloride resin was obtained in the same manner as in Example 1 except that 90g of seed 1 was changed to 90g of seed 1 and 16g of seed 2 in Example 1. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 3
In Example 2, the mixed aqueous solution to be continuously added was 1.52% by weight of a 5% aqueous solution of HS-10 (HS-10: 0.076% by weight), and 13% of a 5% aqueous solution of sodium lauryl sulfate. Except having changed into the mixed aqueous solution of 6 weight% (sodium lauryl sulfate: 0.68 weight%), it carried out similarly to Example 2 and obtained the vinyl chloride resin for pastes. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 4
In Example 1, the mixed aqueous solution to be continuously added was 5.04% by weight of a 5% aqueous solution of nonylpropenylphenol ethylene oxide 20 mol adduct (Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon RN-20) (nonylpropenyl). Phenolethylene oxide 20 mol adduct: 0.252% by weight) and a 5% aqueous solution of sodium lauryl sulfate were changed to a mixed aqueous solution of 10.06% by weight (sodium lauryl sulfate: 0.503% by weight). 1 was performed to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 5
In Example 1, except that the addition amount of the 10% aqueous solution of sodium sulfite added to the polymerized vinyl chloride polymer latex was changed to 5.0 wt% (sodium sulfite: 0.5 wt%). 1 was performed to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 6
In Example 1, 0.5% by weight of a 10% aqueous solution of sodium sulfite (sodium sulfite: 0.05% by weight) added to the vinyl chloride polymer latex after polymerization was changed to 0.25% by weight of a 10% aqueous solution of sodium sulfate. Except having changed to (sodium sulfate: 0.025 weight%), it carried out similarly to Example 1 and obtained the vinyl chloride resin for pastes. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 7
In Example 6, except that the addition amount of 10% aqueous solution of sodium sulfate added to the polymerized vinyl chloride polymer latex was changed to 1.0% by weight (sodium sulfate: 0.1% by weight). 6 was performed to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 8
In Example 6, except that the addition amount of a 10% aqueous solution of sodium sulfate added to the polymerized vinyl chloride polymer latex was changed to 2.5% by weight (sodium sulfate: 0.25% by weight). 6 was performed to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 9
In Example 6, except that the addition amount of a 10% aqueous solution of sodium sulfate added to the polymerized vinyl chloride polymer latex was changed to 10.0% by weight (sodium sulfate: 1.0% by weight). 6 was performed to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Example 10
In Example 7, 1.0% by weight (sodium sulfate: 0.1% by weight) of a 10% aqueous solution of sodium sulfate to be added to the polymerized vinyl chloride polymer latex was 1/1 (by weight of sodium sulfite and sodium sulfate). Ratio) was changed to 10.0% by weight (sodium sulfite, sodium sulfate: 1.0% by weight), and a vinyl chloride resin for paste was obtained in the same manner as in Example 7. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value and a high yield value.

Comparative Example 1
In Example 1, the mixed aqueous solution to be continuously added was changed to 15.2% by weight (sodium lauryl sulfate: 0.76% by weight) of a 5% aqueous solution of sodium lauryl sulfate, and further the vinyl chloride polymer after polymerization. A latex vinyl chloride resin was obtained in the same manner as in Example 1 except that 10% aqueous sodium sulfite solution was not added to the latex. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a high corrected viscosity value and a low yield value.

Comparative Example 2
In Example 2, the mixed aqueous solution to be continuously added was changed to 15.2% by weight (sodium lauryl sulfate: 0.76% by weight) of a 5% aqueous solution of sodium lauryl sulfate, and further the vinyl chloride polymer after polymerization. A latex vinyl chloride resin was obtained in the same manner as in Example 2 except that 10% aqueous sodium sulfite solution was not added to the latex. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a high corrected viscosity value although a high yield value was obtained.

Comparative Example 3
In Example 1, the mixed aqueous solution to be continuously added was changed to 15.2% by weight of a 5% aqueous solution of sodium lauryl sulfate (sodium lauryl sulfate: 0.76% by weight). A vinyl chloride resin for paste was obtained. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a high corrected viscosity value although a high yield value was obtained.

