JPH08217943A - Stable plastisol giving film excellent in toughness and heatresistance - Google Patents

Abstract

PURPOSE: To prepare a plastisol having a good balance between storage stability, film forming properties, and mechanical properties of the film by dispersing a particular butadiene polymer fine particle soft nucleus component and a particular polymer component in a plasticizer.

CONSTITUTION: A plastisol, with a resin fine particle mixture dispersed in a plasticizer, comprising: (A) 1 to 60 pts.wt. butadiene polymer fine particle soft nucleus component; and (B) 40 to 99 pts.wt. nonbutadiene copolymer resin fine particle component prepd. by copolymerizing an unsatd. carboxylic acid compd. with an unsatd. compd. not contg. a carboxyl group. The component A comprises a fine particle of a butadiene polymer or a fine particle of a copolymer, having a glass transition temp. of 25°C or below, of butadiene with an unsatd. carboxylic acid compd. and/or an unsatd. compd. not contg. any carboxyl group, and the component B comprises 3 to 20 pts.wt., based on 100 pts.wt. resin fine particle mixture, unsatd. carboxylic acid compd. and 20 to 96 pts.wt. unsatd. compd. not contg. any carboxyl group.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-vinyl chloride plastisol which can be stored at room temperature for a long period of time and has excellent mechanical properties.

[0002]

2. Description of the Related Art Plastisol means polymer particles dispersed in a liquid plasticizer and, if necessary, 10 parts by weight or less of a volatile organic solvent (diluent) based on the polymer particles. ), A liquid, or a paste-like product produced by adding additives such as fillers and pigments, and changes into a soft solid at room temperature by heating. That is, the polymer particles maintain their original shape without being dissolved or swelled in the plasticizer when stored at room temperature, but quickly absorb the plasticizer and gelate when heated. Utilizing this property suitable for painting and bonding, plastisol is usefully used in the fields of transportation vehicles, ships, toys, processed textile products, packing materials and the like.

The predominant polymer for plastisols is vinyl chloride polymer. This polymer gives a stable plastisol at room temperature for several months or more using the most general-purpose dioctyl phthalate as a plasticizer, and the soft plastic obtained by heating has tough film characteristics excellent in mechanical properties.
However, as the concern about environmental pollution has increased in recent years, the problems of vinyl chloride polymer products have gradually come to the forefront. That is, when a vinyl chloride polymer product is incinerated, hydrochloric acid and dioxin are generated, but both of these substances are harmful to the human body and not only seriously pollute the environment, but also hydrochloric acid corrodes the incinerator. From this perspective, there is a movement to keep out vinyl chloride polymers from products that may enter the municipal waste. Of course, vinyl chloride plastisols are also included therein.

[0004] Since plastisol itself is a product having a very high utility value, as a matter of course, there is a great demand for a plastisol containing no chlorine, that is, a non-vinyl chloride plastisol. However, it is very difficult to highly balance mechanical properties such as performance comparable to vinyl chloride polymer, for example, stability as plastisol, film forming properties, heat resistance of film after film formation, tensile strength, and elongation. It is difficult, and even if a simple polymer or copolymer is used, it cannot reach a practical range, and various devices have been devised.

As an example, for example, US Pat. No. 407.
In 1653, the stability of plastisol and the film forming properties are balanced by an acrylic polymer particle having a structure composed of a core having excellent compatibility with a plasticizer and a shell having poor compatibility with the plasticizer. Trying things. Further, in JP-A-5-27133, an ionic catenary is introduced into the polymer particles to try to balance the stability of plastisol and the mechanical properties of the film without impairing the film forming properties, but in any case, In terms of performance, it has not reached the level of plastisol using vinyl chloride polymer.

[0006] On the other hand, the inventors of the present invention, in Japanese Patent Application No. 4-342508, filed previously, set forth an unsaturated carboxylic acid monomer having a constant weight ratio and an unsaturated group having a functional group capable of reacting with a carboxyl group. Compounds, and particles for plastisol obtained by neutralizing the carboxyl groups of the particles of the unsaturated compound copolymer containing no carboxyl group with an alkali metal salt have the above-mentioned stability, film-forming characteristics, and mechanical characteristics. It has been disclosed that plastisol having extremely excellent heat resistance is provided.

However, even if the plastisol obtained from the above copolymer is used, the properties such as tensile strength and elongation are still insufficient.

As a result of further research on the above-mentioned copolymer composition, the present inventors have found that unsaturated carboxylic acid compounds and unsaturated compounds not containing a carboxyl group, and, if desired, those having a functional group capable of reacting with a carboxyl group. By using polymer particles in which a unit derived from a saturated compound and a unit derived from butadiene coexist as a plastisol polymer particle, the above-mentioned stability and film-forming properties and the mechanical properties of the film are highly balanced. The inventors have found that they can be made and have completed the present invention.

That is, the object of the present invention is to have a chlorine-free polymer composition and to have an excellent balance of high level of storage stability and film-forming properties and mechanical properties of a film, which cannot be achieved by conventional techniques. Is to provide plastisol.

[0010]

The plastisol according to the present invention comprises a butadiene-based polymer fine particle soft nucleus component having a Tg of 25 ° C. or less, an unsaturated carboxylic acid compound, an unsaturated compound containing no carboxyl group, and a desired compound. In some cases, in addition to this, together with each component of the unsaturated compound having a functional group capable of reacting with a carboxyl group, polymer particles coexisted in various modes are dispersed in a plasticizer. It is a thing.

The most important feature of the plastisol according to the present invention is that it contains, as fine particles, a soft core component of a butadiene-based polymer having a Tg of 25 ° C. or lower. An unsaturated carboxylic acid and an unsaturated compound not containing a carboxyl group, and, if desired, a component derived from an unsaturated compound having a functional group capable of reacting with a carboxyl group, are coexistent in various forms. It has been found that a stable sol having excellent mechanical properties can be formed by using the resin fine particles as particles for plastisols. In the plastisol according to the present invention, the resin fine particles as described above are dispersed in a plasticizer to form a film, so that the soft core component (domain layer) of the butadiene-based polymer fine particles can be mixed with other monomers. It is formed in a continuous layer derived from the copolymer component, which is believed to contribute to the improvement of the mechanical properties of the plastisol.

In the plastisol according to the present invention, the first mode in which the butadiene-based polymer fine particle soft nucleus component and other monomer component coexist is a polymerization of the butadiene-based polymer fine particle soft nucleus component and other monomer. The non-butadiene-based copolymer resin fine particle component obtained by the above may be simply mixed.

That is, the first aspect of the present invention is to comprise 1 to 60 parts by weight of (A) butadiene-based polymer fine particle soft core component.
(B) A resin fine particle mixture composed of 40 to 99 parts by weight of a non-butadiene copolymer resin fine particle component obtained by copolymerizing an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group is in a plasticizer. (1) butadiene polymer fine particles obtained by polymerizing a butadiene monomer, wherein the butadiene-based polymer fine particle soft core component (A) is a plastisol dispersed in a glass transition temperature (Tg ) 25 ° C. or less, copolymer fine particles of a butadiene monomer and an unsaturated carboxylic acid compound; (3) Copolymerization of a butadiene monomer having a Tg of 25 ° C. or less and an unsaturated compound containing no carboxyl group Polymer fine particles;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof; The butadiene-based copolymer resin fine particle component (B) does not contain a unit derived from an unsaturated carboxylic acid compound of 3 to 20 parts by weight and a carboxyl group of 20 to 96 parts by weight, per 100 parts by weight of the resin fine particle mixture. It relates to a plastisol, which is a fine particle of a copolymer of an unsaturated carboxylic acid compound and an unsaturated compound having no carboxyl group, which has a unit derived from the unsaturated compound.

