WO1994013742A1

WO1994013742A1 - Stable plastisol

Info

Publication number: WO1994013742A1
Application number: PCT/JP1993/001760
Authority: WO
Inventors: Soichi Muroi
Original assignee: W.R. Grace & Co. - Conn.
Priority date: 1992-12-04
Filing date: 1993-12-03
Publication date: 1994-06-23
Also published as: AU5575694A; JPH06220336A

Abstract

A stable plastisol comprising 100 parts by weight of polymer particles dispersed in 50-200 parts by weight of a plasticizer, wherein the polymer is a copolymer composed of 3-20 parts by weight of an unsaturated carboxylic acid compound and 97-80 parts by weight of an ethylenically unsaturated compound and at least 10 % of the carboxyl groups have been neutralized by an alkali metal compound, and the particles have a number-average diameter of 0.1-100 νm.

Description

Description Stable plastisol Technical field

The present invention relates to a non-vinyl chloride plastisol that can withstand long-term room temperature storage.

BACKGROUND OF THE INVENTION

A plastisol is a liquid or paste-like product made by dispersing polymer particles in a liquid plasticizer and adding a filler and other additives as necessary.The material becomes a soft solid at room temperature by heating. Change. That is, the polymer particles maintain their original shape without dissolving or swelling in the plasticizer when stored at room temperature, but quickly absorb the plasticizer and gel when heated. Utilizing this property, which is suitable for painting and bonding, plastisols are usefully used in fields such as transportation vehicles, ships, toys, and processed textile products.

By far the best polymer for plastisols is vinyl chloride polymer. This polymer provides a stable plastisol for more than a few months at room temperature, with the most common dioctyl phthalate as the plasticizer. The soft plastic obtained by heating this vinyl chloride-based plastisol is tough. However, with the growing interest in environmental pollution, the problems of vinyl chloride polymer products have come to be increasingly highlighted. In other words, when vinyl chloride polymer products are incinerated, hydrochloric acid and dioxin are generated, but these substances are both harmful to the human body and not only severely pollute the environment, but also have the problem that hydrochloric acid corrodes incineration equipment. . From this perspective, there is a movement to exclude vinyl chloride polymers from products that may enter municipal solid waste. Vinyl chloride It is natural that luplastisol is also included in them.

Since plastisol itself is a very valuable product, there is a strong demand for plastisols that do not contain chlorine, that is, non-vinyl chloride plastisols. However, it is very difficult to synthesize polymer particles that give plastisols with performance comparable to that of vinyl chloride polymers, especially storage stability. Simple polymer-copolymer particles have never reached the level of practical use, and various efforts have been made.

As polymer particles for plastisols, acryl polymers and styrene polymers have been proposed as alternatives to vinyl chloride polymers. Of course, simple acrylic polymers cannot satisfy the requirements for plastisol particles, so various conditions are imposed. In German Patent Nos. 2, 454, 235 and 2, 529, 732, the particle size and the particle size determined in relation to T g above 35 ° C. Acryl polymer particles with a defined composition have been proposed. In U.S. Pat.No. 4,071,6563, acryl polymer particles having a core seal structure composed of a core having excellent compatibility with a plasticizer and a seal having poor compatibility with a plasticizer are disclosed. Proposed. In U.S. Pat. No. 4,176,028, plastisol particles obtained by neutralizing acryl polymer particles containing a carboxyl group or an amino group with a volatile gas or a volatile acid in the gas phase. US Pat. No. 4,613,639 proposes a styrene copolymer plastisol particle bonded with a protective colloid. However, none of them have reached the level of vinyl chloride polymers in terms of storage stability.

Purpose of the invention

It is an object of the present invention to provide a plastisol having a chlorine-free polymer composition and having a high level of storage stability that could not be achieved with the prior art. Another object of the present invention is to provide a resin having improved heat resistance by heating. An object of the present invention is to provide a plastisol from which a thisol film can be obtained.

Yet another object of the present invention is to provide a method for producing a plastisol having the characteristics described above.

Summary of the Invention

The plastisol according to the present invention comprises 100 parts by weight of copolymer particles having a number average particle diameter of 0.1 to 100 m dispersed in 50 to 200 parts by weight of a plasticizer. Such a copolymer is formed from 3 to 20 parts by weight of an unsaturated carboxylic acid compound and 97 to 80 parts by weight of a polymerizable unsaturated compound, and at least 10% of its carboxyl groups are neutralized with an alkaline metal compound. It is characterized by having. Another embodiment of the present invention comprises the following steps:

(i) 3 to 20 parts by weight of an unsaturated carboxylic acid compound and 80 to 97 parts by weight of a polymerizable unsaturated compound in water at a temperature of 50 to 95 ° C in the presence of a polymerization initiator. Polymerize to form a polymer dispersion;

(ii) neutralizing at least 10% of the carboxyl groups of the polymer of the polymer monodispersion with an alkaline metal compound at a temperature of 5 to 95 ° C. and a pH of 7 to 14;

(ffi) recovering polymer particles having a number average particle size of 0.1 to 100 / m from the polymer dispersion;

(iv) drying the recovered polymer particles;

(V) 100 parts by weight of the dried polymer particles are dispersed in 50 to 200 parts by weight of a plasticizer;

The present invention relates to a method for producing a plastisol, comprising the steps of:

The ratio of the unsaturated carboxylic acid compound to the polymerizable unsaturated compound constituting the copolymer is 3 to 20 parts by weight of the unsaturated carboxylic acid compound per 97 to 80 parts by weight of the polymerizable unsaturated compound, preferably polymerizable. The amount is from 4 to 12 parts by weight of the unsaturated carboxylic acid compound to 96 to 88 parts by weight of the unsaturated compound. Here, the unsaturated carboxylic acid compound is a single compound Or a mixture of two or more different compounds. The polymerizable unsaturated compound may be a single compound or a mixture of two or more different compounds. If the relative amount of the unsaturated carboxylic acid is less than 3 parts by weight, the viscosity stability of the obtained plastizol becomes poor, while if the relative amount of the unsaturated carboxylic acid exceeds 20 parts by weight, Film formation is poor.

