JP7446098B2 - Vinyl chloride resin composition for paste processing, plastisol for paste processing, and manufacturing method thereof - Google Patents

Description

The present invention relates to a vinyl chloride resin composition used in paste processing, a plastisol used in paste processing, and a method for producing the same.

Paste processing of vinyl chloride resin is carried out by mixing vinyl chloride raw material resin particles for paste processing with a plasticizer to prepare plastisol. At that time, a surfactant may be blended in order to improve the dispersibility of the vinyl chloride raw resin fine particles for paste processing in the plasticizer. As such surfactants, polyoxyethylene alkyl ether type nonionic surfactants are widely used as suitable ones, and phosphate ester type anionic surfactants, which are their phosphoric acid esters, are also used. has been done. These polyoxyethylene chain-containing surfactants generally have a long chain of about 8 repeating oxyethylene units because they have high surfactant ability and are more versatile. ing.

This plastisol is used for low viscosity products such as paints and coating agents. In the case of applications for such low-viscosity products, in order to reduce the viscosity of the resulting plastisol, in addition to the above-mentioned vinyl chloride-based raw material resin particles for paste processing and a plasticizer, vinyl chloride-based blend resin particles for paste processing are added. may be mixed (for example, see Patent Document 1).

Japanese Patent Application Publication No. 11-140256

As mentioned above, when mixing vinyl chloride blend resin particles for paste processing with plastisol, as a surfactant, a nonionic polyoxyethylene alkyl ether with a repeating number of polyoxyethylene units of about 8 as described above is used. When a surfactant or a phosphoric acid ester thereof is used, there is a problem in that when plastisol is stored for a long period of time, a precipitate derived from the vinyl chloride blend resin particles for paste processing is generated.

An object of the present invention is to suppress the generation of sediment derived from vinyl chloride blend resin particles for paste processing in a low viscosity plastisol.

The present inventors used a polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant with a short polyoxyethylene chain and a polyoxyethylene unit repeating number of 1 to 5 as the surfactant. The inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention is as follows.
[1] A vinyl chloride raw material resin for paste processing and a polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (however, the number of repeating polyoxyethylene units is 1 to 5). A vinyl chloride resin composition for paste processing, characterized in that it contains:
[2] The paste according to [1], wherein the polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant is a compound represented by the following formula (1) or (2). Vinyl chloride resin composition for processing.

(In formulas (1) and (2), R represents an alkyl group, an alkenyl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, or an alkaline earth metal, and n is an integer of 1 to 5. and each ethylene group in the polyoxyethylene unit may be substituted with an alkyl group or an alkenyl group.)

[3] The polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant is contained in an amount of 0.01 to 2.0 parts by mass based on 100 parts by mass of vinyl chloride raw material resin for paste processing. The vinyl chloride resin composition for paste processing according to [1] or [2].
[4] The paste according to any one of [1] to [3], wherein the vinyl chloride raw material resin for paste processing is fine particles with an average primary particle diameter of 0.1 to 3.0 μm. Vinyl chloride resin composition for processing.
[5] The vinyl chloride resin composition for paste processing according to any one of [1] to [4], which is in the form of granules.

[6] A vinyl chloride raw material resin for paste processing, a polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (however, the number of repeating polyoxyethylene units is 1 to 5), A plastisol for paste processing, characterized by containing a vinyl chloride blend resin for paste processing and a plasticizer.
[7] The paste according to [6], wherein the polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant is a compound represented by the above formula (1) or (2). Plastisol for processing.
[8] The plastisol for paste processing according to [6] or [7], which has a viscosity of 1500 to 3200 mPa·s.

[9] A method for producing a plastisol for paste processing containing a vinyl chloride raw material resin for paste processing, a vinyl chloride blend resin for paste processing, and a plasticizer, the method comprising:
A method for producing plastisol for paste processing, which comprises blending a polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (with the repeating number of polyoxyethylene units being 1 to 5). .
[10] A polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (provided that the number of repeating polyoxyethylene units is 1 to 5) is added to the aqueous dispersion of vinyl chloride raw material resin for paste processing. ) and drying to prepare vinyl chloride resin granules for paste processing;
a second step of preparing a sol by mixing the vinyl chloride resin granules for paste processing, the vinyl chloride blend resin particles for paste processing, and a plasticizer;
The method for producing plastisol for paste processing according to [9], which comprises:

[11] The polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant is a compound represented by the above formula (1) or (2) [9] or [10] ] The method for producing plastisol for paste processing.