The unsaturated carboxylic acid compound used as a component constituting the resin fine particles of the present invention is considered to contribute to the stability of the obtained plastisol. Examples of unsaturated carboxylic acid compounds that can be used in the present invention include acrylic acid, methacrylic acid, maleic acid and its mono-lower alkyl ester, itaconic acid and its mono-lower alkyl ester, fumaric acid and its mono-lower alkyl ester. Can be mentioned. These unsaturated carboxylic acid compounds can be used alone or as a mixture.

Examples of the unsaturated compound containing no carboxyl group which is used as a component constituting the resin fine particles of the present invention include styrene and its derivatives such as α-methylstyrene; methacrylic acid ester or acrylic acid ester such as methyl methacrylate or acrylate. , Ethyl methacrylate or acrylate, isopropyl methacrylate or acrylate, n-butyl methacrylate or acrylate, isobutyl methacrylate or acrylate, t-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- Chi methacrylate or acrylate; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl caprylate, and vinyl Peragoniru acids such as is. These unsaturated compounds containing no carboxyl group may be used alone or as a mixture.

The fine particle component of the butadiene-based polymer having a Tg of 25 ° C. or lower (which is referred to as “butadiene-based polymer fine particle soft nucleus component” in the present specification) used in the plastisol according to the present invention is (1) ) Fine particles of butadiene polymer obtained by polymerizing butadiene monomer; (2) Fine particles of copolymer of butadiene monomer and unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C or lower; ) Fine particles of a copolymer of a butadiene monomer and an unsaturated compound having no carboxyl group, having a Tg of 25 ° C. or lower;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound having no carboxyl group, having a Tg of 25 ° C. or lower; and a mixture thereof.

When a homopolymer of butadiene is used as the soft core component of the butadiene-based polymer fine particles according to the present invention, the glass transition temperature is 25 ° C. or lower, which is not a problem, but the butadiene monomer and other monomers When the copolymer with is used as the butadiene-based polymer fine particle soft nucleus component according to the present invention, the amount ratio of the butadiene monomer and the other monomer is determined by the glass transition temperature (T
g) must be selected to be below 25 ° C. This amount ratio varies depending on the types of other monomer components, but generally, the butadiene monomer component, the unsaturated carboxylic acid compound component, and the unsaturated compound component not containing a carboxyl group are 40 to 98, respectively. Parts by weight, 1
7 parts by weight and 1 to 53 parts by weight, preferably 50 to 75 parts by weight, 2 to 5 parts by weight, and 20 to 48 parts by weight, respectively.

Further, in the plastisol according to the present invention, as a second mode in which the butadiene-based polymer fine particle soft nucleus component and other monomer component coexist, in the presence of the butadiene-based polymer fine particle soft nucleus component, Examples thereof include a form in which fine particles (which are referred to as “butadiene-based rubber resin fine particles” in the present specification) are formed by copolymerizing another monomer.

That is, the second embodiment of the present invention comprises a total of 40 to 99 parts by weight of an unsaturated carboxylic acid compound and a carboxyl group in the presence of 1 to 60 parts by weight of a butadiene-based polymer fine particle soft core component. Is a plastisol in which butadiene rubber resin fine particles obtained by copolymerizing an unsaturated compound are dispersed in a plasticizer, and the butadiene polymer fine particle component is (1) polymerizing a butadiene monomer. Obtained butadiene polymer fine particles; (2) Copolymer fine particles of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C or lower; (3) Butadiene having a Tg of 25 ° C or lower Fine particles of a copolymer of a monomer and an unsaturated compound not containing a carboxyl group;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound having no carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof; Rubber resin particles
A unit derived from an unsaturated carboxylic acid excluding those contained in the butadiene-based polymer fine particle soft nucleus component and a carboxyl group-containing unit excluding those contained in the butadiene-based polymer fine particle soft nucleus component The present invention relates to a plastisol having units derived from a saturated compound in an amount of 3 to 20 parts by weight and 20 to 96 parts by weight, respectively, per 100 parts by weight of butadiene rubber resin fine particles.

In the second aspect of the present invention described above, copolymerization of another monomer, that is, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, with the butadiene-based polymer fine particle soft core component as a core. Fine particles having a core-shell structure having a shell as a component, or fine particles having a microdomain formation of each component are formed, and by dispersing these fine particles in a plasticizer, stable particles having excellent mechanical properties can be obtained. A sol is formed.

Further, in the plastisol according to the present invention, resin fine particles obtained by mixing the butadiene type rubber resin fine particles formed as described above and the non-butadiene type copolymer resin fine particles are used as the plastisol fine particles. You can also

That is, the third aspect of the present invention is obtained by copolymerizing (A) a butadiene rubber resin fine particle component with (B) an unsaturated carboxylic acid compound and an unsaturated compound containing no carboxyl group. A plastisol in which a resin fine particle mixture composed of a non-butadiene copolymer resin fine particle component is dispersed in a plasticizer, wherein the butadiene rubber resin fine particle component (A) polymerizes (1) a butadiene monomer. (2) Copolymer fine particles of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C. or lower; (3) Tg of 25 ° C. or lower , Fine particles of a copolymer of a butadiene monomer and an unsaturated compound containing no carboxyl group;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and a fine particle of a butadiene polymer selected from a mixture thereof. In the presence of nuclear components,
It is obtained by copolymerizing an unsaturated carboxylic acid compound and an unsaturated compound which does not contain a carboxyl group, and the butadiene-based rubber resin fine particles exclude those contained in the butadiene-based polymer fine particle soft nucleus component. The amount of the unit derived from unsaturated carboxylic acid is 3 to 20 parts by weight per 100 parts by weight of butadiene rubber resin fine particles, and the non-butadiene copolymer resin fine particles are unsaturated carboxylic acid. 3 to 20 units per 100 parts by weight of the non-butadiene-based copolymer resin fine particles.
1 to 60 parts by weight of the units derived from the butadiene-based polymer fine particle component, 100 parts by weight of the resin fine-particle mixture in the resin fine-particle mixture, and the butadiene-based polymer fine particle soft nucleus component. A plastisol characterized in that units derived from unsaturated compounds containing no carboxyl groups, excluding those contained therein, are present in an amount of 20 to 96 parts by weight.

In this case, it is disadvantageous that the butadiene-based rubber resin fine particles and the non-butadiene-based copolymer resin fine particles are separately synthesized and mixed to form the plastisol resin fine particles, which causes an increase in manufacturing cost. On the other hand, it has the advantages described below in adjusting the particle size or particle size distribution of the resin particles.

It is generally difficult to control the particle size of the butadiene rubber resin fine particles, and it is extremely difficult to obtain a large particle size. On the other hand, the applicant
In the above-mentioned Japanese Patent Application No. 4-342508, the average particle size of the dispersed resin particles affects the initial viscosity and stability of the sol when plastisol is formed, so it is important to control the particle size of the dispersed resin particles. The number average primary particle diameter of the dispersed resin fine particles is 0.3 to 20 μm.
It has been disclosed that it is preferable to set m.

In the above-mentioned third aspect of the present invention, a method of separately preparing butadiene rubber resin fine particles and non-butadiene copolymer resin fine particles and mixing them to obtain plastisol particles. Since the average particle diameter is controlled mainly by focusing on the non-butadiene copolymer fine particles, it is easy to control the particle diameter of the resin fine particles for plastisol as the average particle diameter of these two types of fine particles. It will be possible to do.