Comparative Example 4
In a 2.5 L autoclave, 720 g of deionized water, 800 g of vinyl chloride monomer, 0.82% by weight of a 5% aqueous solution of HS-10 as a reactive surfactant (HS-10: 0.041% by weight), surface activity As agents, 0.275 wt% of a 5% aqueous solution of sodium lauryl sulfate (sodium lauryl sulfate: 0.0138 wt%) and 90 g of seed 1 were charged, and the temperature of the reaction mixture was raised to 48 ° C. to initiate polymerization. After the internal temperature reaches 48 ° C., the polymerization conversion rate is up to 85%, and 5% aqueous solution of HS-10 is 11.34% by weight (HS-10: 0.567% by weight), and 5% aqueous solution of sodium lauryl sulfate. Was continuously added as a mixed aqueous solution of 3.78% by weight (sodium lauryl sulfate: 0.189% by weight). The polymerization reaction was stopped when the polymerization pressure dropped by 0.196 MPa from the saturated vapor pressure of vinyl chloride at 48 ° C. Thereafter, unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex, but the polymerization time was long, and the latex was agglomerated and lacked polymerization stability. . Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

Comparative Example 5
In Example 1, a vinyl chloride resin for paste was obtained in the same manner as in Example 1 except that a 10% aqueous solution of sodium sulfite was not added to the polymerized vinyl chloride polymer latex. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  Although the plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value, the yield value was negative, it showed dilatant flow, and was unsuitable for dipping.

Comparative Example 6
In Example 1, except that the addition amount of a 10% aqueous solution of sodium sulfite added to the polymerized vinyl chloride polymer latex was changed to 20.0 parts by weight (sodium sulfite: 2.0% by weight). 1 was performed to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  To 100 parts by weight of the obtained vinyl chloride resin for paste, 90 parts by weight of di-2-ethylhexyl phthalate was blended and kneaded for 90 seconds at a rotation speed of 2000 rpm using a dissolver mixer to prepare plastisol.

  The obtained plastisol was tried to be evaluated under the same conditions as those shown in Example 1. However, no. Since the increase in viscosity exceeding the viscosity measurement range of 2 rotors was observed, No. Evaluation was performed under the same conditions as those shown in Example 1 except that 4 rotors were used. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste showed a high corrected viscosity value although a high yield value was obtained.

Comparative Example 7
In Example 1, 0.5% by weight of a 10% aqueous sodium sulfite solution (sodium sulfite: 0.05% by weight) added to the vinyl chloride polymer latex after polymerization was changed to 0.5% by weight of a 10% aqueous sodium thiosulfate solution. % (Sodium thiosulfate: 0.05% by weight) was performed in the same manner as in Example 1 to obtain a vinyl chloride resin for paste. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  Although the plastisol prepared from the obtained vinyl chloride resin for paste had a low corrected viscosity value, the yield value was negative, it showed dilatant flow, and was unsuitable for dipping.

Comparative Example 8
In Example 1, 0.5% by weight of a 10% aqueous solution of sodium sulfite (sodium sulfite: 0.05% by weight) added to the vinyl chloride polymer latex after polymerization was changed to 0.5% by weight of a 10% aqueous solution of sodium chloride. Except having changed to (sodium chloride: 0.05 weight%), it carried out similarly to Example 1 and obtained the vinyl chloride resin for pastes. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  The obtained vinyl chloride resin for paste was evaluated under the same conditions as those shown in Example 1. The obtained evaluation results are shown in Table 2.

  The plastisol prepared from the obtained vinyl chloride resin for paste had a low yield value although a low corrected viscosity value was obtained.

Comparative Example 9
In Example 1, 0.5% by weight (sodium sulfite: 0.05% by weight) of a 10% aqueous solution of sodium sulfite added to the vinyl chloride polymer latex after polymerization was added to 5.0% by weight of a 10% aqueous solution of polyvinyl alcohol. Except having changed to (polyvinyl alcohol: 0.5 weight%), it carried out similarly to Example 1 description, and obtained the vinyl chloride resin for pastes. Table 1 shows the synthesis conditions of the vinyl chloride resin for paste.

  A plastisol was prepared by blending 90 parts by weight of di-2-ethylhexyl phthalate with 100 parts by weight of the obtained vinyl chloride resin for paste, and kneading for 90 seconds at 2000 rpm using a dissolver mixer.

