JPH09263601A - Production of vinyl chloride polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a vinyl chloride polymer, reducing the generation of stick ing to a roll, excellent in transparency, thermal stability, and absorption of a plasticizer and forming the reduced number of fish eyes by a suspension polymerization of a vinyl chloride-based monomer in the presence of a specified dispersing stabilizer, etc. SOLUTION: A suspension polymerization of a vinyl chloride-based monomer is performed in the presence of a polymerization initiator in an aqueous medium by using a dispersing stabilizer comprising (A) a partially saponified polyvinyl alcohol (PVA) having 70-90mol% degree of saponification and 1,500-3,000 averaged molecular weight, (B) a PVA having 70-90mol% degree of saponification and 300-1,000 average molecular weight and (C) a water-soluble cellulose ether, regulating the total amount of the components A and B to 0.04-0.5 pt.wt. and the amount of the component C to 0.005-0.2 pt.wt. based on 100 pts.wt. vinyl chloride-based monomer and the weight ratio of the components A/B to (1/1)-(20/1) and the weight ratio of the components (A+B)/C to (1/1)-(25/1) and additionally adding 0.005-0.5 pt.wt. higher alcoholic lubricant based on 100 pts.wt. vinyl chloride-based monomer to provide the objective vinyl chloride polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride polymer, and more specifically, it has excellent heat stability, fish eye, plasticizer absorbability, and little sticking of roll during calendar molding. The present invention relates to a method for producing a vinyl chloride polymer.

[0002]

2. Description of the Related Art Vinyl chloride polymers have excellent physical properties.
Due to its mechanical properties, it is used in many fields. As a molding method of the vinyl chloride polymer, calender molding, extrusion molding, injection molding and the like are common,
In recent years, there has been a demand for the development of a vinyl chloride-based polymer that is excellent in heat stability, plasticizer absorbency, fish eye, and has less roll sticking in order to improve quality and productivity in calendar molding applications.

Various methods have been proposed to meet these demands, and Japanese Patent Laid-Open No. 6-65309 and Japanese Patent Laid-Open No. 6-30909 have been proposed.
JP-A-211909 proposes a method of using a specific dispersant as a method of obtaining a molded product having good thermal stability and fish eyes.

Further, JP-A-4-239002 and JP-A-4-239003 propose a method of using a specific metal salt as a method for improving roll adhesion.

[0005]

However, the vinyl chloride polymers obtained by the methods described in JP-A-6-65309 and JP-A-6-211909 have thermal stability, plasticizer absorbability, and fish. Although a molded product having a good eye can be obtained, calender molding has a problem that roll adhesion is remarkably generated and the long-run property during molding is lacking. Further, Japanese Patent Laid-Open No. 4-239002,
The vinyl chloride-based polymer obtained by the method described in JP-A-4-239003 has not sufficiently achieved the effect of improving the roll adhesiveness.

Therefore, an object of the present invention is to provide a method for producing a vinyl chloride polymer which is excellent in heat stability, plasticizer absorbability, fish eye, and has less roll sticking during calendar molding. .

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, in a method for producing a vinyl chloride polymer by suspension polymerization in an aqueous medium,
By using a specific dispersion stabilizer in a specific ratio and further using a higher alcohol-based lubricant, it is excellent in heat stability, plasticizer absorption, and fish eyes, and vinyl chloride-based with less roll adhesion during calendar molding. They have found that a polymer can be obtained, and completed the present invention.

That is, the present invention provides a method for producing a vinyl chloride polymer by carrying out suspension polymerization of a vinyl chloride monomer in an aqueous medium in the presence of a polymerization initiator and a dispersion stabilizer. Partially saponified polyvinyl alcohol (hereinafter referred to as PVA) having a saponification degree of 70 to 90 mol% and an average degree of polymerization of 1500 to 3000 (A), a PVA having a saponification degree of 70 to 90 mol% and an average degree of polymerization of 300 to 1000 ( B) and water-soluble cellulose ether (C) are used in a total amount of 0.04 to 0.5 parts by weight of PVA (A) and PVA (B) per 100 parts by weight of vinyl chloride monomer, water-soluble cellulose The amount of ether (C) used is 0.005 to 0.2 part by weight, and PVA (A) / PVA (B) = 1/1 to 20/1
(Weight ratio), (PVA (A) + PVA (B)) / water-soluble cellulose ether (C) = 1/1 to 25/1 (weight ratio), and the higher alcohol-based lubricant is a vinyl chloride-based monomer The present invention relates to a method for producing a vinyl chloride polymer, which comprises adding 0.005 to 0.5 part by weight to 100 parts by weight of a body.

Hereinafter, the present invention will be described in detail.

The dispersion stabilizer used in the present invention has a saponification degree of 70 to 90 mol% and an average degree of polymerization of 1500 to 300.
0 of PVA (A), 70-90 mol% of saponification degree, PVA (B) of 300-1000 average degree of polymerization, and water-soluble cellulose ether (C).