[12] 0.01 to 2.0 parts by mass of the polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant is blended with respect to 100 parts by mass of the vinyl chloride raw material resin for paste processing. The method for producing plastisol for paste processing according to any one of [9] to [11], characterized by:

According to the present invention, in a low-viscosity plastisol, it is possible to suppress the generation of sediment derived from vinyl chloride blend resin particles for paste processing.

[Vinyl chloride resin composition for paste processing]
The vinyl chloride resin composition for paste processing of the present invention comprises a vinyl chloride raw material resin for paste processing, a polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (however, repeating polyoxyethylene units) The number is 1 to 5).

Examples of the form of the vinyl chloride resin composition for paste processing of the present invention include granules as well as combinations of powders such as a mixture of each powder. In the case of granules, the average particle diameter measured with a laser diffraction/scattering particle size distribution analyzer is preferably 20 to 150 μm, more preferably 30 to 100 μm. In the case of powder, the average particle diameter measured with a laser diffraction/scattering particle size distribution analyzer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

In the production of plastisol using a vinyl chloride blend resin for paste processing, by using the vinyl chloride resin composition for paste processing of the present invention, it is possible to obtain a sol with low viscosity, and also to produce a plastisol that uses a vinyl chloride blend resin for paste processing. Generation of sediment derived from vinyl chloride blend resin particles can be suppressed. Moreover, when made into granules, they have a high apparent density, have excellent air transportability and fluidity, and are easy to handle. Furthermore, even after long-term storage, good dispersibility of the vinyl chloride raw material resin for paste processing in the plasticizer can be maintained.

Hereinafter, in this specification, the vinyl chloride-based raw material resin for paste processing in the present invention will be simply referred to as vinyl chloride-based raw material resin, and the polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (however, The number of repeating polyoxyethylene units is 1 to 5) is simply referred to as a phosphate-type anionic surfactant, and the vinyl chloride blend resin for paste processing is sometimes simply referred to as a vinyl chloride blend resin.

(Vinyl chloride raw material resin for paste processing)
The vinyl chloride raw material resin for paste processing in the present invention includes homopolymers of vinyl chloride as well as copolymers mainly composed of vinyl chloride. Containing vinyl chloride as a main component means, for example, that vinyl chloride accounts for 50% by mass or more, preferably 70% by mass or more.

Monomers that can be copolymerized with vinyl chloride include, for example, olefinic compounds such as ethylene and propylene; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; acrylic acid Unsaturated monocarboxylic acid esters such as methyl, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, and N,N-dimethylaminoethyl methacrylate; acrylamide; Unsaturated amides such as methacrylamide; unsaturated nitrites such as acrylonitrile and methacrylonitrile; unsaturated dicarboxylic acids such as maleic acid and fumaric acid; esters and anhydrides thereof; N-substituted maleimides; vinyl methyl ether, Examples include vinyl ethers such as vinyl ethyl ether; vinylidene compounds such as vinylidene chloride; and the like.

The vinyl chloride-based raw material resin of the present invention can be obtained by polymerizing vinyl chloride alone or a monomer mixture consisting of vinyl chloride and an unsaturated monomer copolymerizable with vinyl chloride by a conventionally known method. can. For example, it can be obtained by emulsion polymerization (including seeded emulsion polymerization) or fine suspension polymerization (including seeded fine suspension polymerization).

The obtained vinyl chloride raw material resin is usually fine particles with an average primary particle diameter of 0.1 to 3.0 μm, preferably fine particles of 0.7 to 2.0 μm. The average particle diameter of the primary particles is measured using a light transmission type centrifugal sedimentation particle size distribution analyzer.

(Polyoxyethylene alkyl ether phosphate/phosphate type anionic surfactant)
The polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant in the present invention has a repeating number of polyoxyethylene units of 1 to 5.
Specifically, those shown in the following formula (1) or (2) can be mentioned.

