JPH0611830B2 - Organosol composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyvinyl chloride-based organosol composition and a method for producing the same.

A conventional organosol composition of this kind is prepared by dispersing a polyvinyl chloride powder in a plasticizer, adding and mixing an organic solvent which does not dissolve the polyvinyl chloride powder for the purpose of adjusting the viscosity, and further if necessary. It is composed of additives such as stabilizers. In use, this composition is applied to an object to be coated with a coater such as a roll coater or a spray, and then heated to melt and gel to form a film.

However, a film formed by such a method generally has poor adhesion to an object to be coated such as iron and aluminum,
There is a problem that after the film is formed, it easily peels off from the surface of the article to be coated. Therefore, in order to solve this problem, an attempt was made to mix an appropriate adhesion-imparting component such as vinyl chloride-vinyl acetate-maleic acid copolymer, acrylic resin, nitrile rubber, and chloroprene rubber into the organosol composition in powder form. Has been done.

If the above-mentioned adhesion-imparting component is mixed in the organosol composition as it is, since the particle size of the component is generally large, the film formed has a fine texture (porosity), which deteriorates the finished appearance. For this reason, the adhesive component is usually mixed in a form of being dissolved in an organic solvent used for the purpose of adjusting the viscosity. And, as the organic solvent, toluene, methyl isobutyl ketone, trichlene,
Solvents that dissolve well the adhesion-imparting components, such as acetate, have been selectively used.

However, the organic solvent as described above has a property of swelling polyvinyl chloride powder, the viscosity of the organosol composition obtained due to this increases with time, and the viscosity suitable for the coating method cannot be obtained. Had.

As a result of intensive studies to overcome the above-mentioned problems, the present inventors have used a specific component as an adhesion-imparting component for improving the adhesiveness to an object to be coated and polychlorinated instead of dissolving it in an organic solvent. When a part or all of the plasticizer for vinyl is heated and dissolved to be mixed with the polyvinyl chloride powder, the above-mentioned copolymer alone is not dissolved as the organic solvent used for the purpose of adjusting the viscosity, but the plasticizer is heated. Since a solvent that is well compatible with the dissolved copolymer and does not dissolve or swell the polyvinyl chloride powder can be selected and used, it is very favorable for the viscosity stability of the resulting organosol composition. Knowing that the results can be obtained, the present invention has been completed.

That is, the present invention relates to 100 parts by weight of polyvinyl chloride powder, 30 to 100 parts by weight of a plasticizer, and vinyl chloride-vinyl acetate-which is thermally dissolved in a part or all of the plasticizer.
0.1 to 20 parts by weight of maleic acid copolymer and a boiling point of 130 to 200 ° C. which is compatible with the heat-melted copolymer and does not dissolve or swell the polyvinyl chloride powder.
5 to 40 parts by weight of an organic solvent, and a second invention relating to a method for obtaining the above composition.

Since the organosol composition of the present invention uses a vinyl chloride-vinyl acetate-maleic acid copolymer as an adhesion-imparting component, it improves the adhesiveness to the surface of various coated objects such as iron and aluminum when formed into a film. While you can
As a constitution in which this copolymer is heat-dissolved in a part or all of the plasticizer, it is well compatible with the heat-melted copolymer as an organic solvent for viscosity adjustment, and dissolves and swells polyvinyl chloride powder. Since a solvent that does not contain a solvent is used, the viscosity of the composition is stabilized, and the thickening phenomenon over time is greatly suppressed, so that there is an advantage that the coating work during film formation can be performed without any problems.

The polyvinyl chloride powder used in the present invention has secondary particles having a particle size of 100 μm or less, usually 5 to 5 μm.
Those having a size of about 70 μm and generally prepared by an emulsion polymerization method are preferably used. Examples of commercially available products include ZEON 121, trade name, manufactured by ZEON CORPORATION, and Vinca P-440, trade name, manufactured by Mitsubishi Monsanto.

As the plasticizer for the polyvinyl chloride powder, any conventionally known one can be used, and examples thereof include a dialkyl ester of phthalic acid (alkyl group having 4 to 11 carbon atoms) and a trialkyl (or phenyl) ester of phosphoric acid. (the number of carbon atoms in the alkyl group _{4~10), C n H 2n +} 1 COOC n
Examples include fatty acid diesters represented by H _2n OOCC _n H _{2n + 1} (n = 4 to 10).