P used as the dispersion stabilizer component in the present invention
VA (A) has a saponification degree of 70 to 90 mol% and a polymerization degree of 15
PVA of 0 to 3000, preferably a saponification degree of 7
It is a PVA having 5 to 90 mol% and a degree of polymerization of 1700 to 2800. Here, when the degree of polymerization of PVA (A) is less than 1500, or when the degree of saponification is less than 70 mol%, the improving effect on the roll adhesion of the obtained vinyl chloride polymer is not sufficient, The polymerization system may also become unstable. On the other hand, when the degree of polymerization exceeds 3,000 or when the degree of saponification exceeds 90 mol%, a lot of fish eyes are generated in the molded product of the obtained vinyl chloride-based polymer and the obtained vinyl chloride is obtained. Coarse particles may be generated in the polymer.

P used as a dispersion stabilizer component in the present invention
VA (B) has a saponification degree of 70 to 90 mol% and a polymerization degree of 3
A PVA of 0 to 1000, preferably a saponification degree of 7
It is a PVA having 0 to 90 mol% and a polymerization degree of 600 to 1000. Here, when the degree of polymerization of PVA (B) is less than 300, or when the degree of saponification is less than 70 mol%,
The effect of improving the roll adhesion of the obtained vinyl chloride polymer is not sufficient, and the polymerization system may become unstable. On the other hand, when the degree of polymerization exceeds 1000 or when the degree of saponification exceeds 90 mol%, the vinyl chloride polymer obtained has a reduced plasticizer absorption amount or the obtained vinyl chloride polymer. A lot of fish eyes occur in the molded products of.

The amount of PVA (A) and PVA (B) used as the dispersion stabilizer component in the present invention is 0.04 to 0 with respect to 100 parts by weight of the vinyl chloride monomer. 0.5 parts by weight, preferably 0.04 to
0.2 parts by weight. The amount of the water-soluble cellulose ether (C) used as the dispersion stabilizer component is 0.005 to 0.2 part by weight, preferably 0.005 to 0. 1 part by weight. Here, the total amount of PVA (A) and PVA (B) used is 0.
When the amount is less than 04 parts by weight, Ca-Z generally used as a stabilizer during molding of the obtained vinyl chloride polymer.
The effect of improving the thermal stability when an n-based metal soap stabilizer is blended is not sufficient. On the other hand, if the amount is more than 0.5 parts by weight, physical properties such as plasticizer absorbability, fish eye, and roll adhesiveness are deteriorated as a whole, which is not preferable. When the amount of the water-soluble cellulose ether (C) used is less than 0.005 parts by weight, deterioration of fish eyes is remarkable, and when it exceeds 0.2 parts by weight, plasticizer absorbability, fish eyes, and roll adhesion. It is not preferable because the physical properties such as properties are deteriorated as a whole.

PVA (A) / PVA in the present invention
The ratio of (B) used is PVA (A) / PVA (B) = 1
/ 1 to 20/1 (weight ratio), preferably 2/1 to 15 /
1 (weight ratio). The amount of PVA (B) used is PVA
When the amount is more than the same amount as (A), the roll adhesion is significantly deteriorated. On the other hand, when the amount is less than 1/20, the plasticizer absorption and the fish eye deteriorate.

Further, (PVA (A) + PVA (B)) /
The proportion of water-soluble cellulose ether (C) used is (PV
A (A) + PVA (B)) / water-soluble cellulose ether (C) = 1/1 to 25/1 (weight ratio), preferably 2 /
It is 1 to 18/1 (weight ratio). When the amount of the water-soluble cellulose ether (C) used is larger than the equivalence of PVA (A) + PVA (B), the polymerization system becomes unstable. On the other hand, 25
If the amount is less than 1 / l, the plasticizer absorption and the fisheye are deteriorated.

PVA (A) used as a dispersion stabilizer component
The PVA (B) and PVA (B) may be used in combination of two or more kinds as long as they are within the ranges described above, or may be modified. Further, the water-soluble cellulose ether (C) may be any one as long as it belongs to the water-soluble cellulose ether, and since the dispersion stability of the polymerization system at the time of polymerization is excellent, the degree of methoxy substitution is 25 to 30% by weight, hydroxypropoxy. Hydroxypropyl methylcellulose having a substitution degree of 5 to 15% by weight and a 2% by weight aqueous solution having a viscosity at 20 ° C. of 10 to 100 cps is preferable.

As the higher alcohol lubricant used in the present invention, any higher alcohol lubricant can be used. Further, at least 1 monovalent alkyl alcohol component having an alkyl group having 8 or more carbon atoms is used because the generation of odor during molding can be suppressed to a low level.
It is preferable that the higher alcohol lubricant contains one or more kinds, for example, a higher alcohol lubricant such as octyl alcohol, dodecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, or one or more kinds of these higher alcohol components. Higher alcohol lubricants can be mentioned. The higher alcohol-based lubricants can be used alone or in combination of two or more.

