JPH03197546A - Film-forming composition - Google Patents

Abstract

PURPOSE:To improve the adhesive properties and solvent solubility by chlorinating a specific copolymer of vinyl chloride with vinyl acetate and/or vinyl propionate in an aq. medium. CONSTITUTION:Vinyl chloride is copolymerized with 5-45wt.% vinyl acetate and/or vinyl propionate in the presence of a polymn. initiator in an aq. medium contg. an oil-sol. chain transfer agent to give a copolymer of vinyl chloride with vinyl acetate and/or vinyl propionate. The copolymer is then washed with water, suspended in an aq. medium, and chlorinated to a chlorine content of 60wt.% or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a solvent-soluble film-forming composition used as a film-forming composition for paints and the like.

[Conventional technology]

Chlorinated vinyl chloride resin (hereinafter abbreviated as CPVC) is a substance manufactured by chlorinating vinyl chloride resin (hereinafter abbreviated as PVC), but CPVC has a higher softening temperature than PVC and has excellent heat resistance. It is something that we have. Furthermore, CPVC maintains the excellent properties of PVC, such as stiffness, creep resistance, and chemical resistance, in high-temperature regions, and is less flammable and generates less smoke even in flames than other resins. It is known as a unique industrial material that has excellent properties not found in other materials, and can also be coated on surfaces to prevent corrosion. However, in order to apply it, it is desirable to dissolve the resin in an organic solvent to make a solution, but conventional CPVC is generally used for molding, and when it is dissolved in an organic solvent to make a solution, the solution becomes cloudy and becomes transparent. I didn't get it. Furthermore, the number of organic solvents that can be used is limited, and a wide range of organic solvents cannot be used. Various improvements have been proposed to overcome this drawback of being difficult to dissolve in solvents. For example, JP-A-62-25791
4 is after suspension polymerization of vinyl chloride and α-olefin.
A method for chlorinating the resulting copolymer to produce a clear solution is disclosed. Furthermore, JP-A-63-10800
No. 4 discloses a method in which a copolymer of vinyl chloride containing ethylene or propylene is produced by a specific production method, and then chlorinated to produce a solution suitable for use as a paint or the like. However, cpvc by these methods
Although the resins have been improved compared to past CPVC, they are still soluble in a wide variety of organic solvents and have not yet been significantly improved.

[Problem to be solved by the invention]

In view of the above-mentioned circumstances, the present invention has been devised to provide a material that is easily soluble in a wide range of organic solvents, forms a transparent film when the solution is dried, and can be applied to applications that require a wide range of viscosity, such as inks, paints, adhesives, etc. It is intended to provide CPVC.

[Means to solve the problem]

It was discovered that if the resulting copolymer resin was subjected to suspension chlorination in an aqueous medium to form a CPVC system, a resin easily soluble in a wide range of organic solvents could be obtained.

Furthermore, in the chlorination stage, we focused on the fact that the surface of the powder resin is likely to be chlorinated and a heterogeneous reactant is formed, so we attempted to constantly peel and renew the surface of the powder resin as a means of chlorinating more uniformly. .

In other words, by constantly circulating the suspension with a crushing pump, or by installing a ball mill etc. in the middle of the circulation system, the powder resin surface is mechanically peeled off and renewed while being chlorinated.
The present invention was completed based on the discovery that the VC system can be more uniformly chlorinated and has improved solubility in organic solvents.

It is also possible to combine the steps of creating a copolymer of vinyl chloride containing 5 to 45% by weight of vinyl and/or propion, and chlorinating the copolymer obtained in a subsequent step. It is already known to produce CPVC resins by a combination of steps.

To copolymerize peonyl, an oil-soluble chain transfer agent is added to an aqueous medium in a polymerization vessel, and then the pressure is reduced, vinyl chloride and vinyl acetate are press-fitted, dispersed in the aqueous medium, and a polymerization initiator is added to copolymerize. Polymerize. The oil-soluble chain transfer agents used here include chlorine compounds and hydroxyl compounds.

Various diene compounds can be used, and organic peroxides or azo compounds can be used as polymerization initiators.

The aqueous medium may contain substances other than those listed above, such as antioxidants, pH
A regulator or the like may be added. The obtained copolymer is washed with water and then transferred to a chlorination step, where chlorine is passed through the copolymer in a suspended state. In the present invention, at this time, the suspension is constantly circulated through a crushing pump, or a ball mill or the like is installed in the middle of the circulation system, and the surface of the powder resin is mechanically peeled and renewed while chlorination is carried out. At this time, chlorination may be promoted by irradiation with ultraviolet rays, hydrochloric acid or the like may be used to increase the solubility of chlorine, and a small amount of a dispersant may be added if necessary. The CPVC system obtained by the method of the present invention is superior to conventional ones in that it is easily soluble in a wide variety of organic solvents and is transparent, and can be used in a wide range of film-forming compositions for inks, paints, adhesives, etc. The reason why the copolymerized amount of vinyl acetate and/or propion is 5% by weight or more is that
This is because if it is less than 45% by weight, the effect of improving solubility in organic solvents, which is a feature of the present invention, cannot be obtained, and if it is less than 45% by weight, it is difficult to copolymerize with vinyl chloride. . The reason why the chlorine content is set to 60% by weight or more is because if it is less than 60% by weight, the transparency will be poor when dissolved in various organic solvents.