The above is a description of the three modes of the present invention in which the butadiene-based polymer fine particle soft core component is mixed with the components derived from two other monomers in the fine particles for plastisol. In the plastisol according to the various aspects of the present invention, in addition to the unsaturated carboxylic acid compound and the unsaturated compound not containing a carboxyl group, a carboxyl group is used as the other monomer component to coexist with the butadiene-based polymer fine particle soft nucleus component. By using an unsaturated compound having a functional group capable of reacting with, it is possible to obtain a higher level of heat resistance.

That is, the fourth aspect of the present invention is to comprise 1 to 60 parts by weight of (A) butadiene-based polymer fine particle soft core component.
(B) Non-butadiene copolymer resin fine particle components 40 to 99 obtained by copolymerizing an unsaturated compound having a functional group capable of reacting with a carboxyl group, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group A plastisol, characterized in that a resin fine particle mixture composed of 1 part by weight is dispersed in a plasticizer, wherein the butadiene-based polymer fine particle soft core component (A) is Fine particles of butadiene polymer obtained by polymerizing the polymer; (2) Fine particles of a copolymer of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C. or lower; (3) Tg of 25 Fine particles of a copolymer of a butadiene monomer and an unsaturated compound having no carboxyl group at a temperature of not higher than 0 ° C;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof; The butadiene-based copolymer resin fine particle component (B) is a unit derived from an unsaturated compound having a functional group capable of reacting with 0.2 to 10 parts by weight of a carboxyl group per 100 parts by weight of the resin fine particle mixture, 3
To 20 parts by weight of units derived from unsaturated carboxylic acid compounds and 10 to 95.8 parts by weight of units derived from unsaturated compounds not containing carboxyl groups. .

The fifth aspect of the present invention is to add 40 to 99 parts by weight of a functional group capable of reacting with a carboxyl group in the total in the presence of 1 to 60 parts by weight of a butadiene-based polymer fine particle soft core component. Unsaturated compounds, unsaturated carboxylic acid compounds,
And a butadiene-based rubber resin fine particle obtained by copolymerizing an unsaturated compound not containing a carboxyl group is a plastisol dispersed in a plasticizer, wherein the butadiene-based polymer fine particle soft nucleus component is (1) butadiene Butadiene polymer particles obtained by polymerizing a monomer; (2) Copolymer particles of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C. or lower; (3) Tg Of 25 ° C. or less, fine particles of a copolymer of a butadiene monomer and an unsaturated compound containing no carboxyl group;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound having no carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof; A unit derived from an unsaturated compound having a functional group capable of reacting with a carboxyl group excluding those contained in the butadiene-based polymer fine particle soft nucleus component in the rubber resin fine particle, in the butadiene-based polymer fine particle soft nucleus component A unit derived from an unsaturated carboxylic acid excluding those contained in, and a unit derived from an unsaturated compound not containing a carboxyl group other than those contained in the butadiene-based polymer fine particle soft nucleus component, 0.2 to 10 parts by weight, 3 to 20 parts by weight, and 10 to 100 parts by weight of the butadiene rubber resin fine particles, respectively.
A plastisol characterized in that it is present in an amount of 95.8 parts by weight.

Further, a sixth aspect of the present invention is (A) a butadiene rubber resin fine particle component, and (B) an unsaturated compound having a functional group capable of reacting with a carboxyl group, an unsaturated carboxylic acid compound and a carboxyl group. Is a plastisol in which a resin fine particle mixture composed of a non-butadiene-based copolymer resin fine particle component obtained by copolymerizing an unsaturated compound not containing a butadiene-based rubber resin fine particle component is dispersed in a plasticizer. (A) is (1) butadiene polymer fine particles obtained by polymerizing a butadiene monomer; (2) a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C. or less. Copolymer fine particles; (3) Copolymer fine particles having a Tg of 25 ° C. or less and containing a butadiene monomer and an unsaturated compound containing no carboxyl group;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and a fine particle of a butadiene polymer selected from a mixture thereof. In the presence of nuclear components,
The butadiene-based rubber resin fine particles are obtained by copolymerizing an unsaturated compound having a functional group capable of reacting with a carboxyl group, an unsaturated carboxylic acid compound and an unsaturated compound having no carboxyl group. It has units derived from unsaturated carboxylic acid excluding those contained in the polymer fine particle soft core component in an amount of 3 to 20 parts by weight per 100 parts by weight of the butadiene rubber resin fine particles, and The butadiene-based copolymer resin fine particles contain a unit derived from an unsaturated carboxylic acid in an amount of 3 to 100 parts by weight per 100 parts by weight of the non-butadiene-based copolymer resin fine particles.
20 parts by weight, in the resin fine particle mixture, a unit derived from the butadiene-based polymer fine particle soft nucleus component, and a carboxyl group excluding those contained in the butadiene-based polymer fine particle soft nucleus component. A unit derived from an unsaturated compound having a reactive functional group, and a unit derived from an unsaturated compound containing no carboxyl group other than those contained in the butadiene-based polymer fine particle soft nucleus component are respectively 1 to 60 parts by weight, 0.2 to 10 parts by weight, and 10 to 100 parts by weight of the resin fine particle mixture.
A plastisol characterized in that it is present in an amount of 95.8 parts by weight.

In the above embodiment, in addition to the unsaturated carboxylic acid compound and the unsaturated compound not containing a carboxyl group, it may react with a carboxyl group as another monomer component to be coexisted with the butadiene-based polymer fine particle soft nucleus component. By using an unsaturated compound having a functional group,
It is possible to obtain a higher level of heat resistance. However, when an unsaturated compound having a functional group capable of reacting with a carboxyl group is used, the film forming temperature is increased by about 10 to 20 ° C. and the elongation of the film is slightly decreased as compared with the case where the unsaturated compound is not used. As such, its use should be determined by the required characteristics required.

Examples of unsaturated compounds capable of reacting with the carboxyl group which can be used in the preparation of the plastisol according to the present invention are glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 2-
Hydroxyethyl acrylate and methacrylate,
2-hydroxypropyl acrylate or methacrylate, N-methylol acrylamide or methacrylamide and its alkoxy compounds are mentioned. These unsaturated compounds can be used alone or as a mixture.

In the plastisol according to the present invention, the butadiene-based polymer fine particle soft nucleus component is considered to contribute to imparting toughness to the formed plastisol film.
The amount of the units derived from the butadiene-based polymer fine particle soft nucleus component in the resin fine particles in the plastisol of the various aspects of the present invention is 1 per 100 parts by weight of the resin fine particles.
-60 parts by weight, preferably 5-20 parts by weight. If the amount of the unit derived from the butadiene-based polymer fine particle soft nucleus component is less than 1 part by weight, the effect of imparting toughness to the formed plastisol film is not exerted, and if it exceeds 60 parts by weight, the formed plastisol film is It becomes brittle.

The amount of the units derived from the unsaturated carboxylic acid in the resin fine particles is 3 to 20 parts by weight per 100 parts by weight of the resin fine particles, excluding those contained in the soft core component of the butadiene-based polymer fine particles. , Preferably 4 to 12 parts by weight. The amount of units derived from unsaturated carboxylic acid is 3
If it is less than parts by weight, a practically acceptable level of storage stability cannot be expected, and if this amount is increased, the storage stability of plastisol improves, but at the same time, it is necessary for heating to form a film. The temperature also rises, and when this amount exceeds 20 parts by weight, it becomes impossible to form a film under practical conditions (heating at a temperature of 250 ° C. or lower for 5 minutes or less).

