JPS63205363A - Vinyl polymer composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which contains a vinyl polymer having a network structure and can form a coating film having excellent flexibility and durability when used as a binder between paints, by subjecting a vinyl polymer having chemical reactive groups and complementary reaction groups to an intramolecular and/or intermolecular reaction. CONSTITUTION:A vinyl polymer compsn. contains a modified vinyl polymer having a network structure, obtd. by subjecting a vinyl polymer having at least one chemical reaction group (A) and at least one complementary reactive group (B) capable of reacting with the group A (e.g., a vinyl polymer having epoxy and carboxyl groups) to an intramolecular and/or intermolecular reaction. When the polymer compsn. is used as a binder resin component, a coating film having excellent finish appearance, flexibility and durability can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new vinyl polymer composition, and in particular, when used as a binder resin component for paints, it forms a coating film with excellent finish, flexibility, and durability. The present invention relates to a vinyl polymer composition.

Although solvent-soluble vinyl polymers have traditionally been well known in the field of paints, conventional vinyl polymers synthesized using known techniques have linear main skeletons. Moreover, since they are bonded by carbon-carbon bonds, there is a problem in that the flexibility of the coating film is poor when used as a paint resin. For this reason, methods such as lowering the glass transition point (Tg) of vinyl polymers have been used to impart flexibility to the paint film, but such methods can significantly reduce the durability of the paint film. There is a problem of deterioration.

However, one point to note is that the present invention solves the above-mentioned problem of poor coating film flexibility when conventional solvent-soluble vinyl polymers are used as coating resins.

The inventors of the present invention have conducted extensive research to solve the above-mentioned problems and to obtain a vinyl polymer composition that is particularly suitable for paints and has excellent flexibility and durability. The inventors have discovered that the above object can be achieved by using a vinyl polymer partially reacted intramolecularly and/or intermolecularly as the base resin, and have completed the present invention. .

Thus, according to the invention, at least one chemically reactive group (A) and at least one complementary reactive group (A) capable of mutually reacting with said chemically reactive group (A) are present in the molecule. B) in its molecule and/or
Alternatively, a vinyl polymer composition for paint, comprising a modified vinyl polymer that has a P-eye structure formed by an intermolecular reaction.

In the present invention, a chemically reactive group (A) is added to the vinyl polymer.
The method for introducing the complementary reactive group (B) is carried out by using the monomer having the reactive group (A) or (B) as a constituent component of the vinyl polymer, and the method is as follows: Typical monomer combinations shown in -1 are used. Specific examples of vinyl monomers having such reactive groups are listed in Table 2 below.

Table-1 Table-1 (Continued) Table-1 (Continued) Table-2 Table-2 (Continued) Combinations of chemically reactive groups (A) and complementary reactive groups (B) listed in Clothing-1 above In view of ease of production, combinations of epoxy groups and carboxyl groups, combinations of hydroxyl groups and incyanate groups, and combinations of alkoxysilane groups and hydroxyl groups are preferred.

Next, in addition to the combination of vinyl monomers having these reactive groups, vinyl monomers to be copolymerized include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene; methyl (meth)acrylate, ethyl (
meth)acrylate, butyl(meth)acrylate, 2
- (Meth)acrylic ester-resistant esters such as ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate; visco) 3F
(Manufactured by Osaka Organic Chemical Co., Ltd., product name, hereinafter the same meaning is indicated)
, 3MF as above, 8F as above, 8MF as above, perfluorocyclohexyl (meth)acrylate, N-2-propyl perfluorooctane sulfonate amide ethyl (meth)
Fluorine-containing vinyl monomers such as acrylate 1, vinyl fluoride, and vinylidene fluoride; N,N'-dimethylamine ethyl (meth)acrylate, N,N'-diethylaminoethyl (meth)acrylate, N,N '-Nitrogen-containing vinyl monomers such as diethyl (meth)acrylamide; vinyl ether monomers such as vinyl ethyl ether and vinyl butyl ether; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Hydroxyl group-containing (meth)acrylic acid esters; lactones such as Plaxel FA-1 (manufactured by Daicel Chemical Industries, Ltd., trade name, hereinafter the same meanings are shown), FA-2 as above, FM-1 as above, FM-2 as above; Examples include modified (meth)acrylic monomers; vinyl acetate, (meth)acrylonitrile, etc., which are appropriately selected and used depending on desired performance.

Mutually reactive reactive groups used in the present invention (
The vinyl monomer having A) or (B) is used in the range of 0.01 to 80% by weight, preferably 0.05 to 50% by weight based on the solid content during polymerization of the vinyl polymer. Ru. If the amount of the vinyl monomer having reactive groups (A) or (B) is too small, the degree of mutual reaction between the reactive groups will be low, and when used in paints, the flexibility and durability of the paint film will deteriorate. No improvement is achieved. On the other hand, if the amount used is too large, the viscosity becomes extremely high and the finish of the coating film deteriorates.