Examples of the polymerizable unsaturated compound which can be used as a monomer constituting the copolymer particles of the blastisol of the present invention include styrene and its derivatives, for example, methyl styrene; methacrylate and acrylate, for example, methyl methacrylate. Or acrylate, ethyl methacrylate or acrylate, isopropyl methacrylate or acrylate, n-butyl methacrylate or acrylate, isobutyl methacrylate or acrylate, tert-butyl methacrylate or acrylate, n-amyl methacrylate or acrylate, isoamyl methacrylate or acrylate N-hexyl methacrylate or acrylate, 2-ethylhexyl methacrylate or acrylate, and n-octyl methacrylate Vinyl esters, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl propronate, vinyl enanthate, vinyl prillate and vinyl pelargonate; acrylonitrile and methacrylonitrile; and butadiene. No. These polymerizable unsaturated compounds may be used alone or as a mixture.

Examples of unsaturated carboxylic oxide compounds that provide the other monomer constituting the copolymer particles include acrylic acid, methacrylic acid, maleic acid and its monoester, itaconic acid and its monoester, fumaric acid and its monoester. Is received.

The copolymer particles according to the invention can be produced by emulsion polymerization or suspension polymerization. Emulsion polymerization consists of 0.2 to 2% by weight of emulsifier and 0.05 to 5% by weight based on the total monomers. % Of the polymerization initiator is heated to 50 to 95 ° C. while stirring, and 25 to 60% by weight of the monomer is added thereto. It takes 3 to 8 hours to complete the polymerization.

Examples of emulsifiers that can be used in the emulsion polymerization include sodium stearate, sodium oleate, sodium laurate, sodium lauryl sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, sodium dodecyl benzene sulfonate, dibutyl sulfosuccinic acid Sodium, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyvinyl alcohol, hydroxyethyl cellulose, sodium polyacrylate, and styrene A sodium salt of a maleic acid copolymer may be used.

Various types of polymerization initiators can be used in emulsion polymerization, for example, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, etc. Water-soluble initiator; the combination of such a water-soluble initiator with an oil-soluble initiator such as benzoyl peroxide, lauroyl peroxide, cumenehydropoxide, diazobisisobutyronitrile, and azobisdimethylnorelonitrile. And a combination of a water-soluble initiator or an oil-soluble initiator with a reducing agent such as sodium sulfite, ammonium sulfite, ferrous oxide, cuprous oxide, sorbic acid, and sucrose.

The size of the copolymer particles obtained in one emulsion polymerization is not so large. The size depends on the selected monomer composition and the method used, but is at most about 0.05 to 0.3 m. Therefore, if larger particles are desired, it is necessary to perform seed polymerization. In seed polymerization, a new emulsifier is added to the dispersion of the already polymerized copolymer particles, the emulsifier is added in an amount that does not generate cells, and then the polymerization initiator is added to the stabilized dispersion. Monomer under the conditions described in The polymerization can be carried out by adding the mixture to a dispersion and polymerizing the mixture. According to this seed polymerization method, the particles can be enlarged almost as calculated. In order to increase the size of the particles as calculated, it is desirable to repeat the seed polymerization as little as possible.

In the suspension polymerization, the monomer having the oil-soluble initiator described above in the amount of 0.05 to 5% by weight based on the total amount of the monomer is added in the amount of 0.5 to 5% by weight based on the total amount of the monomer. Using a water-soluble polymer and / or inorganic fine particles or a water-soluble polymer Z surfactant mixture, the mixture was vigorously stirred at a monomer concentration of 15 to 50% by weight to emulsify in water, and the milk obtained with gentle stirring was used. The suspension can be carried out by heating the suspension at 50-95 for 3-8 hours to complete the polymerization.

Examples of water-soluble polymers that can be used include salts of polyvinyl alcohol, hydroxyethyl cellulose, sodium polyacrylate and styrene-maleic acid copolymer. Examples of the inorganic particles include calcium phosphate, calcium carbonate, magnesium hydroxide, talc, and clay. Further, examples of surfactants include sodium stearate, sodium oleate, sodium laurate, sodium lauryl sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, sodium dodecylbenzenesulfonate, dibutyl sulfo succinate. Examples include sodium acid, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene sorbitan monolaurate.

According to this method, the diameter of the resulting copolymer particles is much larger than that produced by emulsion polymerization. Depending on the monomer composition used and the mixing conditions chosen, the particle size obtained is from a few to a few hundred / zm. Unlike emulsion polymerization, seed polymerization cannot be applied to suspension polymerization, so it is impossible to control the diameter of copolymer particles after the first suspension polymerization is completed. The carboxyl group of the polymer particles obtained by the method described above is obtained by adding an alkali metal compound to the polymer dispersion obtained by the emulsion polymerization or suspension polymerization described above at a temperature of 5 ° C to 95 ° C. Neutralized by addition at temperature and pH 7-14. In the neutralization, an alkaline metal compound is added in the form of an aqueous solution, and the temperature is preferably 15 to 30 ° C.