The amount of units derived from unsaturated compounds not containing a carboxyl group in the resin microparticles of the plastisol of the various embodiments of the present invention is such that the unsaturated compound having a functional group capable of reacting with a carboxyl group is further added. When not used as a monomer component, the resin fine particles 100 except for those contained in the butadiene-based polymer fine particle soft nucleus component are used.
20-96 parts by weight, preferably 60-92, per part by weight
When the unsaturated compound having a functional group capable of reacting with a carboxyl group is used as a further monomer component, 100 parts by weight of the resin fine particles are excluded except those contained in the butadiene-based polymer fine particle soft core component. 10-9 per copy
It is 5.8 parts by weight, preferably 58.0 to 91.7 parts by weight.

Furthermore, in the plastisol of various embodiments of the present invention, when an unsaturated compound having a functional group capable of reacting with a carboxyl group is used as another monomer, the unit derived from such a compound in the resin fine particles is used. The amount is 0.2 to 10 parts by weight, preferably 0.3 to 2 parts by weight, per 100 parts by weight of the resin particles, excluding those contained in the butadiene-based polymer particles soft core component. This amount is 0.
When the amount is less than 2 parts by weight, the heat resistance is not substantially improved, while when the amount exceeds 10 parts by weight, the film forming properties of the film are significantly deteriorated.

In the production of resin fine particles for plastisol according to various aspects of the present invention, a polymerization method in water such as solution polymerization, suspension polymerization or emulsion polymerization can be used, but in the present invention, Particularly, since the particle diameter needs to be controlled and the butadiene-based polymer resin fine particles are an essential component, a method of obtaining the resin fine particles by emulsion polymerization is the most preferable method for producing the resin fine particles.

The butadiene-based polymer fine particle soft-nucleus component used in the plastisols of the various embodiments of the present invention described above includes butadiene alone or with butadiene, an unsaturated carboxylic acid compound and / or a carboxyl group-free carboxyl group. It can be prepared by polymerizing a saturated compound with an emulsion polymerization method as shown below.

The emulsion polymerization for preparing the butadiene-based polymer fine particle soft nucleus component according to the present invention is carried out by emulsifying at 0.2 to 2% by weight and initiating at 0.05 to 5% by weight based on the total monomer mixture. 5 to 95 ° C while stirring the water containing the agent
To 20 to 60% by weight of the monomer mixture, and optionally 0.
It can be performed by adding 1 to 0.5% by weight of a chain transfer agent.

Examples of emulsifiers that can be used in the emulsion polymerization of the present invention include sodium stearate, sodium oleate, sodium laurate, sodium dodecylbenzene sulfonate, sodium dibutyl sulfosuccinate, sodium alkyldiphenyl ether disulfonate, and polyoxy. Examples thereof include ethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene sorbitan monolaurate.

Examples of polymerization initiators that can be used are water-soluble initiators such as ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide and t-butyl hydroperoxide, and water-soluble initiators thereof. A combination of an initiator and a reducing agent such as sodium sulfite, ammonium sulfite, sorbic acid and sucrose may be mentioned.

Further, chain transfer agents that can be used include n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoacetic acid, mercaptoethanol and the like.

The non-butadiene copolymer resin fine particle component in the plastisol of the present invention is an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, and, if necessary, reacts with a carboxyl group. It is possible to prepare an unsaturated compound having a possible functional group by copolymerizing under the same conditions as the preparation of the butadiene-based polymer fine particle soft nucleus component of the present invention described above.

Further, the method for preparing the butadiene-based rubber resin fine particles from the butadiene-based polymer fine particle soft-nucleus component obtained as described above is as follows. The butadiene-based polymer fine particles of the present invention described above are prepared by using the carboxylic acid compound and the unsaturated compound not containing a carboxyl group, and, if necessary, the unsaturated compound having a functional group capable of reacting with a carboxyl group in addition to the unsaturated compound. It can be carried out by copolymerizing under basically the same conditions as the preparation of the soft nucleus component.

However, in the polymerization for preparing the butadiene-based rubber resin fine particles, it is necessary to pay more attention to the amount of the emulsifier to be added.

In the case of preparing fine particles of butadiene rubber resin, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, which are added later to the reaction system, and, if necessary, a carboxyl group and The place of polymerization of an unsaturated compound having a reactive functional group,
It is necessary to limit the amount of the emulsifier to be added to the surface or inside of the butadiene-based polymer fine particle soft nucleus component. It is necessary to make it an amount that does not generate various emulsifier micelles.

The plastisol of the present invention is in the form of a mixture of a butadiene-based polymer fine particle soft nucleus component and a non-butadiene-based copolymer resin fine-particle component, or a butadiene-based rubber resin fine-particle component and a non-butadiene-based copolymer resin. When in the form of a mixture with a fine particle component, such a mixture is prepared by separately forming each component as a latex as described above and then mixing them in a latex state, followed by spray drying or the like. It can be prepared by drying to obtain a mixed powder. Alternatively, the separately prepared latex may be dried by spray drying or the like to be pulverized, and then the powder may be mixed.

In the plastisol of the present invention, the stability of the plastisol can be further enhanced by neutralizing the carboxyl group contained in the resin fine particles prepared as described above with an alkaline metal compound.
However, in this case, the film forming characteristics of the film tend to be slightly deteriorated, and therefore the optimum range of the neutralization degree of the carboxyl group needs to be determined depending on the use of the plastisol. Generally, it is preferable to neutralize at least 5%, preferably 10% to 25%, of the carboxyl groups contained in the resin fine particles. Examples of alkaline metal compounds that can be used for this purpose include monovalent alkaline metal compounds such as sodium hydroxide and potassium hydroxide; divalent alkaline metal compounds such as calcium hydroxide, barium hydroxide, magnesium acetate and acetic acid. Zirconium, zinc ammonium chloride, zinc ammonium acetate, and zirconium ammonium carbonate; 3
Valent alkaline metal compounds such as aluminum hydroxide and basic aluminum acetate.

In this case, a divalent alkali metal compound rather than a monovalent one and a trivalent one rather than a two-valent one give the plastisol excellent stability, but at the same time, there is a tendency that the film forming temperature rises. Therefore, the kind of the alkaline metal compound used for this purpose must be selected as the most suitable one according to the purpose of the plastisol.

The dispersed resin fine particles thus obtained are dispersed in a plasticizer to form a plastisol.

Examples of suitable plasticizers which can be used in the plastisols according to the invention are di-2-ethylhexyl phthalate, dibutyl phthalate, diisooctyl phthalate, butyl cyclohexyl phthalate,
Butyloctyl phthalate, diisononyl phthalate,
Phthalates such as dicapryl phthalate and diisodecyl phthalate; adipates such as di-2-ethylhexyl adipate and diisodecyl adipate; sebacates such as di-2-ethylhexyl sebacate; azelaates such as dioctyl azelate; tri Phosphates such as cresyl phosphate and tri-2-ethylhexyl phosphate; citrates such as tri-2-ethylhexyl citrate and acetyltributyl citrate; acetylated glycerides such as glycerol diacetate monolaurate; epoxidation Examples include epoxidized glycerides such as soybean oil and epoxidized linseed oil.

The plasticizer affects the fluidity, film forming property and film physical properties of the plastisol. Basically, the compatibility between the plasticizer and the polymer is an important factor. If the compatibility is extremely poor, it will not melt to form a continuous film even if heated, but even if the compatibility is slightly poor, practical problems such as plasticizer oozing from the inside to the film surface after film formation Occurs. Therefore, the plasticizer must be carefully selected for its compatibility with the polymer and selected carefully. The amount of the plasticizer added is usually in the range of 50 to 200 parts by weight (phr) with respect to 100 parts by weight of the plastisol resin fine particles.