The amount of the higher alcohol lubricant used is 0.005 to 100 parts by weight of the vinyl chloride monomer.
0.5 parts by weight, preferably 0.05 to 0.2 parts by weight. When the amount of the higher alcohol-based lubricant used is less than 0.005 part by weight, the improving effect on the roll adhesion becomes insufficient, and when it exceeds 0.5 part by weight, the improving effect on the roll adhesion is saturated. However, not only the improvement effect commensurate with the amount used cannot be expected, but another problem such as deterioration of the transparency of the molded product occurs.

The timing of addition of the higher alcohol lubricant in the present invention is not particularly limited, and it may be added at any time before, during, or after the polymerization. or,
There is also no particular limitation on the method of adding the higher alcohol-based lubricant, for example, the higher alcohol-based lubricant as it is, a dispersion of the higher alcohol-based lubricant in water, a solution of the higher alcohol-based lubricant, or the like dissolved in an organic solvent, etc., added collectively, dividedly added, continuously. The method of addition, etc. are mentioned.

In the present invention, a mercapto group and a hydroxyl group are used as a molecular weight modifier during polymerization in order to further improve the thermal stability when a Sn-based stabilizer is added to the resulting vinyl chloride polymer and molded and processed. It is preferable to use a compound having a group in combination. Examples of the compound include 2-
Mercaptoethanol, 3-mercaptopropanol,
4-mercaptobutanol, 1-thioglycerol, thioglycerin and the like can be mentioned.

When the molecular weight modifier is used, the amount used is 0.001 to 0. 0 per 100 parts by weight of the vinyl chloride-based monomer because of its excellent balance between the effect of improving thermal stability and the adhesiveness of the roll. It is preferably 05 parts by weight.

When the molecular weight modifier is used, it may be added at any time before or during the polymerization as long as the polymerization yield is less than 75%. The method of adding the molecular weight modifier is not limited, and examples thereof include a method in which the molecular weight modifier is dissolved in water or an organic solvent as it is, but is added all at once, dividedly, or continuously.

In the present invention, in order to further improve the initial colorability of the vinyl chloride polymer obtained, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant together as an antioxidant. Examples of the phenolic antioxidant include dibutylhydroxytoluene, bisphenol A, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, triethyleneglycol-bis [3- (3- t-butyl-5
-Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,3
5) -Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythyl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 4,4′-butylidene bis- (6-
t-butyl-3-methylphenol) and the like.
These phenolic antioxidants can be used alone or in combination of two or more. Examples of the sulfur-based antioxidant include thiodipropionic acid, lauryl stearyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate and dimyristyl thiodipropionate. These sulfur-based antioxidants can also be used alone or in combination of two or more.

When the antioxidant is used, the amount of the antioxidant used is 100% by weight of the vinyl chloride-based monomer because of its excellent balance between the efficiency of improving the initial colorability and the cost. Is preferably 0.001 to 0.05 parts by weight. Moreover, it is preferable that it is in the range of phenolic antioxidant / sulfur antioxidant = 9/1 to 1/9 (weight ratio).

When the antioxidant is used, it is preferable to add the antioxidant before the recovery of unreacted vinyl chloride at the end of the polymerization. Further, the method of adding the antioxidant is not particularly limited, and examples thereof include a method of adding the antioxidant as it is by emulsifying it in water, or by dissolving it in an organic solvent.

In the production method of the present invention, the suspension polymerization method generally used can be applied as it is. For example, specifically, the following method is used.

Pure water, a dispersion stabilizer and a polymerization initiator are put into a pressure resistant polymerization vessel equipped with a stirrer and put in a reduced pressure state. Next, a vinyl chloride-based monomer is press-fitted, and the inside of the polymerization vessel is heated with stirring to start polymerization. As polymerization conditions at that time, the polymerization temperature is 20 to 90 ° C., and the polymerization time is 1 to 40.
The time can be increased, and after the completion of the polymerization, the unreacted vinyl chloride-based monomer is recovered, and the slurry is taken out and dehydrated and dried to obtain a vinyl chloride-based polymer.

The polymerization initiator used in the present invention may be one generally used as a polymerization initiator in a suspension polymerization method, and examples thereof include diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanate and tert-. Peroxides such as hexyl peroxypivalate and benzoyl peroxide; azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile and the like;
These can be used alone or in combination of two or more.

In the present invention, a vinyl monomer copolymerizable with a vinyl chloride monomer or a polymer capable of graft polymerization with a vinyl chloride monomer may be added and polymerized as required.

The vinyl chloride monomer in the present invention means
A vinyl chloride monomer or a mixture of a vinyl chloride monomer and a vinyl-based monomer copolymerizable with a vinyl chloride monomer.