In formulas (1) and (2), R represents an alkyl group, an alkenyl group, or an aralkyl group. The alkyl group, alkenyl group, or alkyl moiety of the aralkyl group may be linear or branched, and the number of carbon atoms thereof is, for example, preferably 1 to 30, more preferably 5 to 20. Preferably, 10 to 16 are more preferable. Examples of the aryl moiety of the aralkyl group include a phenyl group and a naphthyl group.

M represents a hydrogen atom, an alkali metal, or an alkaline earth metal. Examples of the alkali metal include sodium and potassium, with sodium being preferred. Examples of alkaline earth metals include magnesium and calcium, with magnesium being preferred.
n represents an integer of 1 to 5, preferably an integer of 1 to 4.
Moreover, the ethylene group of the polyoxyethylene unit may be substituted with an alkyl group or an alkenyl group, respectively. That is, the ethylene groups of some polyoxyethylene units may have substituents, or the ethylene groups of all polyoxyethylene units may have substituents. The alkyl group and alkenyl group as a substituent may be linear or branched, and the number of carbon atoms thereof is, for example, preferably 1 to 6, more preferably 1 to 4, 1 -2 is more preferred.

More specifically, the phosphate type anionic surfactant represented by formula (1) or (2) can be represented by the following formula (1A) or (2A).

In formulas (1A) and (2A), the polyoxyethylene units may be the same or different. The structure of the polyoxyethylene unit may be a block structure or a random structure. R ¹ to R ⁴ represent a hydrogen atom, an alkyl group, or an alkenyl group, and may be the same or different. Further, n1 is an integer from 0 to 5, n2 is an integer from 0 to 5, and n1+n2=n. n1 is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more.

In the vinyl chloride resin composition for paste processing of the present invention, the phosphoric acid type anionic surfactant is contained in an amount of 0.01 to 2.0 parts by mass based on 100 parts by mass of the vinyl chloride raw material resin. is preferably contained, and more preferably 0.02 to 1.5 parts by mass. By blending within this range, the effects of the present invention can be fully enjoyed when blended into plastisol.

The method for producing the vinyl chloride resin composition for paste processing of the present invention includes a method of mixing a vinyl chloride raw material resin and a phosphoric acid type anionic surfactant to form a mixed powder, and a method of preparing a mixed powder by mixing a vinyl chloride raw material resin and A method of granulating a phosphate type anionic surfactant into granules can be mentioned. The method for producing the granules is specifically the same as the first step in the method for producing plastisol for paste processing, which will be described later.

[Plastisol for paste processing]
The plastisol for paste processing of the present invention consists of a vinyl chloride-based raw material resin for paste processing, a polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (provided that the number of repeating polyoxyethylene units is 1 to 5 ), a vinyl chloride blend resin, and a plasticizer.

The plastisol for paste processing of the present invention has a low viscosity, and the generation of sediment derived from the vinyl chloride blend resin is suppressed. Moreover, the dispersibility of the vinyl chloride-based raw material resin in the plasticizer is good.

The vinyl chloride resin for paste processing and the polyoxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant are the same as those explained for the vinyl chloride resin composition for paste processing of the present invention. be.

(Vinyl chloride blend resin for paste processing)
As with the vinyl chloride raw material resin, the vinyl chloride blend resin for paste processing in the present invention may be a homopolymer of vinyl chloride or a copolymer mainly composed of vinyl chloride.

The vinyl chloride blend resin has a larger particle size than the vinyl chloride raw material resin, and usually has an average primary particle size of 5.0 to 50.0 μm, and 20.0 to 40.0 μm. It is preferable that there be. The method for measuring the average particle diameter of the primary particles is the same as in the case of vinyl chloride-based raw material resin.

The blending amount of the vinyl chloride blend resin may be appropriately selected depending on the use and the like, and is, for example, 25 to 100 parts by mass per 100 parts by mass of the vinyl chloride raw material resin.

(Plasticizer)
In the paste-processing plastisol of the present invention, conventionally known plasticizers for vinyl chloride resin plastisols can be used.