Further, the fluidity and physical properties of plastisol can be adjusted by adding various additives. If necessary, the above-mentioned properties can be adjusted by adding a surfactant, a pigment, a filler, a foaming agent and a volatile organic solvent. Of these, a volatile organic solvent is often added to adjust the viscosity and the amount of adhesion when dipping or coating the plastisol. However, since the addition of a too large amount of solvent impairs the characteristics of plastisol, it is usually desirable to keep the addition amount within 10 parts by weight with respect to 100 parts by weight of the resin particles for plastisol.

The present invention will be described in more detail by the following comparative examples and examples.

(Comparative Example 1) A glass polymerization apparatus having an internal volume of 1000 ml equipped with a stirrer and a reflux condenser was charged with styrene (hereinafter referred to as "St") / methacrylic acid (hereinafter referred to as "MAA"). 400 g of a mixed monomer having a weight ratio of 93/7 was initially charged with 40 g of distilled water together with 400 g of distilled water, and sodium alkyldiphenyl ether disulfonate was used as an emulsifier in the product (manufactured by Kao Corporation, trade name Perex SS-L: hereinafter referred to as “SSL”). Of 50% aqueous solution of 4% and 4% of 10% aqueous solution of ammonium persulfate were added.

While stirring the mixture at 250 rpm,
After raising the temperature to 90 ° C. and polymerizing for 30 minutes, the remaining monomers were added dropwise over 3 hours. Further, after completion of dropping of the monomer, heating was carried out for 4 hours to complete the polymerization. Polymerization rate is 98%
Met. The number average particle size of the produced latex is 0.5.
It was 3 μm.

In the polymer dispersion thus obtained, 5%
The polymer dispersion was neutralized by adding the sodium hydroxide aqueous solution of 1. to adjust the pH to 9.5. The amount of sodium hydroxide added here was equivalent to the amount that neutralized 10.0% of the carboxyl groups of the copolymerized methacrylic acid. Then, after adjusting the solid content concentration to 12.5%, using a spray dryer (Yamato Scientific Co., Ltd., Parvis GS-31) equipped with a nozzle having a diameter of 711 μm, an inlet temperature of 120 ° C. and an outlet temperature of Spray dried at 60 ° C. The obtained particles were porous secondary particles having a diameter of 5 to 200 μm. This polymer powder was dispersed in di-2-ethylhexyl phthalate (hereinafter referred to as "DOP") to give a plastisol. Amount of DOP added to form plastisol, initial viscosity of the obtained plastisol, storage stability at 25 ° C. (viscosity increase rate), minimum film forming temperature, heat resistant temperature of formed film, 1
The product of the breaking strength and the elongation (tensile product) is shown in the table as a measure of the 00% modulus, the breaking strength, the elongation and the toughness of the formed film. The storage stability of plastisol, the minimum film forming temperature, the heat resistant temperature of the film, the 100% modulus, the breaking strength, and the elongation were measured by the following methods.

(Storage stability) The viscosity of plastisol was 25 using a B-type rotational viscometer (BM type) manufactured by Tokyo Keiki Co., Ltd.
It was measured at ° C. Since plastisol exhibits thixotropic properties, the viscosity was taken as the value when equilibrium was reached. The storage stability is the viscosity measured immediately after the plastisol was left at room temperature for a predetermined time and the viscosity immediately after the plastisol was prepared (initial viscosity).
It is shown by the ratio divided by.

(Minimum film forming 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 and then cooled to visually inspect whether a continuous film was formed. The test raised the heating temperature from 80 ° C. in steps of 10 ° C. and determined the lowest temperature at which a continuous film was formed.

(Heat-resistant temperature) Plastisol at 180 ° C. for 2
It was heated for 0 minutes to prepare a plastisol film sheet having a thickness of about 4 mm. Using this sheet as a sample, TMA
(Seiko Denshi Kogyo 120C) was used to measure the heat resistant temperature. Load 10 using a needle probe with a diameter of 2 mm
It was measured in g. In this case, the sample sheet is cooled to −5 ° C., set on quartz glass, and heated at a rate of 4 ° C./min.
Waiting for the temperature to rise to 0 ° C., the injection was started. The evaluation was carried out using the penetration as a function of this temperature. The penetration rate remained zero at the beginning of the temperature rise, or only proceeded at a slow speed, but when the temperature exceeded the heat-resistant temperature of the sample, the speed rapidly increased and hit the quartz glass and stopped. The heat resistant temperature was the temperature at which the probe penetrated 50% of the thickness of the measurement sample sheet.

(Mechanical Strength) Plastisol at 180 ° C. for 2 hours
A sheet having a thickness of about 2 mm was prepared by heating for 0 minutes, and this was punched with a JIS No. 2 dumbbell to prepare a test sample.
This sample is Autograph AG500 manufactured by Shimadzu Corporation
Using 0B, 100% modulus, breaking strength and elongation were measured according to JIS-K7113 (test speed 100 m
m / min, temperature 25 ° C).

(Comparative Example 2) St / MAA / glycidyl methacrylate (hereinafter referred to as "GMA") (91/7
The procedure of Comparative Example 1 is repeated except that the mixed monomer of (2) is used.
A copolymer dispersion of St / MAA / GMA (91/7/2) was obtained.

The polymerization rate is 98% and the number average particle diameter is 0.5 μm.
It was m.

Further, the obtained dispersion is neutralized with sodium hydroxide and then spray-dried to obtain a polymer powder, which is then DO.
It was blended in P to obtain plastisol. Various properties of the obtained plastisol were measured, and the results are shown in the table.

(Comparative Example 3) Comparative Example except that a mixed monomer of methyl methacrylate (hereinafter referred to as "MMA") / butyl acrylate (hereinafter referred to as "BA") / MAA (83/10/7) was used. MMA / B in the procedure 1
A copolymer dispersion of A / MAA / (83/10/7) was obtained.

Polymerization rate is 98%, number average particle size is 0.45
μm.

Further, the obtained dispersion is neutralized with sodium hydroxide and then spray-dried to obtain a polymer powder, which is then DO.
It was blended in P to obtain plastisol. Various properties of the obtained plastisol were measured and the results are shown in the table.

(Comparative Example 4) A pressure resistant polymerization apparatus made of glass having an internal volume of 2000 ml equipped with a stirrer was used, and a weight ratio of butadiene (hereinafter referred to as "BD") / St / MAA was 1
200 g of 0/83/7 mixed monomer, 0.4 g of lauryl mercaptan, and 792 g of distilled water were charged, and sodium alkyldiphenyl ether disulfonate (manufactured by Kao Corporation, trade name Perex SS-L: hereinafter as “SSL”) was used as an emulsifier. 4 g of a 50% aqueous solution of the above) and 4 g of a 10% aqueous solution of ammonium persulfate were added.

While stirring the mixture at 250 rpm, the temperature was raised to 75 ° C. and the mixture was heated and reacted for 10 hours to complete the polymerization. Polymerization rate is 95%, number average particle size is 0.30 μm
Met.

The obtained copolymer dispersion was neutralized and spray-dried according to the procedure of Comparative Example 1 and then compounded in DOP to form plastisol, and various properties were measured. The results are shown in the table. .

(Example 1) St / BD was added to a pressure resistant polymerization apparatus made of glass with an internal volume of 2000 ml equipped with a stirrer.
(Weight ratio: 25/75) mixed monomer 280 g, lauryl mercaptan 1.4 g, and distilled water 1108 g were charged, and sodium alkyldiphenyl ether disulfonate (manufactured by Kao Corporation, trade name Perex SS-L: hereinafter) as an emulsifier. (Referred to as "SSL") 5.6 g of a 50% aqueous solution and a 10% aqueous solution of ammonium persulfate 11.2
g was added.