Examples of the vinyl monomer copolymerizable with the vinyl chloride monomer include vinyl acetates such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl laurate and vinyl stearate; ethylene, propylene, Olefins such as isobutylene; alkyl or aryl vinyl ethers such as isobutyl vinyl ether, phenyl vinyl ether, octyl vinyl ether; halogenated olefins such as vinylidene chloride, vinyl fluoride, allyl chloride, vinyl bromide; ethyl acrylate, n
-Butyl acrylate, n-butyl methacrylate, 2
-Acrylic acid or methacrylic acid esters such as ethylhexyl acrylate, 2-ethylhexyl methacrylate, stearyl methacrylate; acrylic derivatives such as acrylic acid, methacrylic acid, crotonic acid, acrylonitrile, maleic anhydride, itaconic anhydride and the like. it can.

Examples of polymers which can be graft-copolymerized with vinyl chloride-based monomers include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer, chlorinated polyethylene, polyurethane, polybutadiene-styrene- Methyl methacrylate copolymer (MB
S), polybutadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), polybutyl acrylate, butyl rubber, polystyrene, styrene-butadiene copolymer, crosslinked acrylic rubber and the like.

In the production method of the present invention, in the initial stage of polymerization,
During or after the polymerization, other polymerization additives such as a gelation improver, a pH adjuster, and a scale inhibitor may be used.

[0034]

EXAMPLES The production method of the present invention will be explained based on examples, but the present invention is not limited to these examples.

The thermal stability, plasticizer absorption, fish eye, initial colorability, transparency, and roll tackiness of the vinyl chloride polymers obtained in Examples and Comparative Examples were evaluated by the following methods. It was

-Thermal Stability--Ca-Zn Metal Soap Stabilizer Blending System-100 parts by weight of vinyl chloride polymer, 2 parts by weight of Ca-Zn composite metal soap stabilizer, 3 parts by weight of epoxidized soybean oil, 3 parts by weight of dioctyl phthalate and 0.2 parts by weight of stearic acid are blended, and 150 g of the blend is kneaded with a 6 inch roll having a roll surface temperature of 160 ° C. for 5 minutes to give a thickness of 1 mm.
A sheet molded body of was obtained. The time required for blackening the test piece cut out from the sheet molded body was measured in an oven at 165 ° C.

-Sn-based stabilizer compounding system- 100 parts by weight of a vinyl chloride-based polymer, 3 parts by weight of dibutyltin malate-based stabilizer, and 0.2 parts by weight of a fatty acid ester-based lubricant are blended, and 150 g of the composition is blended on the roll surface. Temperature 1
The mixture was kneaded with a 6 inch roll at 50 ° C. for 5 minutes to obtain a sheet molded body having a thickness of 1 mm. The time required for blackening the test piece cut out from the sheet molded body was measured in an oven at 190 ° C.

-Amount of Plasticizer Absorbed- To the obtained vinyl chloride polymer, an excess amount of plasticizer (dioctyl phthalate; DOP) was added, and the mixture was allowed to stand at room temperature for 10 minutes and then centrifuged (produced by Domestic Centrifuge Co., Ltd.). ) With 30
The plasticizer not absorbed by the polymer was removed by centrifugation at 00 rpm. The amount of plasticizer retained in the vinyl chloride polymer after centrifugation was measured, and the ratio of the plasticizer to the polymer was expressed as a percentage, which was taken as the plasticizer absorption amount.

-Fish eye- 100 parts by weight of vinyl chloride polymer, 40 parts by weight of di-2-ethylhexyl phthalate, 3 parts by weight of Ca-Zn complex metal soap stabilizer, and a small amount of ultramarine blue were mixed, and then the roll was heated at 160 ° C. The number of fish eyes recognized in 50 cm ^{2 of the} sheet obtained by kneading for 3 minutes was counted.

-Initial Coloring and Transparency- 100 parts by weight of vinyl chloride polymer, 3 parts by weight of dibutyltin malate stabilizer, and 0.2 parts by weight of fatty acid ester lubricant are blended, and 150 g of the blend is blended on the roll surface. Temperature 1
The mixture was kneaded with a 6 inch roll at 50 ° C. for 5 minutes to obtain a sheet molded body having a thickness of 1 mm. Subsequently, the sheet molded bodies were laminated and a 5 mm press molded body was obtained by pressing at 175 ° C.
The initial colorability was determined by measuring the yellow value (YI) of this molded product with a color difference meter (Nippon Denshoku Industries Co., Ltd., trade name 1001DP). The smaller the YI value, the better the initial colorability.

The transparency was determined by measuring the haze value of this molded product with a turbidimeter. The smaller the haze value, the better the transparency.

-Roll Adhesion- 4 parts by weight of dibutyltin malate stabilizer and 1.5 parts of fatty acid ester lubricant per 100 parts by weight of vinyl chloride polymer.
Parts by weight were compounded. Surface temperature of this compounded composition is 185 ° C.
The composition was wrapped around a roll with a 2-inch 8-inch roll (manufactured by Kansai Roll Co., Ltd.) and kneaded for 5 minutes, and the sheet was taken out. Then, the same operation was repeated five times to evaluate the ease of peeling of the sheet.

