JPH07122037B2 - Unsaturated polyester resin putty composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an unsaturated polyester resin putty composition.

[0002]

2. Description of the Related Art Conventionally, when an unsaturated polyester resin putty for a steel sheet is used as a rustproof steel sheet, there is a drawback that heat resistance and adhesion are deteriorated and water resistance is poor.

In order to improve this, unsaturated polyester resins having excellent water resistance have been developed by increasing the acid value of unsaturated polyester resins, or by epoxy modification or urethane modification to improve heat-resistant adhesion. , Unsaturated polyester resin putty for rustproof steel sheet using these unsaturated polyester resins is commercially available.

However, the theoretical elucidation of these unsaturated polyester resin putties for rustproof steel sheets is not clear yet. Some aging will occur during storage, and the curing time will be longer than in the initial production. 2. When applied to a rustproof steel plate, hardening of the feather edge (thin film) portion is required for a longer time than that of the thick film portion. 3. When the surface of anticorrosion treated steel plate is polished and applied to the zinc or zinc alloy surface,
The heat-resistant adhesion and the curability of the feather edge (thin film) part are significantly deteriorated. There is a problem.

In order to improve these problems, mixing of an unsaturated polyester resin for a rust-proof steel sheet with an unsaturated polyester resin excellent in curability and storability is being studied and carried out. Unsaturation for anti-rust treated steel plate that satisfies all of curability, storage stability, adhesiveness, curability of feather edge (thin film) part, and water resistance due to the problem that the adhesion with the anti-rust treated steel plate deteriorates. The polyester resin putty is in a state of not appearing at present.

[0006]

[Means for Solving Problems] In comparison between the case where the unsaturated polyester resin putty for steel sheet is applied to a steel sheet and a rust-proof steel sheet, there is no great difference in the hardenability between the feather edge (thin film) portion and the thick film portion in the steel sheet. However, in the rust-prevented steel sheet, a remarkable difference is observed in the curability from the feather edge (thin film) portion.

Further, comparing the increase in curing time during storage between the unsaturated polyester resin putty for steel plate and the unsaturated polyester resin putty for rust-prevented steel plate, the unsaturated polyester resin putty for steel plate shows a short time immediately after production. Although an increase in the curing time is observed, it immediately saturates, and the increase in the curing time thereafter is slight, whereas in the unsaturated polyester resin putty for rust-prevented steel sheet, the curing time of the unsaturated polyester resin putty does not saturate immediately after production. It is recognized that the increase will continue.

Further, it is presumed that the unsaturated polyester resin for rust-preventive steel sheets has a large number of functional groups and polar groups introduced therein in order to improve the adhesion, as compared with the unsaturated polyester resin for steel sheets.

From the above comparative study and estimation, the inventors have found that the problem of the unsaturated polyester resin putty for anticorrosive steel plates is that the change in curability with time is due to the metal salt used as a curing accelerator for the unsaturated polyester resin. , Or metal ions,
It was speculated that the effect of the resin polar portion or the resin polarity on the filler or the like over time, or the promotion effect of the curing accelerator due to coordination, etc. decreased. Further, the delay in the hardening of the feather edge (thin film) portion was presumed to be that the above-mentioned metal salt or metal ion was adsorbed or coordinated on the surface of the rust-prevented steel plate, and thus the hardening accelerating property was reduced.

If this assumption is correct, the unsaturated polyester resin putty composition system is more easily adsorbed or coordinated than the metal salt or metal ion used as a curing accelerator, and the curability and physical properties are less affected. Unsaturation for rust-proof treated steel sheets with excellent curability at the feather edge (thin film) part, with little increase in curing time due to aging during storage if a metal salt or metal ion is added in an appropriate amount during the production of putty As a result of diligent research based on the prediction that a polyester resin putty will be obtained, the addition of a salt of a specific metal to the unsaturated polyester resin putty causes a slight increase in the curing time due to aging during storage and a feather edge (thin film). It was found that an unsaturated polyester resin putty for rust-preventing steel sheet, which has excellent curability of the) part and good adhesion, is obtained, and the present invention has been completed. This has led to the.

That is, the present invention relates to an ethylenically unsaturated monomer
.About.25 parts by weight, unsaturated polyester resin 20 to 50 parts by weight, filler 30 to 70 parts by weight, metal salt (as metal concentration 8%) 0.3 to 3 parts by weight as a curing accelerator, and copper as a storage stabilizer. The present invention relates to an unsaturated polyester resin putty composition for a rustproof steel sheet, which contains 0.001 to 2 parts by weight as an essential component.

As the ethylenically unsaturated monomer used in the present invention, an unsaturated polyester resin is dissolved and curable,
It is appropriately selected depending on the appropriateness of viscosity, ease of handling, and physical properties of the cured resin, but it is known unsaturated such as styrene, vinyltoluene, monochlorostyrene, diallyl phthalate, methyl methacrylate, etc., and one kind or a combination of two or more kinds thereof. An ethylenically unsaturated monomer for polyester resin is used. The unsaturated polyester resin may be appropriately selected from the commercially available products for rustproof steel plate putty according to the purpose.