Next, the polymer particles thus neutralized are dried into powdery plastisol polymer particles, usually by using a spray dryer.

The number average particle diameter of the particles (primary particles) produced by emulsion polymerization or suspension polymerization is usually 0.1 to 100 / zm, preferably 0.3 to 20 m. If the particle size is less than 0.1 m, the viscosity stability of a plastisol is poor. The diameter of the particles obtained by spray drying ranges from a few meters to several hundreds / m, but these particles are secondary particles in which many primary particles are agglomerated. When these secondary particles are dispersed in the plasticizer, they are dispersed into the primary particles except for a part by stirring. Therefore, important factors that govern the important performance of the plastisol, such as the amount of plasticizer required for plastization, the flowability and storage stability of the plastisol, and the rate of film formation (ie, the rate of plasticizer absorption). Is the size of the primary particle. The larger the primary particles, the smaller the amount of plasticizer required for plastisol formation and the better the storage stability of the plastisol, but the slower the plasticizer absorption rate and the longer the heating time required for film formation. You will need it. Therefore, there should be a suitable region where the extremes are compromised, but according to the study of the present inventors, the optimum number average particle size is 0.1 0m to 100 lm, preferably 0.3 好ましく m. m〜20〃m.

Simply introducing a carboxyl group into the polymer by copolymerization of a polymerizable unsaturated compound and an unsaturated carboxylic acid compound does not provide the desired plastisol storage stability and high heat resistance of the plastisol film. Only by neutralizing the carboxyl groups of the polymer with an alkali metal compound will the storage stability and It is possible to achieve the object of the present invention of improving the heat resistance of the plastisol film. Examples of the alkali metal compounds that can be used for this purpose include monovalent alkali metal compounds such as sodium hydroxide and hydroxide hydroxide; divalent alkali metal compounds such as water Calcium oxide, barium hydroxide, magnesium acetate, zirconium acetate, zinc ammonium chloride, zinc ammonium acetate, zirconium ammonium acetate and zirconium ammonium carbonate; trivalent alkaline metal compounds, Examples include aluminum hydroxide and basic aluminum acetate. Alkaline metals, which are divalent rather than monovalent, and trivalent than divalent, are preferred in that they provide excellent stability and a high heat resistance temperature and also increase the film formation temperature. Therefore, the type of alkaline metal used must be selected according to the purpose of the plastisol.

The degree of neutralization of the carboxy group also has a significant effect on important plastisol performance. The higher the neutrality, the better the storage stability and the heat resistance of the plastisol film, but at the same time the higher the film formation temperature. Also, in actual neutralization, it is practically impossible to neutralize 100% of the carboxyl groups of the polymer. The degree of neutralization depends on the type of unsaturated carboxylic acid compound used and the particle size of the polymer. For example, if the number average particle size of the styrene polymer particles copolymerized with 7% by weight of methacrylic acid is about 0.5 / zm, the degree of neutralization is about 18%. Further, if the styrene polymer particles are copolymerized with 7% by weight of acrylic acid, the degree of neutralization is 73% when the number average particle diameter is about 0.7 m. This is probably because only the carboxyl groups on the surface or near the surface of the polymer particles can be neutralized by the alkaline metal compound, and the alkaline metal ions penetrate deep inside the particle and remove the lipoxyl groups there. It is probably because it cannot be neutralized. In addition, the copolymer particles copolymerized with acrylic acid, which is more hydrophilic, have a much higher degree of neutralization than the copolymer particles copolymerized with methacrylic acid. This is probably because more carboxyl groups are distributed on or near the surface of the polymer particles copolymerized with the phosphoric acid. In practice, the degree of neutralization need not necessarily be 100%, but in the plastisol of the present invention, at least 10% of the carboxy groups of the polymer must be neutralized. If the degree of neutralization is 10% or less, a plastisol having storage stability sufficient for practical use and a plastisol film having sufficient heat resistance cannot be obtained. In practice, it is preferable to have a degree of neutralization of 10 to 80%.

It is desirable that the secondary particles produced by spray drying be as easily dispersible as possible in the primary particles during plastisol preparation. This is because the secondary particles are porous and absorb plasticizers that are not related to fluidization, so that the amount of plasticizer used increases. As the use of plasticizer increases, the plastisol film becomes more flexible and less adaptable to applications requiring a tough film. In order to produce secondary particles that easily break down into primary particles, it is desirable that the spray drying temperature be as low as possible and the Tg of the polymer be as high as possible. However, there is a lower limit on the spray drying temperature in order to obtain polymer particles dried by spray drying. The spray drying temperature is at least 50 ° C, so the Tg of the polymer is of course limited. As mentioned above, the spray drying temperature should be at least 50 ° C.

The plastisol copolymer particles thus obtained are dispersed in a plasticizer to form a blastisol. Examples of suitable plasticizers that can be used in the present invention include di-2-ethylhexyl phthalate, dibutyl phthalate, diisooctyl phthalate, butylcyclohexyl phthalate, butyl octyl phthalate, diisononyl phthalate, dicapryl phthalate, and diisodecyl phthalate. Phthalates such as ethates; adipates such as di-2-ethylhexyl adipate and diisodecyl adipate; sebacates such as di-2-ethylhexyl sebaguet; dioctylase Azelaic acid esters such as citrate; Phosphate esters such as resyl phosphate and tree 2-ethylhexyl phosphate; citrate esters such as tree 2-ethylhexyl citrate and acetyl tributyl site; glycerol diacetate monolau And epoxidized glycerides such as epoxidized soybean oil and epoxidized linseed oil.