While stirring the mixture at 250 rpm, the temperature was raised to 75 ° C. and the mixture was heated and reacted for 10 hours to complete the polymerization to obtain a butadiene copolymer soft core fine particle dispersion A.
The polymerization rate was 99%, and the number average particle size was 0.20 μm.

Next, in the presence of the obtained butadiene copolymer soft core particles, polymerization of a mixed monomer of St / MMA = 92.6 / 7.4 was carried out under the following conditions.

Butadiene copolymer soft nucleus particle dispersion A 5
0 g (solid content of about 10.0 g), distilled water 410 g, SS
After being charged with 0.4 g of an L-50% aqueous solution into a glass polymerization apparatus having an internal volume of 1000 ml equipped with a stirrer and a reflux condenser, 190 g of a mixed monomer of St / MAA = 92.6 / 7.4 and ammonium persulfate 3.8 g of 10% aqueous solution was added, and the mixture was stirred at 250 rpm, the temperature was raised to 90 ° C. and heated for 8 hours to carry out polymerization.
A butadiene rubber resin copolymer dispersion B was obtained. In this case, the polymerization rate was 99%, and the final composition of the obtained dispersion liquid was BD copolymer soft core particles / St / MAA = 5/88 /
Considered to be 7. The number average particle diameter of the obtained dispersion was 0.35 μm.

The solid content concentration of the obtained dispersion is 12.5%.
After that, a spray dryer (Yamato Scientific Co., Ltd., Parvis GS-3) equipped with a nozzle having a diameter of 711 μm was installed.
Using 1), spray drying was performed at an inlet temperature of 120 ° C and an outlet temperature of 60 ° C. The obtained particles were porous secondary particles having a diameter of 5 to 200 μm. This polymer powder was
Plastisol was dispersed in 2-ethylhexyl phthalate (hereinafter referred to as "DOP"). The amount of DOP added to form the plastisol and the various properties of the resulting plastisol are shown in the table.

Example 2 A polymer dispersion was prepared by adding 5% aqueous sodium hydroxide solution to the butadiene rubber resin copolymer dispersion B obtained in Example 1 to adjust the pH to 9.5. The liquid was neutralized. The amount of sodium hydroxide added here was equivalent to the amount that neutralized 20.0% of the carboxyl groups of the copolymerized methacrylic acid.

By the same procedure as in Example 1, the copolymer resin particles were spray-dried and dispersed in DOP to obtain plastisol.

Examples 3 and 4 According to the procedure of Example 1, in the presence of 50 g of butadiene copolymer soft core particle dispersion A (solid content 10.0 g), St / MAA / GMA =
Using 190 g of a mixed monomer of 91.6 / 7.4 / 1.0, BD copolymer soft core particles / St / MAA / GMA =
A 5/87/7/1 butadiene rubber resin copolymer dispersion was synthesized. (Polymerization rate 99%, number average particle size 0.33
μm) The obtained copolymer dispersion was divided into two, and one was spray-dried according to the procedure of spray-drying in Example 1 to obtain a butadiene rubber resin copolymer powder, which was then dispersed in DOP. To obtain the plastisol of Example 3, the other copolymer dispersion was neutralized and spray-dried according to the procedure of Example 2, and then D
It was dispersed in OP to obtain the plastisol of Example 4.

Various properties of these plastisols were measured,
The results are shown in the table.

Example 5 A pressure resistant polymerization apparatus made of glass and having an internal volume of 2000 ml equipped with a stirrer, BD monomer 280 g, lauryl mercaptan 1.4 g, distilled water 11
08 g was charged, and as an emulsifier, 5.6 g of a 50% aqueous solution of sodium alkyldiphenyl ether disulfonate (manufactured by Kao Corporation, trade name Perex SS-L: hereinafter referred to as “SSL”) and a 10% aqueous solution of ammonium persulfate 11. 2 g was added.

While stirring the mixture at 250 rpm, the temperature was raised to 75 ° C. and the mixture was heated and reacted for 10 hours to complete the polymerization to obtain a butadiene polymer soft nucleus fine particle dispersion C. The polymerization rate was 99%, and the number average particle size was 0.20 μm.

Next, in the presence of the butadiene polymer soft core particles, the procedure of Example 1 was repeated except that the butadiene polymer soft core particle dispersion C was used in place of the butadiene copolymer soft core particle dispersion A. St / MAA = 92.6 /
Polymerization of the mixed monomer of 7.4 is carried out to produce BD soft nucleus particles /
A dispersion liquid of St / MAA = 5/88/7 was obtained (polymerization rate was 99%, number average particle size was 0.35 μm).

The butadiene rubber resin copolymer dispersion thus obtained was spray dried according to the procedure of Example 1 to obtain a copolymer powder, which was then dispersed in DOP to obtain a plastisol.

Various properties of the obtained plastisol were measured,
The results are shown in the table.

Example 6 St / BD obtained in Example 1 =
25/75 Butadiene Copolymer Soft Nucleus Particle Dispersion A50
0 g (solid content 100 g), SSL 50% aqueous solution 4 g
Along with the stirrer and reflux condenser, the internal volume 10
After charging to a 00 ml glass polymerization device, St / MA
A: 100 / g of mixed monomer of 86/14, 2.0 g of 10% aqueous solution of ammonium persulfate were added, and the mixture was added to 250
While stirring at rpm, the temperature was raised to 90 ° C. and heated for 8 hours to carry out polymerization, and BD copolymer soft core particles / St / M
A butadiene rubber resin fine particle dispersion D with AA = 50/43/7 was obtained (polymerization rate: 99%, number average particle diameter: 0.34).
μm).

Next, according to Comparative Example 1, St / MAA = 9
A 3/7 non-butadiene copolymer particle dispersion E was synthesized (polymerization rate: 98%, number average particle size: 0.53 μm).
Using the resulting dispersions D and E, the weight ratio of the copolymer component contained in the mixture was adjusted so that butadiene-based rubber resin fine particles / non-butadiene-based copolymer particles = 10/90. , 30 parts by weight of Dispersion D and 182 parts by weight of Dispersion E, and then spray-dried according to the procedure of Example 1, BD rubber resin copolymer particles and St / MAA non-butadiene copolymer particles To obtain mixed resin fine particles. The composition of the obtained mixed resin fine particles was 5 parts by weight of butadiene copolymer soft core fine particles per 100 parts by weight of the mixed resin fine particles,
In the preparation of Dispersions D and E, 88 parts by weight of the unit derived from the St monomer polymerized and 7 parts by weight of the unit derived from the MAA monomer were used.

This mixed resin fine particle powder was dispersed in DOP to form a plastisol, and its various properties were measured. The results are shown in the table.

(Example 7) Using the butadiene copolymer soft core particle dispersion A obtained in Example 1 and following the procedure of Example 1, St / MAA in the presence of butadiene copolymer soft core particles. = 92.2 / 7.8 mixed monomers were polymerized. In this example, 100 g (solid content 20 g) of the butadiene copolymer soft nucleus particle dispersion A and 180 g of the St / MAA mixed monomer were used for the polymerization, and the butadiene copolymer soft nucleus fine particles / St / MAA
A dispersion liquid of butadiene-based rubber resin copolymer particles of 10/83/7 was obtained. The resulting copolymer dispersion was spray dried according to the procedure of Example 1 to obtain a copolymer powder and then DO
It was dispersed in P to obtain plastisol.

Various properties of this plastisol were measured, and the results are shown in the table.