Evaluation Criteria for Calendar Workability ○ No tackiness (peeling without problems).

ΔSlightly sticky (easy peeling).

X Large adhesion (slightly difficult peeling).

XX Strong adhesion (difficulty peeling).

Example 1 140 parts by weight of pure water, a saponification degree of 80 mol% and a polymerization degree of 260 were placed in a stainless steel autoclave having an internal volume of 500 liters.
0.07 parts by weight of PVA, 73 mol% of saponification degree, 0.01 parts by weight of PVA having a polymerization degree of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
Hydroxypropyl methylcellulose (hereinafter, H
0.01 parts by weight (abbreviated as PMC) was used, and 0.025 parts by weight of tert-hexyl peroxypivalate was added to make a vacuum. Then, 100 parts by weight of a vinyl chloride monomer was charged, and the inside of the autoclave was heated to 65 ° C. with stirring to carry out polymerization. When the pressure in the autoclave dropped 2.0 kg / cm ² from the pressure in the steady state of the polymerization reaction, 0.02 parts by weight of dibutylhydroxytoluene (hereinafter abbreviated as BHT) was added, and the unreacted vinyl chloride monomer was added. Recovered. The polymerization time was 6 hours.

Before recovering unreacted vinyl chloride monomer,
As a higher alcohol-based lubricant, a higher alcohol-based lubricant mainly composed of a higher alcohol component having an alkyl chain having 16 to 18 carbon atoms (manufactured by Kao Corporation, trade name Calcol 8688)
Was added to the vinyl chloride polymer in an amount of 0.1 part by weight, and the slurry was taken out from the autoclave and dehydrated and dried to obtain a vinyl chloride polymer at a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The obtained vinyl chloride polymer was Ca--Zn.
It was excellent in heat stability, plasticizer absorbability and fish eye when the metal soap stabilizer was blended, and the roll adhesiveness was improved.

Example 2 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0 PVA 0.06 parts by weight, saponification degree 73 mol%, polymerization degree 800 PVA 0.02 parts by weight, hydroxypropoxy substitution degree 9.5% by weight, 2% by weight aqueous solution having a viscosity of 50 cps at 20 ° C. 0.01 parts by weight of HPMC, which is a higher alcohol lubricant, mainly having 12 to 1 carbon atoms.
Higher alcohol lubricant consisting of higher alcohol component of alkyl chain of 6 (Kalcoal 425, manufactured by Kao Corporation)
0) 0.15 part by weight, octadecyl-3- (3,5-di-t-butyl-4) as a phenolic antioxidant.
-Hydroxyphenyl) propionate (Ciba-Geigy Co., Ltd., trade name Irganox 1076) (hereinafter, I
rg. (Abbreviated as 1076) was used in the same manner as in Example 1 except that 0.02 part by weight was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The obtained vinyl chloride polymer was Ca--Zn.
It was excellent in heat stability, plasticizer absorbability and fish eye when the metal soap stabilizer was blended, and the roll adhesiveness was improved.

Example 3 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.04 parts by weight of PVA having a saponification degree of 73 mol%, 0.04 parts by weight of PVA having a degree of polymerization of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
0.005 parts by weight of HPMC, which is a higher alcohol-based lubricant, and a higher alcohol-based lubricant (Kalcole 6850, trade name, manufactured by Kao Corporation) mainly composed of a higher alcohol component of an alkyl chain having 16 to 18 carbon atoms. 0.1 part by weight, as a phenolic antioxidant, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4)
-Hydroxyphenyl) propionate] (Ciba-Geigy Co., Ltd., trade name Irganox 245) (hereinafter, I
rg. (Abbreviated as 245) except that 0.02 part by weight was used, and a vinyl chloride polymer was obtained with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The obtained vinyl chloride polymer was Ca--Zn.
It was excellent in heat stability, plasticizer absorbability and fish eye when the metal soap stabilizer was blended, and the roll adhesiveness was improved.

Example 4 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.07 parts by weight of PVA, 73 mol% of saponification degree, 0.01 parts by weight of PVA having a polymerization degree of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
0.02 parts by weight of HPMC, which is a higher alcohol-based lubricant, and a higher alcohol-based lubricant (Kalcole 6870, manufactured by Kao Co., Ltd.) mainly composed of a higher alcohol component having an alkyl chain having 16 to 18 carbon atoms. .05 parts by weight, bisphenol A as a phenolic antioxidant
Was performed in the same manner as in Example 1 except that 0.02 part by weight of was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The resulting vinyl chloride polymer was Ca--Zn.
It was excellent in heat stability, plasticizer absorbability and fish eye when the metal soap stabilizer was blended, and the roll adhesiveness was improved.