In the present invention, for example, dibutyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, diundecyl phthalate, butylbenzyl phthalate, dinonyl phthalate , phthalic acid derivatives such as dicyclohexyl phthalate; isophthalic acid derivatives such as di-(2-ethylhexyl) isophthalate, diisooctyl isophthalate; di-(2-ethylhexyl)tetrahydrophthalate, di-n-octyltetrahydrophthalate, diisodecyltetrahydro Tetrahydrophthalic acid derivatives such as phthalate; adipic acid derivatives such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate; di-(2-ethylhexyl) azelate, diisooctyl azelate, Azelaic acid derivatives such as di-n-hexyl azelate; sebacic acid derivatives such as di-n-butyl sebacate, di-(2-ethylhexyl) sebacate; di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- - Maleic acid derivatives such as (2-ethylhexyl) maleate; fumaric acid derivatives such as di-n-butyl fumarate, di-(2-ethylhexyl) fumarate; tri-(2-ethylhexyl) trimellitate, tri-n-octyltri Trimellitic acid derivatives such as mellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, triisononyl trimellitate; tetra-(2-ethylhexyl)pyromellitate, tetra- Pyromellitic acid derivatives such as n-octylpyromellitate; citric acid derivatives such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-(2-ethylhexyl) citrate; monomethyl itaconate, mono Itaconic acid derivatives such as butyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di-(2-ethylhexyl) itaconate; oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate; glyceryl Ricinoleic acid derivatives such as monoricinoleate, diethylene glycol monoricinolate; stearic acid derivatives such as glycerin monostearate, diethylene glycol distearate; other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester; Phosphoric acid derivatives such as triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, tris(chloroethyl) phosphate; diethylene glycol dibenzoate, dipropylene glycol dibenzoate, Glycol derivatives such as triethylene glycol dibenzoate and dibutyl methylene bisthioglycolate; Glycerin derivatives such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate; Polyesters such as adipic acid polyester, sebacic acid polyester, and phthalic acid polyester Polymerizable plasticizers such as partially hydrogenated terphenyl, adhesive plasticizers, diallyl phthalate, and acrylic monomers and oligomers can also be used.

Among these, phthalate-based plasticizers are preferred. Note that these plasticizers may be used alone or in combination of two or more.
The amount of plasticizer to be blended may be appropriately selected depending on the intended use, and is, for example, 40 to 250 parts by mass per 100 parts by mass of the vinyl chloride raw material resin.

(Other ingredients)
The plastisol for paste processing of the present invention may contain various other components. Examples include heat stabilizers, fillers, foaming agents, foaming accelerators, viscosity modifiers, adhesion agents, colorants, diluents, ultraviolet absorbers, antioxidants, and reinforcing agents.

The plastisol for paste processing of the present invention is a low-viscosity sol containing a vinyl chloride blend resin, and the viscosity is, for example, 1500 to 3200 mPa·s, preferably 1500 to 3000 Pa·s, and 1500 to 2500 Pa·s. More preferred. This viscosity is measured by the measuring method shown in the examples.

Since the plastisol for paste processing of the present invention is a low viscosity sol, it is useful for low viscosity products such as paints and coating agents.

[Method for manufacturing plastisol for paste processing]
The method for producing a plastisol for paste processing of the present invention is a method for producing a plastisol for paste processing, which contains a vinyl chloride-based raw material resin for paste processing, a vinyl chloride blend resin for paste processing, and a plasticizer. An oxyethylene alkyl ether phosphoric acid/phosphate type anionic surfactant (provided that the number of repeating polyoxyethylene units is 1 to 5) is blended.
Each component is the same as that described for the plastisol for paste processing of the present invention.

The phosphoric acid type anionic surfactant may be blended at any stage in the production of plastisol, for example, it may be blended in advance with the vinyl chloride raw material resin, or it may be blended with the vinyl chloride blend resin. Alternatively, it may be blended at the same time as the vinyl chloride raw material resin, vinyl chloride blend resin, and plasticizer. Among these, a method of blending the resin into the vinyl chloride raw material resin in advance is preferred.

Specifically, as a method of pre-blending a phosphoric acid type anionic surfactant into a vinyl chloride raw material resin, the phosphoric acid type anionic surfactant is added to an aqueous dispersion of a vinyl chloride raw material resin for paste processing. A first step of blending and drying to prepare vinyl chloride resin granules for paste processing, such vinyl chloride resin granules for paste processing, vinyl chloride blend resin particles for paste processing, and a plasticizer. A second step of mixing to prepare a sol can be mentioned.