Plasticizers affect plastisol flow, film formation and film properties. Basically, the compatibility of the plasticizer with the polymer is an important factor. If the compatibility is extremely poor, it will not melt and form a continuous film even when heated, but even if the compatibility is slightly poor, there will be practical problems such as the plasticizer oozing out of the film surface from inside after the film is formed. Occurs. Therefore, it is important to carefully consider the compatibility of the plasticizer with the polymer and carefully select it. The amount of the plasticizer is usually in the range of 50 to 200 parts by weight based on 100 parts by weight of the plastisol polymer particles.

The fluidity and film properties of plastisols can be adjusted with various additives. If necessary or desired, the above properties are adjusted by adding additives such as surfactants, pigments, fillers, foaming agents and solvents. Among them, the solvent is functionally the same as the plasticizer, but volatilizes after the film is formed, so that the fluidity of the plastisol can be improved without softening the formed film. However, the addition of too much solvent impairs the characteristics of the plastisol, so the amount of solvent added should be kept within 10 parts by weight per 100 parts by weight of the plastisol polymer.

Example

Hereinafter, the present invention will be described in more detail with reference to Comparative Examples and Examples. “Parts” are “parts by weight” unless otherwise indicated.

Comparative Example 1 200 g of styrene (hereinafter referred to as “St”) and 592 g of distilled water were charged into a 1,000 ml glass polymerization apparatus equipped with a stirrer and a reflux condenser, and alkyl diphenyle as an emulsifier was added thereto. Add 4 g of a 50% aqueous solution of sodium terdisulfonate (trade name: Verex SS-L, manufactured by Kao Corporation) and 4 g of a 10% aqueous solution of ammonium persulfate, and stir the mixture at 250 rpm. ° C. After heating for 4 hours, no reflux of styrene was observed. Further, the reaction was continued under the same conditions for 2 hours to complete the polymerization. The solid content of the polystyrene dispersion thus obtained was 24.5% by weight (polymerization rate: 97%). The number average particle diameter was 0.05 when measured with an electrophoretic light scattering photometer ELS-800 manufactured by Otsuka Electronics Co., Ltd.

Adjust the solids concentration to 12.5% and use a spray dryer (Palvis mini G S35 type, manufactured by Yamato Scientific Co., Ltd.) equipped with a nozzle with a diameter of 711 / im, inlet temperature 120 ° C, outlet The particles were spray dried at a temperature of 60 ° C. The obtained particles were porous secondary particles having a diameter of 5 m to 200 m.

The polymer powder for plastisol thus obtained was dispersed in di-2-ethylhexyl phthalate (hereinafter referred to as "DOP") to make it into a plastisol. No dispersion of polymer particles was obtained.

Comparative Examples 2 to 4

The procedure of Comparative Example 1 was repeated using a mixed monomer of StZ methacrylic acid (hereinafter referred to as “MAA”) (93Z7) to obtain a StZMAA (93/7) copolymer dispersion. The polymerization rate was 98%, and the number average particle diameter was 0.06 μm.

The polymer dispersion thus obtained was divided into three parts. In Comparative Example 2, one of them was used as is, in Comparative Example 3, the other was neutralized with sodium hydroxide, and in Comparative Example 4, the other was neutralized with calcium hydroxide. . Hydroxylation For neutralization with sodium, the pH was adjusted to 9.5 by adding a 5% aqueous NaOH solution. The amount of sodium hydroxide added here was equivalent to the amount that neutralized 29% of the carboxyl groups of the copolymerized methacrylic acid. When calcium hydroxide was used, a saturated aqueous solution of calcium hydroxide was neutralized with an equivalent amount of sodium hydroxide. Finally, the concentration of the solid content was adjusted to 12.5%, and the obtained polymer dispersion was spray-dried under the same conditions as in Comparative Example 1 to obtain plastisol polymer particles.

The plastisol polymer particles thus obtained were dispersed in D0P to obtain plastizol. Tables 1 and 2 summarize the amount of DOP added to make a plastisol, its initial viscosity, storage stability at 23 ° C (viscosity increase rate), minimum film formation temperature, heat resistance temperature, and film transparency. Shown. The storage stability, minimum film formation temperature and heat resistance temperature were measured by the following methods.

Storage stability

The viscosity of plastisol was measured at room temperature (23 ° C) using a B-type rotary viscometer manufactured by Tokyo Keiki Co., Ltd. Since plastisols exhibit thixotropic properties, the viscosity was taken as the value when equilibrium was reached. The storage stability was expressed as a ratio obtained by dividing the viscosity measured after leaving the plastisol at room temperature for a predetermined period of time by the viscosity immediately after the preparation of the plastisol (initial viscosity).

Minimum film formation temperature

Several samples were prepared by coating plastisol on aluminum foil to a thickness of about 1 mm. This sample was heated at a predetermined temperature for 10 minutes, cooled, and visually inspected to see if it was formed into a continuous film. The test was started at 80 ° C, and the heating temperature was increased in 10 ° C increments to determine the lowest temperature at which a continuous film was formed.

Heatproof temperature

The plastisol was heated at 180 ° C for 20 minutes to make a plastisol sheet about 4 mm thick. Using this sheet as a sample, TMA (120 C ) Was used to measure the heat resistance temperature. The measurement was carried out at a weight of 1 Og using a probe with a needle of 2 mm in diameter as a probe.