(Example 8) Instead of the butadiene copolymer soft core particle dispersion A used in Example 7, the butadiene polymer soft core particle dispersion C obtained in Example 5 was used. According to the procedure, butadiene polymer soft core fine particles / St / M
A butadiene rubber resin copolymer dispersion with AA = 10/8/3/7 was obtained. The resulting copolymer dispersion was spray dried according to the procedure of Example 1 to obtain a copolymer powder and then DO
It was dispersed in P to obtain plastisol.

Various properties of this plastisol were measured, and the results are shown in the table.

(Example 9) Dispersion D obtained in Example 6
And dispersion E so that the weight ratio of the resin fine particle components contained in the mixture is butadiene rubber resin particles / non-butadiene copolymer particles = 20/80.
6 parts by weight of Dispersion D and 161.6 parts by weight of Dispersion E were mixed and then spray dried according to the procedure of Example 1 to give B
Mixed resin fine particles of D rubber resin copolymer particles and St / MAA non-butadiene copolymer particles were obtained. In this example, the composition of the obtained mixed resin fine particles was 10 parts by weight of the butadiene copolymer soft core fine particles per 100 parts by weight of the mixed resin fine particles, and the St monomer which was polymerized in the preparation of the dispersions D and E. And 83 units by weight, and 7 units by weight of units derived from the MAA monomer.

This mixed resin fine particle powder was dispersed in DOP to give a plastisol, and its various properties were measured. The results are shown in the table.

(Examples 10 and 11) BD / fumaric acid (hereinafter referred to as "FA") = 9 according to the procedure of Example 1.
BD / FA = 98/2 with 8/2 mixed monomer
A butadiene copolymer soft nucleus particle dispersion liquid F was obtained. The polymerization rate was 98%, and the particle size of the butadiene copolymer soft core particles in this dispersion F was 0.2 μm.

Then, according to the procedure of Example 1, polymerization of the mixed monomer of St / MAA = 90/10 was carried out in the presence of the obtained butadiene copolymer soft nucleus particle dispersion F. In this example, 300 g (solid content 60 g)
Dispersion liquid F, 140 g of a mixed monomer of St / MAA, 240 g of distilled water, 2.4 g of a 50% aqueous solution of SSL, and 2.8 g of a 10% aqueous solution of ammonium persulfate were used to carry out polymerization to obtain butadiene copolymer soft core fine particles / St / MAA =
A dispersion liquid of 30/63/7 butadiene-based rubber resin fine particles was obtained. The obtained copolymer dispersion was divided into two, and one of them was spray-dried according to the procedure of spray-drying of Example 1 to obtain a copolymer powder, which was then dispersed in DOP to be dispersed in plastisol of Example 10. And the other copolymer dispersion was used in Example 2
The plastisol of Example 11 was prepared by neutralizing and spray-drying according to the procedure of 1. and dispersing in DOP.

Various properties of these plastisols were measured,
The results are shown in the table.

Example 12 The butadiene polymer soft core particle dispersion C obtained in Example 5 was used in place of the butadiene copolymer dispersion used in Example 7, St / MAA = 92.2 /
MMA / BA / MMA instead of 7.8 mixed monomer
= 81.1 / 11.1 / 7.8 mixed monomer,
According to the procedure of Example 7, a butadiene rubber resin copolymer dispersion of butadiene copolymer soft core fine particles / MMA / BA / MAA = 10/73/10/7 was obtained. The obtained copolymer dispersion was neutralized and spray-dried according to the procedure of Example 2 to obtain a copolymer powder, which was then dispersed in DOP to give a plastisol.

Various properties of this plastisol were measured, and the results are shown in the table.

Example 13 Butadiene copolymer soft core fine particles / St / MAA = 10/8 according to the procedure of Example 7.
After a 3/7 butadiene rubber resin copolymer particle dispersion was prepared, the obtained copolymer dispersion was neutralized and spray-dried according to the procedure of Example 2 to obtain a copolymer powder. , Acetyltributyl citrate (hereinafter referred to as “ATBC”) to obtain a plastisol. Various properties of this plastisol were measured, and the results are shown in the table.

(Example 14) The copolymer powder obtained in Example 13 was dispersed in glycerol diacetate monolaurate (hereinafter referred to as "GML") to obtain plastisol, and its various properties were measured. Is shown in the table.

(Example 15) The copolymer powder obtained in Example 13 was dispersed in epoxidized soybean oil (hereinafter referred to as "ESO") to obtain plastisol, and its various properties were measured and the results are shown in Table 1. It was shown to.

(Example 16) The copolymer powder obtained in Example 13 was dispersed in epoxidized linseed oil (hereinafter referred to as "ELS") to obtain plastisol, and its various properties were measured and the results are shown in Table 1. It was shown to.

[0102]

[Table 1]

[Table 2]

[Table 3]

[Table 4] As is clear from the above Comparative Examples and Examples, the plastisol is formed by coexisting the butadiene-based polymer fine particle soft nucleus component with a unit derived from an unsaturated carboxylic acid compound and an unsaturated compound containing no carboxyl group. As a result, the balance between storage stability, which is a practically important property for plastisols, film forming characteristics, and mechanical strength of the formed film could be increased to a surprising level. By using the plastisol of the present invention, it is possible to dramatically increase the 100% modulus and breaking strength of the film while maintaining excellent storage stability and film forming characteristics, and it is an index of the toughness of the film. The stretched product could be increased more than 3 times. Further, in the plastisol according to the present invention, when a unit derived from an unsaturated compound having a functional group capable of reacting with a carboxyl group is further present as another constituent unit, the film forming property of the film is 10 ° C to 20 ° C. Although it was lowered, a higher level of heat resistance could be imparted.

The balance as a high-level plastisol obtained by the present invention is such that resin fine particles in which a resin fine particle soft nucleus component of a butadiene-based polymer having a Tg of 25 ° C. or less is present as a part of the constituents are used as plastisol fine particles. It is achieved by using it.

Claims (10)