Here, the aqueous dispersion refers to a dispersion using a dispersion medium mainly composed of water. A dispersion medium mainly composed of water refers to one in which water accounts for 50% by mass or more of the entire dispersion medium, preferably 70% by mass or more, and more preferably 90% or more.
The content of the vinyl chloride raw material resin in the aqueous dispersion is preferably 30 to 70% by mass, more preferably 35 to 65% by mass, and 40 to 60% by mass of the entire dispersion. It is more preferable that

Further, in the first step, the aqueous dispersion of the vinyl chloride raw material resin for paste processing containing the phosphate-type anionic surfactant is usually dried by spray drying. As the spray dryer, any known spray dryer used in the technical field may be used, and the spray type may be a rotating disk type, a two-fluid nozzle type, or a pressure nozzle type. good. This spray drying usually yields granules with an average particle size of about 20 to 150 μm.

Further, in the first step, it is preferable to mix 0.01 to 2.0 parts by mass of the phosphoric acid type anionic surfactant to 100 parts by mass of the vinyl chloride raw material resin, and preferably 0.02 to 1.0 parts by mass. It is more preferable to mix 5 parts by mass. By blending within this range, desired granules can be easily produced, and the effects of the present invention can be fully enjoyed when the granules obtained in the first step are blended into plastisol.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1]
In a pressure-resistant reactor with a stainless steel stirrer and jacket, 100 parts of deionized water, 0.7 parts of sodium dodecylbenzenesulfonate, 1.0 parts of lauryl alcohol/myristyl alcohol mixture, and di-(2-ethylhexyl) peroxydi After charging 0.05 parts of carbonate and degassing under reduced pressure, 100 parts of vinyl chloride monomer was charged and mixed and stirred. After homogenizing this mixture with a homogenizer, it was transferred to another degassed pressure reactor, and the temperature was raised to 47°C to polymerize. After the polymerization conversion rate reached 85%, unreacted monomers were removed. An aqueous dispersion of vinyl chloride-based raw material resin (vinyl chloride polymer aqueous dispersion) having an average primary particle diameter of 1.0 μm and a solid content concentration of 43% by weight was obtained. The primary particle diameter of the vinyl chloride raw material resin dispersed in this vinyl chloride polymer aqueous dispersion was 1.0 μm as measured by a light transmission centrifugal sedimentation particle size distribution analyzer.

Add 0.3 phr of an aqueous solution of polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number: 2) to the above vinyl chloride polymer aqueous dispersion (polyoxyethylene lauryl ether phosphoric acid: 0% per 100 parts by mass of vinyl chloride polymer) .3 parts by mass) was added and sufficiently stirred and dispersed, and then spray-dried with a spray dryer at an inlet temperature of 150°C, an outlet temperature of 55°C, and an atomizer rotation speed of 19,000 rpm to obtain vinyl chloride resin granules for paste processing. The average particle diameter of the vinyl chloride resin granules for paste processing was 70 μm as measured using a laser diffraction/scattering particle diameter distribution analyzer.

[Example 2]
Vinyl chloride resin granules for paste processing were obtained in the same manner as in Example 1, except that the amount of polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number: 2) was changed to 0.03 phr.
[Example 3]
Vinyl chloride resin granules for paste processing were obtained in the same manner as in Example 1, except that the amount of polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number: 2) was changed to 1.2 phr.

[Example 4]
The vinyl chloride resin granules for paste processing obtained in Example 1 were crushed using a pulverizer (AIIW manufactured by Dalton Co., Ltd.) to obtain a paste with an average particle size of 2.0 μm as measured by a laser diffraction/scattering particle size distribution analyzer. A vinyl chloride resin powder for processing was obtained.
[Example 5]
A vinyl chloride resin for paste processing was prepared in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 2) was changed to polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 1). Granules were obtained.

[Example 6]
A vinyl chloride resin for paste processing was prepared in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 2) was changed to polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 4). Granules were obtained.
[Example 7]
Vinyl chloride for paste processing was prepared in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 2) was changed to sodium polyoxyethylene lauryl ether phosphate (number of polyoxyethylene units: 2). Resin granules were obtained.