The resin employed in the present invention has more voids inside the polymer particles or has smaller particle diameters, which is a preferable condition for producing the effects of the present invention.

〔Example〕

Hereinafter, the detailed explanation of the present invention will be explained with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 A glass reactor was filled with 5 fl [1 part of pure water and an average polymerization degree of 8].
00, 100 parts of vinyl chloride-vinyl acetate copolymer containing 6-ply vinyl acetate was added, and the inside of the container was purged with nitrogen while stirring, then irradiated with light at normal pressure, and chlorinated by blowing chlorine at 70°C. I did it. At this time, in order to chlorinate more uniformly, the suspension is constantly circulated by a crushing pump, and a ball mill is installed in the middle of the circulation system to mechanically peel and renew the powder resin surface while chlorinating. Ta. Chlorine content is 68% by weight
The chlorination reaction was stopped when the reaction temperature reached 1, and the remaining chlorine was removed and then dried to obtain a sample.

Example 2 500 parts of pure water and an average degree of polymerization of 400 in a glass reactor
Then, 100 parts of vinyl chloride-vinyl propionate copolymer containing 28% vinyl propionate was added, the inside of the container was purged with nitrogen while stirring, and then irradiated with light at normal pressure.
Chlorination was carried out by blowing chlorine. At that time, the suspension is constantly circulated with a crushing pump for the purpose of more uniform chlorination, and a sand mill is installed in the middle of the circulation system to mechanically peel off and renew the powder resin surface while chlorinating it. I did it. When the chlorine content reached 65% by weight, the chlorination reaction was stopped, residual chlorine was removed, and the sample was dried to obtain a sample.

Example 3 500 parts of pure water and an average degree of polymerization of 200 in a glass reactor
Then, 100 parts of vinyl chloride/vinyl acetate copolymer containing 45% by weight of vinyl acetate was added, and the inside of the container was purged with nitrogen while stirring, then irradiated with light at normal pressure, and chlorinated by blowing in chlorine at 70°C. Ta. At this time, in order to chlorinate more uniformly, the suspension is constantly circulated by a crushing pump, and a ball mill is installed in the middle of the circulation system to mechanically peel and renew the powder resin surface while chlorinating. Ta. The chlorination reaction was stopped when the chlorine content reached 62% by weight, and after removing the remaining chlorine,
A sample was obtained by drying.

Comparative Example 1 - 500 parts of pure water in a glass reactor and an average degree of polymerization of 600
100 parts of vinyl chloride resin was added, and the inside of the container was purged with nitrogen while stirring, then irradiated with light at normal pressure, and chlorine was blown into the container at 70° C. for chlorination.

At that time, in order to chlorinate more uniformly, the suspension is constantly circulated using a crushing pump, and a sand mill is installed in the middle of the circulation system to mechanically peel off and renew the powder resin surface while chlorinating. Ta. When the chlorine content reached 66% by weight, the chlorination reaction was stopped, residual chlorine was removed, and the sample was dried to obtain a sample.

Comparative Example 2 500 parts of pure water in a glass reactor and an average degree of polymerization of 600
100 parts of vinyl chloride-ethylene copolymer were added, and after vacuum degassing, nitrogen was introduced into the container to bring the pressure to normal pressure, and chlorine was blown into the container at 70° C. while irradiating it with a high-pressure mercury lamp. When the chlorine content reached 63% by weight, the chlorination reaction was stopped, residual chlorine was removed, and a sample was obtained by drying.

Table 1 shows the results of dissolving the CPVC resins obtained in Examples 1 to 3 and Comparative Examples 1 to 2 in various solvents. In addition, grab-eye ink was prepared with the following ink composition.

Toluene predetermined viscosity correction amount (α) 75 + α Note) Carmino 6BN: After kneading for 2 hours with Toyo Ink Manufacturing KK sand mill, 20
The ink was adjusted to ±2 seconds and applied to a PP film to form an ink film of 5-7 μm.

After thoroughly drying this at room temperature, the performance was investigated and the results are shown in Table 2.

Table-1 Solubility results in various solvents 0 PP film ink suitability procedure amendment (voluntary) April 12, 1990 1. Case indication 1999 Patent Application No. 336903 2. Name of invention Coating Relationship with the Case of Person Who Amends Forming Composition 3° Patent Applicant Address 4-5 Marunouchi-chome, Chiyoda-ku, Tokyo
Name (234) Sanyo Kokusaku Pulp Co., Ltd. From the results in Tables 1 and 2 above, the composition of the present invention has excellent properties as a printing ink composition for polyolefins that are not found in conventional CPVC resins. 16 Kanda Kita Jimono-cho, Chiyoda-ku 101 Ei Building 3rd floor Adhesiveness.

It is found that it has solvent solubility.

5. Subject of correction

Claims (2)

[Claims] (1) A vinyl chloride-vinyl acetate and/or vinyl propionate copolymer containing 5 to 45% by weight of vinyl acetate and/or vinyl propionate is suspended in an aqueous medium with a chlorine content of 60% by weight or more. A solvent-soluble film-forming composition obtained by chlorinating up to (2) The composition according to claim 1, which is chlorinated while being pulverized.