[Claims] 1. A non-butadiene obtained by copolymerizing (A) 1 to 60 parts by weight of a butadiene polymer fine particle soft core component with (B) an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group. -Based copolymer resin fine particle component 40
Is a plastisol in which a resin fine particle mixture composed of ˜99 parts by weight is dispersed in a plasticizer, wherein the butadiene-based polymer fine particle soft nucleus component (A) is (1) polymerized with a butadiene monomer. Obtained butadiene polymer fine particles; (2) Copolymer fine particles of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C or lower; (3) Butadiene having a Tg of 25 ° C or lower Fine particles of a copolymer of a monomer and an unsaturated compound not containing a carboxyl group;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof; The butadiene-based copolymer resin fine particle component (B) does not contain a unit derived from an unsaturated carboxylic acid compound of 3 to 20 parts by weight and a carboxyl group of 20 to 96 parts by weight, per 100 parts by weight of the resin fine particle mixture. A plastisol, which is a fine particle of a copolymer of an unsaturated carboxylic acid compound and an unsaturated compound having no carboxyl group, which has a unit derived from an unsaturated compound. 2. A butadiene-based polymer fine particle soft nucleus component 1 to 1.
In the presence of 60 parts by weight, a total of 40 to 99 parts by weight of an unsaturated carboxylic acid compound and a butadiene-based rubber resin fine particle obtained by copolymerizing an unsaturated compound not containing a carboxyl group are dispersed in a plasticizer. Which is a plastisol, wherein the butadiene polymer fine particle component is (1) butadiene polymer fine particles obtained by polymerizing a butadiene monomer; (2) a single butadiene polymer having a glass transition temperature (Tg) of 25 ° C. or lower. Copolymer microparticles of a monomer and an unsaturated carboxylic acid compound; (3) Copolymer microparticles of a butadiene monomer and an unsaturated compound containing no carboxyl group, having a Tg of 25 ° C or lower;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound, and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof; The rubber resin fine particles are units derived from unsaturated carboxylic acid excluding those contained in the butadiene-based polymer fine particle soft nucleus component, and the carboxyl excluding those contained in the butadiene-based polymer fine particle soft nucleus component. A unit derived from an unsaturated compound not containing a group is 3 units per 100 parts by weight of the butadiene rubber resin fine particles.
Plastisol, characterized in that it has an amount of -20 parts by weight and 20-96 parts by weight. 3. A non-butadiene copolymer resin fine particle component obtained by copolymerizing (A) a butadiene rubber resin fine particle component with (B) an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group. A butadiene-based rubber resin fine particle component (A), which is a plastisol in which a resin fine particle mixture composed of (1) is obtained by polymerizing a butadiene monomer; (2) Fine particles of a copolymer of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C or lower; (3) a butadiene monomer and a carboxyl group having a Tg of 25 ° C or lower. Copolymer fine particles with unsaturated compound not contained;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and a fine particle of a butadiene polymer selected from a mixture thereof. In the presence of nuclear components,
It is obtained by copolymerizing an unsaturated carboxylic acid compound and an unsaturated compound which does not contain a carboxyl group, and the butadiene-based rubber resin fine particles exclude those contained in the butadiene-based polymer fine particle soft nucleus component. The amount of the unit derived from unsaturated carboxylic acid is 3 to 20 parts by weight per 100 parts by weight of butadiene rubber resin fine particles, and the non-butadiene copolymer resin fine particles are unsaturated carboxylic acid. The amount of the unit derived from is in an amount of 3 to 20 parts by weight per 100 parts by weight of the non-butadiene-based copolymer resin fine particles.
1 to 60 parts by weight of the unit derived from the butadiene-based polymer fine particle component per part by weight, and derived from an unsaturated compound containing no carboxyl group other than those contained in the butadiene-based polymer fine particle soft nucleus component Unit is 20-9
A plastisol which is present in an amount of 6 parts by weight. 4. A butadiene-based polymer fine particle soft core component 1 to 60 parts by weight, and (B) an unsaturated compound having a functional group capable of reacting with a carboxyl group, an unsaturated carboxylic acid compound and a carboxyl group. Non-Butadiene Copolymer Resin Fine Particle Component 4 Obtained by Copolymerizing Unsaturated Compound
0 to 99 parts by weight of a resin fine particle mixture,
A plastisol characterized by being dispersed in a plasticizer, wherein the butadiene-based polymer fine particle soft nucleus component (A) is (1) a butadiene polymer fine particle obtained by polymerizing a butadiene monomer; (2) Fine particles of a copolymer of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C or lower; (3) a butadiene monomer and a carboxyl group having a Tg of 25 ° C or lower. Copolymer fine particles with unsaturated compound not contained;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound having no carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof. The butadiene-based copolymer resin fine particle component (B) is
0.2 to 10 per 100 parts by weight of the resin fine particle mixture
10 parts by weight of a unit derived from an unsaturated compound having a functional group capable of reacting with a carboxyl group, 3 to 20 parts by weight of an unsaturated carboxylic acid compound, and 10 to 9 parts by weight.
A plastisol having units derived from unsaturated compounds which do not contain 5.8 parts by weight of carboxyl groups. 5. A butadiene-based polymer fine particle soft nucleus component 1 to
A total of 40 to 99 parts by weight of unsaturated compounds with functional groups capable of reacting with carboxyl groups in the presence of 60 parts by weight,
A plastisol in which butadiene rubber resin fine particles obtained by copolymerizing an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group are dispersed in a plasticizer. (1) Fine particles of butadiene polymer obtained by polymerizing a butadiene monomer; (2) Copolymer of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C. or lower. Fine particles; (3) Fine particles of a copolymer having a Tg of 25 ° C. or less and containing a butadiene monomer and an unsaturated compound containing no carboxyl group;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound, and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and fine particles selected from a mixture thereof; A unit derived from an unsaturated compound having a functional group capable of reacting with a carboxyl group excluding those contained in the butadiene-based polymer fine particle soft nucleus component in the rubber resin fine particle, in the butadiene-based polymer fine particle soft nucleus component A unit derived from an unsaturated carboxylic acid excluding those contained in, and a unit derived from an unsaturated compound not containing a carboxyl group other than those contained in the butadiene-based polymer fine particle soft nucleus component, 0.2 to 10 parts by weight, 3 to 20 parts by weight, and 10 to 95.8 parts by weight, respectively, per 100 parts by weight of the butadiene-based rubber resin fine particles. Plastisols, characterized in that present in an amount of. 6. A copolymer of (A) a butadiene rubber resin fine particle component, (B) an unsaturated compound having a functional group capable of reacting with a carboxyl group, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group. Is a plastisol in which a resin fine particle mixture composed of a non-butadiene copolymer resin fine particle component obtained by the above is dispersed in a plasticizer, wherein the butadiene rubber resin fine particle component (A) is (1) butadiene Butadiene polymer particles obtained by polymerizing a monomer; (2) Copolymer particles of a butadiene monomer and an unsaturated carboxylic acid compound having a glass transition temperature (Tg) of 25 ° C. or lower; (3) Tg Of 25 ° C. or less, fine particles of a copolymer of a butadiene monomer and an unsaturated compound containing no carboxyl group;
And (4) fine particles of a copolymer of a butadiene monomer, an unsaturated carboxylic acid compound and an unsaturated compound not containing a carboxyl group, having a Tg of 25 ° C. or lower; and a fine particle of a butadiene polymer selected from a mixture thereof. In the presence of nuclear components,
The butadiene-based rubber resin fine particles are obtained by copolymerizing an unsaturated compound having a functional group capable of reacting with a carboxyl group, an unsaturated carboxylic acid compound, and an unsaturated compound not containing a carboxyl group. It has units derived from unsaturated carboxylic acid excluding those contained in the polymer fine particle soft core component in an amount of 3 to 20 parts by weight per 100 parts by weight of the butadiene rubber resin fine particles, and The butadiene-based copolymer resin fine particles have units derived from unsaturated carboxylic acid in an amount of 3 to 20 parts by weight per 100 parts by weight of the non-butadiene-based copolymer resin fine particles. , Units derived from the butadiene-based polymer fine particle soft nucleus component, units excluding those contained in the butadiene-based polymer fine particle soft nucleus component A unit derived from an unsaturated compound having a functional group capable of reacting with a voxyl group, and a unit derived from an unsaturated compound containing no carboxyl group except those contained in the soft core component of butadiene-based polymer fine particles , 1 to 60 parts by weight, and 0.2 to 1 per 100 parts by weight of the resin fine particle mixture, respectively.
A plastisol characterized in that it is present in an amount of 0 parts by weight, and 10 to 95.8 parts by weight. 7. The plastisol according to claim 1, wherein the resin fine particle mixture is produced by emulsion polymerization. 8. The plastisol according to claim 1, wherein at least 5% of the carboxyl groups contained in the resin fine particle mixture are neutralized with an alkaline metal compound. 9. The plastisol according to claim 8, wherein 10 to 25% of the carboxyl groups contained in the resin fine particle mixture are neutralized with an alkaline metal compound. 10. The resin fine particle mixture 10 having an amount of plasticizer of 10.
50 to 200 parts by weight of plastisol with respect to 0 parts by weight.