[Example 8]
A chloride for paste processing was prepared in the same manner as in Example 1 except that polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number 2) was changed to polyoxypropylene lauryl ether phosphoric acid phosphoric acid (polyoxyethylene unit number 2). Vinyl resin granules were obtained.

[Comparative example 1]
Vinyl chloride resin granules for paste processing were obtained in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number: 2) was not added.
[Comparative example 2]
A vinyl chloride resin for paste processing was prepared in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 2) was changed to polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 7). Granules were obtained.

[Comparative example 3]
The vinyl chloride resin granules for paste processing obtained in Comparative Example 2 were crushed using a pulverizer (AIIW manufactured by Dalton Co., Ltd.) to obtain vinyl chloride resin powder for paste processing.
[Comparative example 4]
PVC resin granules for paste processing were prepared in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (number of polyoxyethylene units: 2) was changed to polyoxyethylene lauryl ether (number of polyoxyethylene units: 7). Obtained.

[Comparative example 5]
Vinyl chloride resin granules for paste processing were obtained in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number: 2) was changed to polyethylene glycol (average molecular weight: about 20,000).
[Comparative Example 6]
Vinyl chloride resin granules for paste processing were obtained in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number: 2) was changed to polyethylene glycol (average molecular weight: about 300).

[Comparative Example 7]
Vinyl chloride resin granules for paste processing were obtained in the same manner as in Example 1, except that polyoxyethylene lauryl ether phosphoric acid (polyoxyethylene unit number: 2) was changed to polyvinyl alcohol.

Regarding the vinyl chloride resin compositions (granules, powder) for paste processing of Examples 1 to 8 and Comparative Examples 1 to 7 above, (1) paste viscosity, (2) plastisol sedimentation property, (3) apparent density, and ( 4) Dispersibility in plasticizer was evaluated by the following method.

(1) Paste viscosity In a 500 ml plastic cup, 50 parts by weight of vinyl chloride resin composition for paste processing (granules, powder), vinyl chloride blend resin [PBZXA manufactured by Shin Daiichi PVC Co., Ltd. Average particle diameter of primary particles 35 μm] 50 parts by weight of di-(2-ethylhexyl) phthalate (DOP manufactured by J-Plus Co., Ltd.) as a plasticizer, and 2 parts by weight of a liquid barium-zinc heat stabilizer were added, and a propeller stirring blade was attached. After kneading with a mechanically controlled stirrer for 10 minutes, plastisol was obtained by kneading with a vacuum deaerator for 5 minutes. After standing for 1 hour in an atmosphere with a temperature of 23°C and a humidity of 50% RH, the plastisol was thoroughly stirred and tested using a Brookfield viscometer (LVDV-3T manufactured by Hideko Seiki Co., Ltd.) rotor No. The viscosity was measured at 4 and 6 rpm.

(2) Sedimentation property of plastisol Weighed 200 g of plastisol prepared in the same manner as in (1) above into a 150 ml plastic container, left it for 7 days at a temperature of 23°C and a humidity of 50% RH, and then turned the container upside down. The plastisol was discharged for 5 minutes, and the mass of the residue in the container was measured and the presence or absence of deposits was confirmed. The sedimentation rate of plastisol was determined using the following formula.

Sol sedimentation rate (%) = (mass of plastisol remaining in container ÷ 200 x 100)

(3) Apparent Density The obtained vinyl chloride resin composition for paste processing was measured using a JIS Kasa specific gravity meter (Tsutsui Rikagaku Kikai Co., Ltd.) according to the method of JIS K7365 to determine the apparent density.

(4) Dispersibility in plasticizer Three months after production, the obtained vinyl chloride resin composition for paste processing was dispersed in bis(2-ethylhexyl) adipate as a plasticizer, and laser diffraction/scattering particles were dispersed in bis(2-ethylhexyl) adipate as a plasticizer. The sample was placed in a size distribution measuring device (LA-960 manufactured by Horiba, Ltd.) and subjected to ultrasonic waves for 5 minutes to measure the particle size distribution and determine the proportion of particles with a diameter of 10 μm or less.

The results are shown in Table 1.

The paste viscosity of the vinyl chloride resin granules for paste processing of Examples 1 to 3 and 5 to 8 was sufficiently low, and no deposits derived from the vinyl chloride blend resin were observed in the plastisol after standing for 7 days. Ta. Furthermore, the resin granules had a high apparent density and maintained high dispersibility even after 3 months.