The sample sheet was cooled to 15 ° C, set, and heated at a rate of 4 ° CZ. Waiting for the temperature to rise to 0 ° C started the penetration and measured the penetration as a function of temperature. The penetration will remain at zero at the beginning of the temperature rise or only at a slow speed, but once the temperature exceeds the heat resistance temperature of the sample sheet, the speed will increase rapidly and the quartz glass And stopped. The heat-resistant temperature was the temperature at which the probe penetrated 50% of the thickness of the sample sheet.

Comparative Example 5

Using the unneutralized copolymer dispersion of Comparative Example 2 as a seed, the particle size of the polymer particles was enlarged by a commonly used seed polymerization method. Since the surface tension of the unneutralized copolymer dispersion of Comparative Example 2 used as a seed was 65 dyne Zcm, a 10% aqueous solution of sodium alkyldiphenyl ether disulfonate was added first to reduce the surface tension of this surfactant. The surface tension below the critical micelle concentration of was reduced to 30 dyne / cm to stabilize the copolymer monodisperse, and then the concentration was adjusted to 20%. To 5 g of the stabilized seed copolymer monodispersion, add 592 g of distilled water, 200 g of StZMAA (93/7) mixed monomer, and 4 g of a 10% aqueous solution of ammonium persulfate, and stir at 250 rpm. The temperature was raised to 90 ° C. After heating at 90 ° C for 4 hours, no reflux of styrene was observed. Further, the reaction was continued under the same conditions for 2 hours to complete the polymerization. The polymerization rate was 98%, and the number average particle size was 0.23 / zm. Using this as a seed polymer dispersion, the same procedure as above was used to seed polymer the seed polymer particles once more with a 20-fold mixture of StNOMAA (93/7) and polymer particles. Was enlarged. The polymerization rate was 98%, and the number average particle size was 0.53 / m.

Plastisol polymer particles were obtained by the method described in Comparative Example 2, and then DOP was blended with the polymer particles to obtain a plastisol. Performance related to this plastisol Are shown in Tables 1 and 2.

Comparative Examples 6 and 7

Except that a mixed monomer of St / MAA (97.8 / 2.2) was used as the monomer, the StZMAA (97.8 / 2) was used in accordance with the first stage seed polymerization method of Comparative Example 5. .2) A copolymer dispersion was obtained. The polymerization rate was 98%, and the number average particle size was 0.26 zm. In Comparative Example 6, the product was neutralized with sodium hydroxide in the same manner as in Comparative Example 3, and in Comparative Example 7, the product was neutralized with calcium hydroxide in the same manner as in Comparative Example 4. Thisol polymer particles were obtained. The polymer particles were blended into DOP to form a plastisol. Tables 1 and 2 show the performance of plastisol. Examples 1 and 2

Regarding the copolymer dispersion obtained in Comparative Example 5, sodium hydroxide was used in Example 1 as in Comparative Example 3, and calcium hydroxide was used in Example 2 in the same manner as in Comparative Example 4. After neutralization, the neutralized polymer particles were spray-dried into plastisol polymer particles, and the polymer particles were dispersed in D0P to form plastisols, and their properties were measured. The results are shown in Tables 1 and 2.

Example 3

The plastisol polymer particles of Example 1 were dispersed in glycerol diacetate monolaurate (hereinafter referred to as "GDML") in place of D0P to obtain a plastisol. The performance of the plastisol thus obtained is shown in Tables 1 and 2. Examples 4 and 5

The plastisol polymer particles obtained in Examples 1 and 2 were each dispersed in diisononyl diphthalate (hereinafter, referred to as “D INP”) in place of DOP to obtain a plastisol. The performance of the plastisol thus obtained is shown in Tables 1 and 2.

Examples 6 and 7 A StZMAA (96/4) copolymer dispersion was synthesized according to the two-stage seed polymerization method of Comparative Example 5, except that a mixed monomer of StZMAA (96/4) was used as the monomer. The obtained copolymer dispersion was neutralized with sodium hydroxide in Example 6 as in Comparative Example 3, and neutralized with calcium hydroxide in Example 7 as in Comparative Example 4. Thereafter, the neutralized polymer particles were spray-dried to obtain blastisol polymer particles. Various properties were measured as a plastisol by dispersing the polymer particles in D0P. The results are shown in Tables 1 and 2. c Examples 8 and 9

A StZMAA (91/9) copolymer dispersion was synthesized according to the two-stage seed polymerization method of Comparative Example 5, except that a mixed monomer of St / MAA (91/9) was used as the monomer. did. The obtained copolymer dispersion was neutralized with sodium hydroxide in Example 8 as in Comparative Example 3 and neutralized with calcium hydroxide in Example 9 as in Comparative Example 4. Thereafter, the neutralized polymer particles were spray-dried to obtain plastisol polymer particles. Then, various properties were measured by dispersing the polymer particles in DOP to form a plastisol. The results are shown in Tables 1 and 2.

Examples 10 and 11

A St / MAA (88/12) copolymer dispersion was synthesized according to the two-stage seed polymerization method of Comparative Example 5, except that a monomer mixture of StZMAA (88/12) was used as the monomer. . The obtained copolymer dispersion was neutralized with sodium hydroxide in Example 10 in the same manner as in Comparative Example 3 and neutralized with calcium hydroxide in Example 11 in the same manner as in Comparative Example 4. Thereafter, the neutralized polymer particles were spray-dried to obtain plastisol polymer particles. Next, the polymer particles were dispersed in DOP to form plastisols, and their properties were measured. The result is a table This is shown in Table 1 and Table 2.