The vinyl polymer having reactive groups (A) and (B) is
It can be produced by polymerizing the vinyl monomer described above using a radical polymerization initiator by a conventionally known method.

For example, polymerization can be easily carried out by dropping a mixture of the monomer and a radical polymerization initiator (for example, azoisobutyronitrile, etc.) into a heated and stirred solvent (solution polymerization).

Here, the reaction between the reactive groups (A) and (B) present in the vinyl polymer to form the modified vinyl polymer is as follows:
Although it may occur to some extent during the polymerization of vinyl monomers, in general, the polymerization reaction rate of vinyl monomers is much higher, so a network formed by the reaction between reactive groups (A) and (B) is formed after the vinyl polymer is formed. Reactive group (A
The general conditions for the reaction of (B) with Needless to say, the scales have changed.

The network structure of the modified vinyl polymer having a network structure used in the present invention does not need to be uniformly formed in the polymer, but may be formed partially. The number average molecular weight of this modified vinyl polymer is usually 1.000 to about 50.
．． 000, preferably in the range from about 1,000 to 30,000.

The modified vinyl polymer having a network structure provided by the present invention can be used as it is as a coating composition in combination with a known curing agent such as an amine resin.

EXAMPLES The present invention will now be explained in more detail with reference to Examples and Comparative Examples. Parts and % in Examples and Comparative Examples
Both are parts by weight and % by weight.

Vinyl 7! A 1-11 A solvent having the composition shown in Table 3 below is heated to 120°C, and a mixture of monomers and a reactive group reaction catalyst having the composition shown in Table 3 and a radical polymerization initiator are separately added to it. was added over 4 hours, and polymerized for an additional 2 hours at the same temperature.

Vinyl 7, - Person 4-1 A solvent having the composition shown in Table 3 is heated to 120°C, and a mixture consisting of a monomer and a radical polymerization initiator having the composition shown in Table 3 is added dropwise thereto over 4 hours. Then, polymerization was further carried out at the same temperature for two more hours, then a reaction catalyst having a reactive group was added, and the reaction was further carried out at the same temperature for 4 hours.

Vinyl 7, -2~3'' and 5; A solvent having the composition shown in Table 3 is heated to 120'O, and a mixture consisting of a monomer and a radical polymerization initiator having the composition shown in Table 3 is added to it for 4
The mixture was added dropwise over a period of time, and polymerization was continued for an additional 2 hours at the same temperature.

l5 Example 1 A coating composition was prepared by mixing and dispersing the following composition.

Beni-Ichieki 11 Houki Resin 1 140 Knee Pants 203E (Note 1) 50 Swazol #
1000 (Note 2) 20 Modaflow (Note 3) 0.05 (Note 1) Made by Mitsui Toatsu Chemical ■ Melamine Face (solid content 60%) (Note 2) Made by Maruzen Petrochemical Forest Aromatic solvent (Note 3) Monsanto ■ Surface conditioner The paint composition thus obtained is applied to a zinc phosphate treated steel sheet (
Swasol #1 was applied to a test piece prepared by applying cationic electrodeposition and intermediate coating to Bt #137) and sanding.
000: The viscosity was adjusted to 25 seconds using a #4 Ford cup using a solvent mixed with n-butanol at a ratio of 2:1 (by weight), and the coating was applied to a final coating of 35 seconds. This was baked at 140°C for 30 minutes to prepare a test piece for testing. The test results are shown in Table 4 below.

Examples 2 to 4 and Comparative Example 1 Coating compositions were obtained in the same manner as in Example 1 except that Resins 2 to 5 were used in place of Resin 1, respectively.

Tests similar to those in Example 1 were conducted using this coating composition, and the test results are shown in Table 4 below.

As is clear from Table 4, the coating composition made of a modified vinyl polymer with a network structure imparts excellent flexibility to the coating film without any loss in durability. Can be done.

Claims (1)

[Claims] 1. At least one chemically reactive group (A) and at least one complementary reactive group (A) capable of mutually reacting with the chemically reactive group (A) in the molecule. A vinyl polymer composition characterized in that it contains a modified vinyl polymer in which a network structure is formed by reacting the vinyl polymer containing B) intramolecularly and/or intermolecularly. 2. The vinyl polymer composition according to claim 1, wherein the combination of reactive groups (A) and (B) that can react with each other is an epoxy group and a carboxyl group. 3. The vinyl polymer composition according to claim 1, wherein the combination of reactive groups (A) and (B) that can react with each other is a hydroxyl group and an isocyanate group. 4. The vinyl polymer composition according to claim 1, wherein the combination of reactive groups (A) and (B) that can react with each other is a hydroxyl group and an alkoxysilane group.