In addition, as shown in Examples 1 to 3, the paste viscosity was lower as the amount of phosphoric acid type anionic surfactant added was large, but even when the amount added was small, sufficient viscosity reducing effect was exhibited. . Further, the apparent density was higher as the amount of the phosphate anionic surfactant added was higher, and even when the amount added was smaller, the apparent density was relatively high.
Furthermore, the resin granules (Example 3) exhibited higher apparent density than the resin powder (Example 4).

As mentioned above, although the vinyl chloride resin powder for paste processing of Example 4 was inferior in apparent density, it was superior in paste viscosity, plastisol sedimentation after 7 days of standing, and dispersibility after 3 months, compared to before pulverization. The physical properties were equivalent to those of the resin granules (Example 3).

On the other hand, in Comparative Example 1 in which the phosphoric acid type anionic surfactant of the present invention was not added, the paste viscosity was high and the apparent density was low.
Furthermore, in Comparative Example 2 using a phosphoric acid type anionic surfactant (7 polyoxyethylene units), deposits were observed in the plastisol after standing for 7 days. Therefore, considering the results of Examples 1, 5, and 6 together, it is considered that the number of polyoxyethylene units is preferably about 1 to 5.
In Comparative Example 3, in which the resin granules of Comparative Example 2 were crushed, deposits were observed in the plastisol after being left standing for 7 days, as in Comparative Example 2. Moreover, the apparent density was lower than that of Comparative Example 2.

In Comparative Example 4 using a nonionic surfactant (polyoxyethylene unit number: 7) that is not a phosphoric acid type, the paste viscosity was low, but deposits were observed in the plastisol after standing for 7 days. .
In Comparative Examples 5 to 7 using water-soluble polymers, a significant increase in paste viscosity was observed in all cases. Further, the dispersibility of the resin granules after 3 months had decreased in all cases.

The vinyl chloride resin composition for paste processing and the plastisol for paste processing of the present invention are industrially useful because they can be used for paste processing of vinyl chloride resin.

Claims (4)

PVC raw material resin particles for paste processing with an average primary particle size of 0.1 to 3.0 μm , a phosphoric acid type anionic surfactant, and an average primary particle size of 5.0 to 50.0 μm A plastisol for paste processing containing vinyl chloride blend resin particles for paste processing and a plasticizer,
A plastisol for paste processing, wherein the phosphoric acid type anionic surfactant is a compound represented by the following formula (1A).
(In formula (1A), R represents an alkyl group, an alkenyl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, or an alkaline earth metal, n1 is an integer of 0 to 5, and n2 is an integer from 0 to 5, n1+n2 is an integer from 1 to 5, and R ¹ to R ⁴ represent a hydrogen atom or an alkyl group.) Vinyl chloride raw material resin particles for paste processing with an average primary particle diameter of 0.1 to 3.0 μm and vinyl chloride blend resin particles for paste processing with an average primary particle diameter of 5.0 to 50.0 μm A method for producing a plastisol for paste processing, comprising: and a plasticizer,
A method for producing plastisol for paste processing, which comprises blending a phosphate-type anionic surfactant that is a compound represented by the following formula (1A).
(In formula (1A), R represents an alkyl group, an alkenyl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, or an alkaline earth metal, n1 is an integer of 0 to 5, and n2 is an integer from 0 to 5, n1+n2 is an integer from 1 to 5, and R ¹ to R ⁴ represent a hydrogen atom or an alkyl group.) A first step of blending a phosphoric acid type anionic surfactant into an aqueous dispersion of fine particles of vinyl chloride raw material resin for paste processing, and drying the mixture to prepare vinyl chloride resin granules for paste processing;
a second step of preparing a sol by mixing the vinyl chloride resin granules for paste processing, the vinyl chloride blend resin particles for paste processing, and a plasticizer;
3. The method for producing plastisol for paste processing according to claim 2 , comprising: 4. The method according to claim 2 or 3 , wherein the phosphoric acid type anionic surfactant is blended in an amount of 0.01 to 2.0 parts by mass based on 100 parts by mass of the vinyl chloride raw resin fine particles for paste processing. A method for producing plastisol for paste processing.