  The obtained plastisol was tried to be evaluated under the same conditions as those shown in Example 1. However, no. Since the increase in viscosity exceeding the viscosity measurement range of 2 rotors was observed, No. Evaluation was performed under the same conditions as those shown in Example 1 except that 4 rotors were used. The obtained evaluation results are shown in Table 2.

  Although the plastisol prepared from the obtained vinyl chloride resin for paste showed a high yield value, it was accompanied by a significant increase in the corrected viscosity and was no longer suitable for dipping.

Comparative Example 10
To 100 parts by weight of the vinyl chloride resin for paste obtained in Comparative Example 5, 90 parts by weight of di-2-ethylhexyl phthalate and 0.5 parts by weight of a thixotropic agent (Aerosil # 200 (made by Nippon Aerosil Co., Ltd.)) Using a dissolver mixer, kneading was performed for 90 seconds at a rotational speed of 2000 rpm to prepare a plastisol.

  The obtained plastisol was tried to be evaluated under the same conditions as those shown in Example 1. However, no. Since the increase in viscosity exceeding the viscosity measurement range of 2 rotors was observed, No. Evaluation was performed under the same conditions as those shown in Example 1 except that 3 rotors were used. The obtained evaluation results are shown in Table 2.

The plastisol prepared from the obtained vinyl chloride resin for paste had a high corrected viscosity although it exhibited a high yield value.

Claims (7)

A reactive surfactant represented by the following general formula [I] is contained in an amount of 0.01% to 0.5% by weight, and sodium sulfate and / or sodium sulfite is 0.01% to 1.0% by weight. A vinyl chloride resin for paste containing, obtained by mixing 90 parts by weight of di-2-ethylhexyl phthalate with 100 parts by weight of the resin and kneading for 90 seconds at a rotation speed of 2000 rpm using a dissolver mixer. The obtained plastisol was allowed to stand at 25 ° C. for 2 hours, and the corrected viscosity determined by the following formula (1) from the viscosity measured with a BM viscometer was 100 mPa · s or more and less than 1000 mPa · s, and the following formula (2) A vinyl chloride resin for paste, characterized in that the yield value required is 10 mPa or more.
Corrected viscosity V ₉ = 2V ′ ₁₂ −V ′ ₆ (1)
Yield value Y = 12 (V ′ ₆ −V ′ ₁₂ ) (2)
(In the formula, V ′ ₆ is a BM type viscometer, using a No. 2 rotor, viscosity (mPa · s) at a rotation speed of 6 rpm, V ′ ₁₂ is a BM type viscometer, No. 2 rotor Used and shows viscosity (mPa · s) at 12 rpm.)

Wherein R is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 200, M is hydrogen, an alkali metal sulfonate or (Sulphonic acid ammonium salt.) The reactive surface activity represented by the general formula [I] in the case of seeding fine suspension polymerization of a vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith in an aqueous medium The agent according to claim 1, wherein 0.01% to 0.5% by weight of the agent is added, and 0.01% to 1.0% by weight of sodium sulfate and / or sodium sulfite is further added. Manufacturing method of vinyl chloride resin for paste. Adding the reactive surfactant represented by the general formula [I] continuously or collectively in an aqueous medium before the start of polymerization and / or a polymerization reaction with a polymerization conversion of 85% or less after reaching a predetermined polymerization temperature. The method for producing a vinyl chloride resin for paste according to claim 2, wherein Surfactant used for the reactive surfactant represented by the general formula [I] to the reactive surfactant / other general vinyl chloride polymerization system for paste = 1/20 to 2/1 (weight ratio) The method for producing a vinyl chloride resin for paste according to claim 2 or 3, characterized in that it is added in the range of 5. The method for producing a vinyl chloride resin for paste according to claim 2, wherein sodium sulfate and / or sodium sulfite is added to the latex after completion of the polymerization reaction. 6. The method for producing a vinyl chloride resin for paste according to claim 5, wherein sodium sulfate and / or sodium sulfite are added individually or mixed at an arbitrary ratio. A vinyl chloride resin composition for paste, comprising 30 parts by weight to 300 parts by weight of a plasticizer based on 100 parts by weight of the vinyl chloride resin for paste according to claim 1.