Examples 12 and 13

A StZMAA (85/15) copolymer dispersion was synthesized according to the two-stage seed polymerization method of Comparative Example 5, except that a mixed monomer of the monomer St / MAA (85/15) was used. The obtained copolymer dispersion was neutralized with sodium hydroxide in Example 12 in the same manner as in Comparative Example 3, and neutralized with calcium hydroxide in Example 13 in the same manner as in Comparative Example 4. Thus, the neutralized polymer particles were spray-dried to obtain plastisol polymer particles. Next, the polymer particles were dispersed in DOP to obtain plastisols, and their properties were measured. The results are shown in Tables 1 and 2.

Examples 14 and 15

Except that a mixed monomer of StZ acrylic acid (hereinafter referred to as "AA") (94.5.5 / 5.5.5) was used as the monomer, the StZAA (94.5.5 / 5.5) A copolymer dispersion was synthesized. The obtained copolymer dispersion was neutralized with sodium hydroxide in Example 14 as in Comparative Example 3 and with calcium hydroxide in Example 15 as in Comparative Example 4, respectively. Then, the neutralized polymer particles were spray-dried to obtain plastisol polymer particles. Next, the polymer particles were dispersed in DOP to obtain plastizol, and their properties were measured. The results are shown in Tables 1 and 2.

Examples 16 and 17

A StZAA (93/7) copolymer dispersion was synthesized according to the two-stage seed polymerization method of Comparative Example 5, except that a mixed monomer of StZAA (93/7) was used as the monomer. The obtained copolymer dispersion was neutralized with sodium hydroxide in Example 16 in the same manner as in Comparative Example 3 and neutralized with calcium hydroxide in Example 17 in the same manner as in Comparative Example 4. And then spray-dry the neutralized polymer particles To obtain plastisol polymer particles. Next, the polymer particles were dispersed in D0P to obtain plastisols, and their properties were measured. The results are shown in Tables 1 and 2.

Examples 18 and 19

According to the two-stage seed polymerization method of Comparative Example 5, except that a monomer mixture of St-nobutyl acrylate (hereinafter referred to as “BA”) MAA (88/5/7) was used as the monomer. A StZBAZMAA (88/5/7) copolymer dispersion was synthesized. The obtained copolymer dispersion was neutralized with sodium hydroxide in Example 18 in the same manner as in Comparative Example 3, and neutralized with calcium hydroxide in Example 19 in the same manner as in Comparative Example 4. Thereafter, the neutralized polymer particles were spray-dried to obtain plastisol polymer particles. Then, various properties were measured as a plastisol by dispersing the polymer particles in DOP. The results are shown in Tables 1 and 2. Examples 20 and 21

MMA / MAA (93/7) was used according to the two-stage seed polymerization method of Comparative Example 5, except that a monomer mixture of methyl methacrylate (hereinafter referred to as “MMA”) / MAA (93/1) was used as the monomer. ) A copolymer dispersion was synthesized. In the obtained copolymer dispersion, sodium hydroxide was used in Example 20 as in Comparative Example 3, and calcium hydroxide was used in Example 21 as in Comparative Example 4. After the addition, the neutralized polymer particles were spray-dried to obtain plastisol polymer particles. Next, the polymer particles were dispersed in acetyltributyl citrate (hereinafter referred to as "ATBC") to measure various properties as a plastisol. The results are shown in Tables 1 and 2.

Examples 22 and 23

The latex obtained in Comparative Example 5 was neutralized with sodium hydroxide in the same manner as in Comparative Example 3, and then spray-dried to obtain plastisol polymer particles. Example 22 In Example 23, epoxidized soybean oil (hereinafter, referred to as “ESB”) (Asahi Denka Kogyo Co., Ltd., Nedo, Adeiki Saiza 1-130P) was used. In Example 23, epoxidized soybean oil (hereinafter, “ELS”) The polymer particles were dispersed in (Adeiki Sizer 1-118 OA manufactured by Asahi Denka Kogyo Co., Ltd.) to form plastisols, and their properties were measured. The results are shown in Tables 1 and 2.

Example Monomer composition Primary neutralization Plasticizer Particle size

St MMA BA AA MAA Alkaline Neutralization rate Type phr

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4 U.04 shi a uiu 2 11 UUr 1UU

Q

b U, O naUn onU nnp 1 ΠΠ Thigh tyij ¾ 丄 Q

U.O and 3, υιυ 2 onU nnp IlU

U. OZ iiaUJtl 91 n 1 / nUr 1 丄 Π uΠu tfEt ^ Uli οδ n CO

U.O ta Unj 2 UUr 丄丄 U Example 12 85 15 0.51 NaOH 23 D0P 110 Example 13 85 15 0.51 Ca (0H) ₂ 23 D0P 120 Example 14 94.5 5.5 0.61 NaOH 67 D0P 120 Example 15 94.5 5.5 0.61 Ca (0H) ₂ 67 D0P 130 Example 16 93 7 0.72 NaOH 73 D0P 120 Example 17 93 7 0.72 Ca (0H) ₂ 73 D0P 130 Example 18 88-5 7 0,57 NaOH 18 D0P 90 Example 19 88 -5 7 0.57 Ca (0H) ₂ 18 D0P 100 Example 20-93-7 0.78 NaOH 22 ATBC 110 Example 21-93-7 0.78 Ca (0H) ₂ 22 ATBC 120 Example 22 93 7 0.53 NaOH 18 ESB 90 Example 23 93 7 0.53 NaOH 18 ELS 90 Table 2 Example Viscosity increase rate at the initial 23 （(fold) ft ί £ Film Temperature resistance Film number Viscosity Forming temperature (X) Transparency Boise 7 after 30 after 60 after (

ta 1

Comparative Example 1 1 1 1 Comparison 一 4Uil,

Kellification 80 or less 55 Transparent

04 Get #le rt, 1 note

90 90 62 Almost transparent ΐ> Δ 11/110 110 81 Translucent

901 gap

LLi. 80 or less 55 Transparent lob / τΊΐ,

Kell 1 80 53 Almost transparent Comparative Example 7 202 Kellification 90 61 Translucent Example π