Example 5 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.075 parts by weight of PVA of 0, saponification degree of 73 mol%,
0.005 parts by weight of PVA having a degree of polymerization of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, and a 2% by weight aqueous solution have a viscosity of 50 cp at 20 ° C.
was used in the same manner as in Example 4 except that 0.02 parts by weight of HPMC of s was used and 0.05 parts by weight of Calcol 8688 was used as a higher alcohol-based lubricant. Got united.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The vinyl chloride polymer obtained was Ca--Zn.
It was excellent in heat stability, plasticizer absorbability and fish eye when the metal soap stabilizer was blended, and the roll adhesiveness was improved.

Example 6 As a higher alcohol lubricant, a higher alcohol lubricant mainly composed of a higher alcohol component having an alkyl chain having 16 to 18 carbon atoms (Kao Corporation, trade name Calcol 8665)
0.05 part by weight, as a phenolic antioxidant, I
rg. 245 as 0.02 part by weight, as a molecular weight modifier,
2-mercaptoethanol (hereinafter abbreviated as ME) was added to 0.
A vinyl chloride polymer was obtained in the same manner as in Example 2 except that the polymerization temperature was 63 ° C. using 01 parts by weight, and the polymerization conversion rate was about 85%.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The obtained vinyl chloride polymer was Ca--Zn.
Excellent heat stability, plasticizer absorbency and fisheye when compounded with metal-based soap stabilizer, improved roll adhesion, and also excellent thermal stability when compounded with Sn-based stabilizer. there were.

Example 7 0.05 parts by weight of Calcol 6870 as a higher alcohol lubricant, and Ir as a phenolic antioxidant
g. 0.01 parts by weight of 245, dilauryl thiodipropionate (hereinafter referred to as DLTP) as a sulfur-based antioxidant.
Abbreviated) was used in the same manner as in Example 6 to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The obtained vinyl chloride polymer was Ca--Zn.
It has excellent heat stability, plasticizer absorbency and fisheye when compounded with metal-based metal stabilizer, and has improved roll adhesiveness. Furthermore, it has excellent thermal stability and initial colorability when compounded with Sn-based stabilizer. It was excellent.

Example 8 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 220 were used.
0.06 parts by weight of PVA of 0, 73 mol% of saponification degree, 0.02 parts by weight of PVA of polymerization degree of 600, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
0.01 parts by weight of HPMC, 0.05 parts by weight of Calcol 8688 as a higher alcohol lubricant, and Irg. 1076
Was used in the same manner as in Example 7 except that 0.01 part by weight of distearyl thiodipropionate (hereinafter abbreviated as DSTP) was used as a sulfur-based antioxidant.
A vinyl chloride polymer was obtained with a polymerization conversion of about 85%.

The polymerization conditions are shown in Table 1. The evaluation results of the obtained vinyl chloride polymer are shown in Table 5.

The obtained vinyl chloride polymer was Ca--Zn.
It has excellent heat stability, plasticizer absorbency and fisheye when compounded with metal-based metal stabilizer, and has improved roll adhesiveness. Furthermore, it has excellent thermal stability and initial colorability when compounded with Sn-based stabilizer. It was excellent.

Example 9 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 220
0.06 parts by weight of PVA having a saponification degree of 80 mol%, 0.02 parts by weight of PVA having a degree of polymerization of 600, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
0.01 parts by weight of HPMC is used, and 0.05 parts by weight of Calcol 6870 as a higher alcohol lubricant.
As a phenolic antioxidant, Irg. 1076 to 0.
01 parts by weight of dimyristyl thiodipropionate (hereinafter abbreviated as DMTP) as a sulfur-based antioxidant of 0.0
Example 8 was repeated except that 1 part by weight was used.
% Of vinyl chloride polymer was obtained at a polymerization conversion of 0.1%.

The polymerization conditions are shown in Table 2. Table 6 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer was Ca--Zn.
It has excellent heat stability, plasticizer absorbency and fisheye when compounded with metal-based metal stabilizer, and has improved roll adhesiveness. Furthermore, it has excellent thermal stability and initial colorability when compounded with Sn-based stabilizer. It was excellent.

Example 10 As a dispersion stabilizer, the degree of saponification was 80 mol% and the degree of polymerization was 220.
0.06 parts by weight of PVA of 0, 88 mol% of saponification degree, 0.02 parts by weight of PVA of polymerization degree of 600, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
0.01 parts by weight of HPMC, which is 0.1 parts by weight of Calcol 6870 as a higher alcohol lubricant,
As a phenolic antioxidant, Irg. 1076 to 0.
01 parts by weight, DLTP as a sulfur-based antioxidant 0.0
Example 8 was repeated except that 1 part by weight was used.
% Of vinyl chloride polymer was obtained at a polymerization conversion of 0.1%.

The polymerization conditions are shown in Table 2. Table 6 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer was Ca--Zn.
It has excellent heat stability, plasticizer absorbency and fisheye when compounded with metal-based metal stabilizer, and has improved roll adhesiveness. Furthermore, it has excellent thermal stability and initial colorability when compounded with Sn-based stabilizer. It was excellent.