The vinyl chloride-vinyl acetate-maleic acid copolymer used as the adhesion-imparting component in the present invention has an average degree of polymerization of 300 to 6 measured by the Ostwald viscosity method.
00, preferably 400 to 500 is preferably used. If the degree of polymerization is too low, the adhesion-imparting function will be reduced,
On the other hand, if it is too high, the solubility in the plasticizer is lowered, so that both are not preferable.

The monomer composition of the copolymer is generally 80 to 95% by weight of vinyl chloride, preferably 88 to 92% by weight,
1 to 10% by weight of vinyl acetate, preferably 4 to 8% by weight,
The amount of maleic acid (maleic anhydride) is 1 to 10% by weight, preferably 2 to 6% by weight. Examples of commercial products of copolymers having such a monomer composition include Denki Vinyl 1000C, trade name, manufactured by Denki Kagaku Co., Ltd., ZEON 400 × 110A, trade name, manufactured by ZEON CORPORATION.

The copolymer is heat-dissolved in the plasticizer, and the plasticizer may be the total amount or a part thereof to be blended in the organosol composition. It is more preferable to use 1 to 20% by weight, particularly preferably 5 to 10% by weight, of the total amount of the plasticizer for dissolving the copolymer, from the viewpoint of stability or dispersibility of the organosolui.

The organic solvent used for the purpose of adjusting the viscosity in the present invention does not directly dissolve the above-mentioned copolymer, but is well compatible with the plasticizer in a state of being thermally dissolved, and does not dissolve or swell the polyvinyl chloride powder. Boiling point is 130 ~ 200 ℃
It is not particularly limited as long as it is one. Examples of the suitable organic solvent include mineral spirits and petroleum naphtha.

The reason why the boiling point of the organic solvent is limited to 130 to 200 ° C. is that when the boiling point is less than 130 ° C., it volatilizes during the preparation or storage of the composition and hinders the preparation work and environmental hygiene, as well as changes with time. This is because the viscosity tends to change (increase) easily, and when the temperature exceeds 200 ° C., this solvent is less likely to volatilize during film formation, which may impair the film formation work and may cause thermal damage to the object to be coated. This is because.

The organosol composition of the present invention contains the above-mentioned polyvinyl chloride powder, plasticizer, copolymer and organic solvent as essential components, and the blending ratio of these essential components is preferably in the following range. That is, with respect to 100 parts by weight of polyvinyl chloride powder, the plasticizer content is 30 to
100 parts by weight, preferably 40 to 70 parts by weight, copolymer 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, organic solvent 5 to 40 parts by weight, preferably 15 to 30 parts by weight. .

In addition to the above-mentioned essential components, conventionally known additives may be added to the above-mentioned organosol composition of the present invention. Typical of these additives are stabilizers such as dibutyltin laurate, dibutyltin malate and metallic soaps such as calcium and zinc. The stabilizer is generally used in a proportion of 0.5 to 5 parts by weight based on 100 parts by weight of polyvinyl chloride powder.

Next, as a method for obtaining the organosol composition of the present invention comprising the above-mentioned blending components, first, the above copolymer is thermally dissolved in a part or all of the plasticizer. That is, both are usually dissolved and mixed while being heated to 80 to 120 ° C. Next, polyvinyl chloride powder or this and the remaining plasticizer are added to this dissolved mixture, and when an additive such as a stabilizer is used, this additive is also added and uniformly mixed and dispersed. The temperature at this time may be in the range of 5 to 40 ° C. Finally, the above-mentioned organic solvent for viscosity adjustment is added and mixed to obtain an organosol composition, which is the object of the present invention, with little change in viscosity over time.

The organosol composition of the present invention thus obtained usually has a viscosity of 0.5 to 10 poise (25 ° C.). According to this composition, for example, a conventional coating such as a roll coater or a spray is used. Forming a film with excellent adhesiveness to the object to be coated by applying it to the object to be coated at a temperature of 40 ° C or less using a machine and then heating and melting it at a temperature of 200 to 300 ° C to cause gelation. You can

Hereinafter, examples of the present invention will be described to more specifically describe. In the following, "parts" means "parts by weight". The viscosity described below means the value measured by a BL type rotational viscometer.

Example 1 80 parts of dioctyl phthalate was added to a vinyl chloride-vinyl acetate-maleic acid copolymer (Zeon 4 manufactured by Nippon Zeon Co., Ltd.).
Twenty parts (00 × 110 A) were dissolved and mixed at about 100 ° C.
To 40 parts of this dissolved mixture, 100 parts of polyvinyl chloride powder (Zeon 121 manufactured by Nippon Zeon Co., Ltd., product name: Zeon 121), 34 parts of dioctyl phthalate and 2 parts of dibutyltin dilaurate were added and uniformly mixed and dispersed by a stirrer. It was Thereafter, 10 parts of mineral spirits were added and mixed well to obtain an organosol composition of the present invention having a viscosity of 5 poise at 25 ° C.