In general, an unsaturated polyester resin for a rust-prevented steel sheet is superior in adhesiveness to a steel sheet and an anti-rust treated steel sheet, as compared with an unsaturated polyester resin for a steel sheet putty. This resin composition has a higher acid value than a resin for a general unsaturated polyester resin putty, and it is considered that a part of the resin composition is epoxy-modified or urethane-modified. Although talc is mainly used as the filler, titanium oxide, a hollow inorganic filler and the like are appropriately mixed in order to improve the concealing power and the polishing property. The curing accelerator may be any one generally used for unsaturated polyester resins, and typically includes metal soaps such as cobalt naphthenate, cobalt octylate, and manganese naphthenate.

As the storage stabilizer, a metal salt containing copper of Group IB of the periodic table is used. Examples of this metal salt include copper naphthenate, copper octylate, copper sulfate, copper formate, copper acetate, and acetylacetone copper. Other appropriate amounts of dialkylanilines, quinones, colorants, etc. are added as auxiliary agents.

Generally, in an unsaturated polyester resin putty, a curing agent is added and kneaded immediately before its use. Examples of the curing agent include methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, tertiary-butyl perbenzoate and the like. Can be given.

[0016]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. "Parts" in Examples and Comparative Examples
And "%" are based on weight.

Example 1 Unsaturated polyester resin for putty (60% ethylenically unsaturated monomer solution) [Dainippon Ink and Chemicals, Inc., trade name: Polylite CN-729] 38.00 parts cobalt octoate (8% including cobalt) 0.35 parts (including 8% copper) copper naphthenate 0.30 parts N, N-dimethylaniline 0.05 parts of additives Polylite [Dainippon Ink and Chemicals, Inc., trade Name: Polylite RS 404]
0.50 parts, styrene monomer 0.5 parts, titanium oxide 3.4 parts, and talc 57.50 parts were added and kneaded with a stirrer to produce an unsaturated polyester resin putty composition, which was then sealed. It was left for 1 month under the conditions of 38 ° C and 50 ° C. To this, 2.0% of cyclohexanone peroxide (Kawaguchi Chemical Co., Ltd., trade name: Cypox PL) was added, and pot life, curing time, heat-resistant adhesion, and (water resistance) were examined.

The potting life was 20 ± 1 ° C., the time until the fluidity disappeared, and the curability was # 8.
0 Heat-resistant adhesiveness is 3
0 minutes gap interval 2mm 8.5.1 Go Release th process after heating JIS K 5400, the temperature of merit 10 is obtained (where the maximum temperature 140 ° C., the lowest temperature was 60 ° C.), the test plate A composite electrogalvanized steel sheet (Nippon Steel Corp., trade name: Zinclite and Excellite) was polished with # 80 abrasive paper and then solvent degreased. The results are shown in Table 1.

Example 2: Unsaturated polyester resin for putty (66% ethylenically unsaturated monomer solution) [Japan Synthetic Chemical Industry Co., Ltd., trade name: prototype TN-481] 38.0
Cobalt octylate (containing 8% cobalt) in 0 part.
7 parts, copper naphthenate (containing 8% copper) 0.30 parts, N, N
-Dimethylaniline 0.05 part, polylite additive [Dainippon Ink and Chemicals, Inc., trade name: Polylite RS-404] 0.5 part, styrene monomer 0.5 part,
3.4 parts of titanium oxide and 57.50 parts of talc were added and kneaded with a stirrer to produce an unsaturated polyester resin putty composition, which was allowed to stand under the same conditions as in Example 1 and then the same method as in Example 1. Was evaluated. The results are shown in Table 2.

Comparative Example 1: Unsaturated polyester resin for putty (60% ethylenically unsaturated monomer solution) [Dainippon Ink and Chemicals, Inc., trade name: Polylite CN-729]
38.00 parts cobalt octylate (containing 8% cobalt) 0.35 parts N, N-dimethylaniline 0.05 parts,
Polylite additive [Dainippon Ink and Chemicals, Inc.,
Product name: Polylite RS 404] 0.50 parts, styrene monomer 0.5 parts, titanium oxide 3.4 parts, talc 5
After adding 7.50 parts and kneading with a stirrer, an unsaturated polyester resin putty composition was produced, allowed to stand under the same conditions as in Example 1, and then evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2: Unsaturated polyester resin for putty (66% ethylenically unsaturated monomer solution) [Japan Synthetic Chemical Industry Co., Ltd., trade name: prototype TN-481] 38.0
Cobalt octylate (containing 8% cobalt) in 0 part.
7 parts, N, N-dimethylaniline 0.05 part, additive for polylite [Dainippon Ink and Chemicals, Inc., trade name:
Polylite RS 404] 0.5 part, styrene monomer 0.5 part, titanium oxide 3.4 part, talc 57.50 part are added and kneaded with a stirrer to produce an unsaturated polyester resin putty composition, After standing under the same conditions as in Example 1, evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

As described above, the unsaturated polyester resin putty composition according to the present invention has excellent adhesion to rust-prevented steel sheets, especially galvanized steel sheets, and has a feather edge (thin film) portion. It has excellent curing properties, a slight delay in curing rate due to aging during storage, and good water resistance.

Claims (1)

[Claims] 1. An ethylenically unsaturated monomer 0 to 25 parts by weight, an unsaturated polyester resin 20 to 50 parts by weight, a filler 30 to 70 parts by weight, a metal salt (containing 8% metal) 0.3 to 3
An unsaturated polyester resin putty composition comprising a metal salt containing copper in an amount of 1 part by weight as an essential component.