1 289 1.00 丄. 53 2.05 90 62 Almost transparent Example 2 310 1.00 1.26 1.88 110 81 Translucent Example 3 308 1.00 1.67 2.23 90 58 Translucent 8

Example 4 298 1.00 1.58 2.03 90 63 Translucent Example 5 284 1.00 1.09 1.47 110 84 Translucent Example 6 50 1.00 1.62 2.21 80 59 Almost Transparent Example 7 80 1.00 1.33 l. 83 100 77 Translucent Example 8 218 1.00 丄. 10 丄, 22 100 71 Translucent Example 9 231 1. π π U. n 9oo 1. U4 130 95 Translucent Example 10 1 η 1

228 1, UπU u. Yy 1.0

o 110 79 Translucent Example 11 262 1. UU nu, n yo 丄, uo 170 101 Translucent Example 12 218 丄. υυ 丄. 1 丄. 3 QfiD 190 86 Translucent Example 13 132 1 丄. π υπυ u.yo u.yo 200 114 Translucent Example 14 187 1.00 1.13 1.26 120 86 Opaque Example 15 231 1.00 1.01 1.01 140 92 Opaque Example 16 222 1.00 1 22 1.22 190 92 Opaque Example 17 263 1.00 0.98 0.98 200 or more 123 Opaque Example 18 278 1.00 2.32 Gelation 80 53 Almost transparent Example 19 281 1.00 1. 98 Gelation 90 78 Translucent Example 20 195 1.00 1.78 3.76 90 66 Translucent Example 21 188 1.00 1.32 2.62 110 87 Translucent Example 22 68 1.00 1. 24 1.68 80 82 Translucent Example 23 62 1.00 1.26 1.72 80 78 Translucent As is clear from the above Comparative Examples and Examples, storage stability, which is an important property of plastisols for practical use, depends on the type of unsaturated carboxylic acid compound used and the amount of unsaturated carboxylic acid in the copolymer. It is governed by the type of neutralizing alkaline metal compound and the primary particle size. For unsaturated carboxylic acid compounds, the greater the amount of unsaturated carboxylic acid compound in the copolymer, the better the storage stability. Even if the amount is the same, an unsaturated carboxylic acid compound that easily distributes on the particle surface, that is, an unsaturated carboxylic acid of an alkaline metal compound that provides a high t and a neutralization rate provides a higher storage stability. Even if a carboxyl group is introduced into the polymer by using the compound, high storage stability cannot be expected if the carboxyl group remains unneutralized, but the carboxyl group is neutralized with an alkali metal compound to store the plastisol. Stability is significantly improved. In terms of improving stability, the higher the valence of the alkali metal used for neutralization, the more effective. Regarding the particle size, the larger the particle size, the better the storage stability. However, when the number average particle size exceeds 0.3 m, the effect of improving the storage stability is not so remarkable.

Among the ways to increase this storage stability are the selection of unsaturated carboxylic acid compounds that are easily distributed on the particle surface, the amount of highly unsaturated carboxylic acid compounds in copolymerization, and the use of higher valent alkali metal compounds. Sum also tends to increase the heat resistance of the plastisol film. However, this direction also impairs the formability of the plastisol film. If the minimum film formation temperature exceeds 250 ° C. by heating for 5 minutes, practical problems will arise. Therefore, an appropriate compromise is needed to balance storage stability, film formability, and film heat resistance, which are important for the performance as a plastisol.

In the present invention, the amount ratio of the unsaturated carboxylic acid compound in the copolymer is from 80 to 97 parts by weight of the polymerizable unsaturated compound and from 3 to 20 parts by weight, preferably from 20 to 97 parts by weight of the polymerizable unsaturated compound. Unsaturated calcium based on 8 to 96 parts by weight The boronic acid compound is 4 to 12 parts by weight, and the primary particles have a number average particle diameter of 0.1! ! 〜100〃m, preferably 0.3〃20〜m. Such a copolymer is made into a water-dispersed liquid, the carboxyl groups in the copolymer are neutralized with an alkali metal compound that provides a required heat-resistant temperature, and then the dispersion is spray-dried to obtain a plastisol polymer. Prolonged storage stability at room temperature is ensured by forming the particles into a plastisol with the addition of plasticizers and, where appropriate, additives.

As described above, according to the present invention, a plastisol having a high level of storage stability, which cannot be achieved by the conventional technology, and a high heat resistance and excellent weather resistance are obtained by a polymer composition containing no chlorine. A plastisol film can be provided. This plastisol substitutes for applications in the fields of transport vehicles, ships, toys, and processed textile products, where vinyl chloride-based plastisols were conventionally used, and contributes not only to environmental pollution but also to its high heat resistance temperature. Utilizing the excellent weather resistance and the new technology, it is possible to develop new applications that have not been possible with vinyl chloride plastisols.