Comparative Example 1 20 parts of the vinyl chloride-vinyl acetate-maleic acid copolymer used in Example 1 was dissolved in a mixed solvent of 40 parts of methyl isobutyl ketone and 40 parts of toluene. To 40 parts of this solution, 100 parts of the polyvinyl chloride powder used in Example 1, 70 parts of dioctyl phthalate and 2 parts of dibutyltin dilaurate were added at 20 ° C. or lower, and uniformly mixed and dispersed by a stirrer to obtain 25 A comparative organosol composition having a viscosity of 5 poise at ° C was obtained.

Example 2 1 part of 14 parts of the vinyl chloride-vinyl acetate-maleic acid copolymer used in Example 1 was added to 86 parts of tricresyl sulfonate.
The mixture was dissolved and mixed at 20 ° C. To 35 parts of this dissolution mixture, 2
Under 5 ° C., 100 parts of the polyvinyl chloride powder used in Example 1, 20 parts of tricresyl phosphate and 1 part of dibutyl maleate were added and uniformly mixed and dispersed by a stirrer. Then, 20 parts of petroleum naphtha (trade name: Swasol # 1000, manufactured by Showa Sekiyu KK) was added and mixed well to obtain an organosol composition of the present invention having a viscosity of 2 poise at 25 ° C.

Comparative Example 2 14 parts of the vinyl chloride-vinyl acetate-maleic acid copolymer used in Example 2 was dissolved and mixed at 65 ° C in a mixed solvent of 30 parts of methyl isobutyl ketone and 56 parts of toluene. To 35 parts of this solution, 100 parts of the polyvinyl chloride powder used in Example 2 respectively, 50 parts of tricresyl oxoate and 1 part of dibutyl maleate were added at 25 ° C., and uniformly mixed and dispersed by a stirrer. By doing so, a comparative organosol composition having a viscosity of 2 poise at 25 ° C. was obtained.

Example 3 To 95 parts of dioctyl adipate was added 110 parts of 5 parts of the vinyl chloride-vinyl acetate-maleic acid copolymer used in Example 1.
Dissolved and mixed below. To 40 parts of this dissolved mixture, 100 parts of the polyvinyl chloride powder used in Example 1, 22 parts of dioctyl adipate and 1 part of dibutyl laurate were added at 30 ° C., and uniformly mixed and dispersed by a stirrer. Then, 15 parts of mineral slips were added and mixed well to obtain an organosol composition of the present invention having a viscosity of 7 poise at 25 ° C.

Comparative Example 3 5 parts of the vinyl chloride-vinyl acetate-maleic acid copolymer used in Example 3 was dissolved and mixed at 70 ° C. in a mixed solvent of 50 parts of methyl isobutyl ketone and 45 parts of toluene. To 40 parts of this solution, 100 parts of polyvinyl chloride powder used in Example 3, 60 parts of dioctyl adipate and 1 part of dibutyl laurate were added at 30 ° C., and uniformly mixed and dispersed by a stirrer, A comparative organosol composition having a viscosity of 7 poise at 25 ° C. was obtained.

The results of examining the change with time (25 ° C.) of the viscosity of each of the organosol compositions obtained in the above Examples and Comparative Examples are as shown in the following table.

As is clear from the above results, it is understood that the organosol composition of the present invention has a significantly suppressed change in viscosity over time as compared with the conventional one.

Claims (2)

[Claims] 1. 100 parts by weight of polyvinyl chloride powder, 30 to 100 parts by weight of a plasticizer, and a vinyl chloride-vinyl acetate-maleic acid copolymer 0.1 which is thermally dissolved in a part or all of the plasticizer. ˜20 parts by weight and 5 to 40 parts by weight of an organic solvent having a boiling point of 130 to 200 ° C. which is compatible with the heat-dissolved copolymer and does not dissolve or swell the polyvinyl chloride powder. An organosol composition comprising: 2. A vinyl chloride as a part or all of the plasticizer.
A vinyl acetate-maleic acid copolymer is heat-dissolved, polyvinyl chloride powder or this and the rest of the plasticizer are added and mixed, and then the mixture is made compatible with the heat-melted copolymer and the polychlorinated product is added. A method for producing an organosol composition, which comprises adding and mixing an organic solvent having a boiling point of 130 to 200 ° C. that does not dissolve or swell vinyl powder.