Comparative Example 1 A vinyl chloride polymer was obtained in the same manner as in Example 1 except that the higher alcohol lubricant was not used and the polymerization conversion rate was about 85%.

The polymerization conditions are shown in Table 3. Table 7 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had a problem in roll tackiness.

Comparative Example 2 As a higher alcohol type lubricant, 2 parts of Calcol 8688 were used.
The same procedure as in Example 1 was carried out except that the amount by weight was about 85%.
A vinyl chloride polymer was obtained at a polymerization conversion ratio of.

The polymerization conditions are shown in Table 3. Table 7 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer was inferior in transparency.

Comparative Example 3 As a dispersion stabilizer, a saponification degree of 73 mol% and a polymerization degree of 800
Of PVA of 0.06 parts by weight, methoxy substitution of 29% by weight, hydroxypropoxy substitution of 9.5% by weight, and 2% by weight of a 2% by weight aqueous solution having a viscosity of 50 cps at 20 ° C.
Example 1 was repeated except that 0.02 part by weight of MC was used, but vinyl chloride polymer particles could not be obtained due to blocking during polymerization.

Comparative Example 4 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
HP having 0.1 parts by weight of PVA of 0, methoxy substitution of 29 weight%, hydroxypropoxy substitution of 9.5 weight% and 2 weight% of an aqueous solution having a viscosity of 50 cps at 20 ° C.
A vinyl chloride polymer was obtained in the same manner as in Example 1 except that 0.01 part by weight of MC was used, with a polymerization conversion of about 85%.

The polymerization conditions are shown in Table 3. Table 7 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had problems in plasticizer absorbency and fish eye.

Comparative Example 5 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0 PVA 0.08 parts by weight, saponification degree 73 mol%, and polymerization degree 800 PVA 0.02 parts by weight except that the same procedure as in Example 1 was carried out at a polymerization conversion rate of about 85% vinyl chloride. A polymer was obtained.

The polymerization conditions are shown in Table 3. Table 7 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had problems in plasticizer absorbency and fish eye.

Comparative Example 6 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 600 were used.
0.07 parts by weight of PVA, saponification degree of 73 mol%, 0.01 parts by weight of PVA having a degree of polymerization of 800, and methoxy substitution degree of 2
9% by weight, hydroxypropoxy substitution degree 9.5% by weight,
The same procedure as in Example 1 was carried out except that 0.01 part by weight of HPMC having a viscosity of 50 cps at 20 ° C. in a 2% by weight aqueous solution was used. However, vinyl chloride polymer particles were blocked during polymerization and no vinyl chloride polymer particles were obtained.

Comparative Example 7 As a dispersion stabilizer, a saponification degree of 93 mol% and a polymerization degree of 350 were used.
0.07 parts by weight of PVA, 73 mol% of saponification degree, 0.01 parts by weight of PVA having a polymerization degree of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
The same procedure as in Example 1 was carried out except that 0.01 part by weight of HPMC was used, but vinyl chloride polymer particles could not be obtained due to blocking during polymerization.

Comparative Example 8 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.07 parts by weight of PVA with a degree of saponification of 47 mol%, 0.01 parts by weight of PVA with a degree of polymerization of 250, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
The same procedure as in Example 1 was carried out except that 0.01 part by weight of HPMC was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 3. Table 7 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had a problem in roll tackiness.

Comparative Example 9 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.07 parts by weight of PVA with a saponification degree of 80 mol%, 0.01 parts by weight of PVA with a degree of polymerization of 1500, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
The same procedure as in Example 1 was carried out except that 0.01 part by weight of HPMC was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 4. Table 8 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had problems in plasticizer absorbency and fish eye.

Comparative Example 10 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.02 parts by weight of PVA with a saponification degree of 73 mol%, 0.01 parts by weight of PVA with a degree of polymerization of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
The same procedure as in Example 1 was carried out except that 0.03 part by weight of HPMC was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 4. Table 8 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer was Ca--Zn.
The thermal stability at the time of compounding the metal soap stabilizer was poor.

Comparative Example 11 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0 PVA of 0.4 parts by weight, saponification degree of 73 mol%, polymerization degree of 800 PVA of 0.2 parts by weight, methoxy substitution degree of 29
% By weight, hydroxypropoxy substitution degree: 9.5% by weight, 2
A vinyl chloride polymer was obtained in the same manner as in Example 1 except that 0.03 part by weight of HPMC having a viscosity of 50 cps at 20 ° C. in an aqueous solution of 50% by weight was used.

The polymerization conditions are shown in Table 4. Table 8 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had problems in plasticizer absorbency, fish eye, transparency, initial colorability, thermal stability when compounded with a Sn-based stabilizer, and roll tackiness.