Claims

The scope of the claims

1. A copolymer of 3 to 20 parts by weight of an unsaturated carboxylic acid compound and 97 to 80 parts by weight of a polymerizable unsaturated compound, wherein at least 10% of the carboxyl groups are alkali metal compounds. 100 parts by weight of copolymer particles having a number average particle diameter of 0.1 lzm to 100 / m, which is neutralized, are dispersed in 50 to 200 parts by weight of a plasticizer. Plastisol.

2. The unsaturated carboxylic acid compound constituting the copolymer is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid and its monoester, itaconic acid and its monoester, fumaric acid and its monoester. The plastisol according to claim 1.

3. The plastisol according to claim 2, wherein the unsaturated carboxylic acid compound is acrylic acid.

4. The plastisol according to claim 2, wherein the unsaturated carboxylic acid compound is methacrylic acid.

5. The brass according to claim 1, wherein said polymerizable unsaturated compound is selected from the group consisting of styrene and its derivatives, methacrylic acid ester, acrylic acid ester, vinyl ester, acrylonitrile, methacrylonitrile and butadiene. Stisol.

6. The blastisol according to claim 5, wherein the polymerizable unsaturated compound is styrene.

7. The plastisol according to claim 5, wherein the methacrylate is methyl methacrylate.

8. The plastisol according to claim 5, wherein the acrylate is n-butyl acrylate.

9. The plastisol according to claim 1, wherein the alkaline metal compound is a monovalent alkaline metal compound.

10. The plastisol according to claim 9, wherein said monovalent alkali metal compound is sodium hydroxide.

11. The plastisol according to claim 1, wherein the alkali metal compound is a divalent alkali metal compound.

12. The plastisol according to claim 11, wherein said divalent alkaline metal compound is calcium hydroxide.

13. The plasticizer according to claim 11, wherein said plasticizer is selected from the group consisting of phthalates, adipic esters, sebacic esters, azelaic esters, phosphoric esters, citrate esters, acetylated glycerides and epoxidized glycerides. The plastisol according to item 1.

14. The phthalic acid ester is a group consisting of di-2-ethylhexyl phthalate, dibutyl phthalate, diisooctyl phthalate, butylcyclohexyl phthalate, butyoctyl phthalate, diisononyl phthalate, dicapryl phthalate and diisodecyl phthalate The plastisol according to claim 13, which is selected from the group consisting of:

15. The plastisol according to claim 14, wherein said phthalic acid ester is di-2-ethylhexyl phthalate.

16. The plastisol according to claim 14, wherein said phthalic acid ester is diisononyl diphthalate.

17. The plastisol according to claim 13, wherein said citrate is acetyltributyl citrate.

18. The plastisol according to claim 13, wherein said acetylated glyceride is glycerol diacetate monolaurate.

19. The plastisol according to claim 13, wherein said epoxidized glyceride is epoxidized soybean oil.

20. The plastisol according to claim 13, wherein the epoxidized glyceride is an epoxidized linseed oil.

21. A blastisol according to claim 1 wherein the particles of the copolymer have a number average particle size of 0.3 to 20 zm.

22. The following steps:

(ii) neutralizing at least 10% of the carboxyl groups of the polymer of the polymer dispersion with an alkali metal compound at a temperature of 5 to 95 ° C. and a ρ of 7 to 14;

(iii) recovering a polymer particle having a number average particle diameter of 0.1 to 100 m from the polymer dispersion;

(iv) drying the recovered polymer particles;

A method for producing a plastisol, comprising a step.

23. Step (i) is carried out in the presence of 0.2 to 2% by weight of emulsifier, based on the total amount of unsaturated carboxylic acid compound and polymerizable unsaturated compound, at a monomer concentration of 25 to 60% by weight, The method according to claim 22, which is carried out by emulsion polymerization.

24. The method according to claim 23, wherein step (i) is repeated at least twice.

25. In step (i), 0.5 to 5% by weight, based on the total amount of the unsaturated carboxylic acid compound and the polymerizable unsaturated compound, of a mixture of a water-soluble polymer, inorganic fine particles and a water-soluble polymer and a surfactant. In the presence of at least one selected from the group consisting of 1 22. The process according to claim 22, which is carried out by suspension polymerization at a monomer concentration of 5 to 50% by weight.

26. The method according to claim 22, wherein steps (ffi) and (i) are performed simultaneously by spray drying.

27. The method of claim 1, wherein the unsaturated carboxylic acid compound in step (i) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid and its monoester, itaconic acid and its monoester, fumaric acid and its monoester. Method according to paragraph 22.

28. The method according to claim 2, wherein the polymerizable unsaturated compound in step (i) is selected from the group consisting of styrene and its derivatives, methacrylic acid esters, acrylic acid esters, vinyl esters, acrylonitrile, methacrylonitrile, and butadiene. The method described in paragraph 2.

29. The method according to claim 22, wherein the alkaline metal compound in step (ii) is added to the polymer dispersion in the form of an aqueous solution.

30. The claim wherein the alkaline metal compound in step (ϋ) is selected from the group consisting of a monovalent alkaline metal compound, a divalent alkaline metal compound, and a trivalent alkaline metal compound. The method of paragraph 22.

31. The plasticizer in step (V) is selected from the group consisting of phthalates, adipates, sebacates, azelates, phosphates, esters of citrate, acetylated glycerides, and epoxidized glycerides. 22. The method according to claim 22.