Comparative Example 12 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.2 parts by weight of PVA having a degree of saponification of 73 mol%, 0.22 parts by weight of PVA having a degree of polymerization of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution and 2% by weight of aqueous solution. Viscosity at 20 ℃ is 50 cps
The same procedure as in Example 1 was carried out except that 0.22 part by weight of HPMC was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 4. Table 8 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had problems in plasticizer absorbency, fish eye, transparency, initial colorability, thermal stability when compounded with a Sn-based stabilizer, and roll tackiness.

Comparative Example 13 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.02 parts by weight of PVA of 0, 73 mol% of saponification degree, 0.06 parts by weight of PVA of polymerization degree of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
The same procedure as in Example 1 was carried out except that 0.01 part by weight of HPMC was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 4. Table 8 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had a problem in roll tackiness.

Comparative Example 14 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.069 parts by weight of PVA of 0, saponification degree of 73 mol%,
0.003 parts by weight of PVA having a degree of polymerization of 800, methoxy substitution of 29% by weight, hydroxypropoxy substitution of 9.5% by weight, and an aqueous solution of 2% by weight have a viscosity at 20 ° C. of 50 cp.
A vinyl chloride polymer was obtained in the same manner as in Example 1 except that 0.006 parts by weight of HPMC of s was used, and the polymerization conversion rate was about 85%.

The polymerization conditions are shown in Table 4. Table 8 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had problems in plasticizer absorbency and fish eye.

Comparative Example 15 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.025 parts by weight of PVA with a saponification degree of 73 mol%,
0.025 parts by weight of PVA having a degree of polymerization of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, and a 2% by weight aqueous solution have a viscosity at 20 ° C. of 50 cp.
Example 1 was repeated except that 0.1 part by weight of HPMC of s was used, but vinyl chloride polymer particles could not be obtained due to blocking during polymerization.

Comparative Example 16 As a dispersion stabilizer, a saponification degree of 80 mol% and a polymerization degree of 260 were used.
0.14 parts by weight of PVA having a saponification degree of 73 mol%, 0.01 parts by weight of PVA having a degree of polymerization of 800, 29% by weight of methoxy substitution, 9.5% by weight of hydroxypropoxy substitution, 2% by weight aqueous solution Viscosity at 20 ℃ is 50 cps
The same procedure as in Example 1 was carried out except that 0.005 parts by weight of HPMC was used to obtain a vinyl chloride polymer with a polymerization conversion rate of about 85%.

The polymerization conditions are shown in Table 4. Table 8 shows the evaluation results of the obtained vinyl chloride polymer.

The obtained vinyl chloride polymer had problems in plasticizer absorbency and fish eye.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

[0123]

[Table 6]

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[Table 7]

[0125]

[Table 8]

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Industrial Applicability According to the present invention, it is possible to produce a vinyl chloride polymer which is excellent in heat stability, fish eye and plasticizer absorbability while maintaining transparency and has less roll stickiness during calendar molding. And its industrial value is very high.

Claims (5)

[Claims] 1. A method for producing a vinyl chloride polymer by carrying out suspension polymerization of a vinyl chloride monomer in an aqueous medium in the presence of a polymerization initiator and a dispersion stabilizer, as a dispersion stabilizer,
Saponification degree 70-90 mol%, average degree of polymerization 1500-30
00 partially saponified polyvinyl alcohol (hereinafter, PVA
(A), a saponification degree of 70 to 90 mol%, an average degree of polymerization of 300 to 1000, and a water-soluble cellulose ether (C) with respect to 100 parts by weight of a vinyl chloride monomer. ) And PVA (B) in total usage of 0.
04-0.5 parts by weight, water-soluble cellulose ether (C)
The amount of PVA used is 0.005-0.2 parts by weight, and PVA
(A) / PVA (B) = 1/1 to 20/1 (weight ratio),
(PVA (A) + PVA (B)) / water-soluble cellulose ether (C) = 1/1 to 25/1 (weight ratio), and a higher alcohol lubricant is used as the vinyl chloride monomer 100.
A method for producing a vinyl chloride polymer, which comprises adding 0.005 to 0.5 part by weight to parts by weight. 2. As the water-soluble cellulose ether, hydroxypropylmethyl cellulose having a viscosity of 10 to 100 cps at 20 ° C. of an aqueous solution of methoxy substitution of 25 to 30% by weight, hydroxypropoxy substitution of 5 to 15% by weight, and 2% by weight is used. The method for producing a vinyl chloride polymer according to claim 1, wherein 3. The chloride according to claim 1, wherein a higher alcohol lubricant containing a monovalent alkyl alcohol component having an alkyl group having 8 or more carbon atoms is used as the higher alcohol lubricant. A method for producing a vinyl polymer. 4. The method for producing a vinyl chloride polymer according to claim 1, wherein a compound having a mercapto group and a hydroxyl group is further added as a molecular weight modifier. 5. The method for producing a vinyl chloride polymer according to claim 1, wherein a phenol-based antioxidant and a sulfur-based antioxidant are used in combination as the antioxidant and further added.