JPS59102962A - Coating resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition giving weather-resistant and flexible coating film to steel plate, etc., and useful as a clear paint, color paint, etc., by using a copolymer composed of specific amounts of a fluoroolefin, a specific monocarboxylic acid vinyl ester, etc., as an essential component. CONSTITUTION:The objective composition is prepared by compounding (A) 100pts.wt. of a copolymer composed of (i) 5-70pts.wt. of a fluoroolefin, (ii) 10-95pts.wt. of the vinyl ester of a monocarboxylic acid containing a 6-18C alkyl group (e.g. versatic acid vinyl ester), (iii) 0-40pts.wt. of a vinyl monomer containing functional group [e.g. beta-hydroxyethyl (meth)acrylate] and (iv) 0- 85pts.wt. of other vinyl monomer copolymerizable with the above monomers, and if necessary, (B) a curing agent. The amount of the curing agent is selected for example to give the ratio of (the equivalent number of the functiolnal group in the curing agent)/(the equivalent number of the functional group in the base resin) of 0.5-2.0.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new and useful resin composition for coatings, and its object is to provide a coating film with excellent weather resistance and flexibility. We provide solution-type and material-use resin condensates.

Acrylic resin paints are widely used in a variety of fields due to their excellent properties, including zero properties. It is desired to develop weather-resistant general and grade-1 knob paints as maintenance-free paints.

Until now, such paints have been developed in which polyhynylidene fluoride fine powder is mixed with an acrylic resin BN solution, but due to the dispersion type, the appearance of the paint film is inferior. There were drawbacks.

However, in view of these actual circumstances, the present inventors
As a result of our research, we discovered that a co-polymerization of a fluoroolefin and a specific molar carboxylic acid vinyl ester is soluble in organic solvents and provides a coating film with excellent weather resistance and flexibility. The invention was finally completed.

That is, the present invention provides (i) fluoroolefins 5 to 70
parts by weight, (ii) 10 to 95 parts of vinyl ester of monocarboxylic acid having an alkyl group of C6 to C77, 1ii) 0 to 40 parts by weight of a vinyl monomer having a functional group, and (iv) h reporter. As an essential component, a copolymer (A) obtained by copolymerizing 0 to 85 parts by weight of other vinyl monomers copolymerizable with the monomer in a total amount of 100 parts by weight, The present invention also provides a resin composition for a solution-type coating, which also contains a curing agent (B) if necessary.

Here, typical examples of the fluoroolefins (i) include fluorinated ethylene, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene.

During use of the flumeroolefin (i), the total amount of monomers is reduced to 100% from the viewpoint of weather resistance 4t and solubility.
When setting the ffrri portion, it is appropriate to set it within the range of 5 to 7 (single-layer type portion, preferably 10 to C0T1? portion).

In addition, vinyl esters of monocarboxylic acids (11
) Typical examples include vinyl caprate, vinyl caprylate, vinyl caprate, vinyl parzate, vinyl laurate, and vinyl stearate. Vinyl ticate is preferred.

and ζ, during use of such vinyl ester (ii), at least 10 parts by weight from rjX such as solubility,
Preferably at least 20 folds are required and 1I
Usually, 10 to 95 parts by weight is used.

By the way, in the IL+ composition of the present invention, the above curing agent (1
3) is also used in combination to make the composition of the present invention a crosslinked type.
When used, it is necessary to copolymerize with a vinyl monomer (iii) having a functional group capable of reacting with the curing agent (Δ);
) Typical examples include β-hydroxyedyl (meth)acrylate, β-hydroxypropyl (
Monomers containing a hydroxyl group such as meth)acrylate or allyl alcohol; monomers containing a carboxyl group such as hafester of fumaric acid, (meth)acrylic acid-itaconic acid, crotonic acid or maleic acid;
Monomers containing glycidyl groups such as glycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate or allylglycidyl; monomers containing phosphoric acid groups such as phosphoric acid esters such as β-hydroxyethyl methacrylate; These include N-medirol (meth)acrylamide and N-itoxymethyl (meth)acrylamide.

The amount of the vinyl monomer (iii) to be used should be kept to 40 folds or less from the viewpoint of flexibility.

Further, as the other vinyl monomers (iv) mentioned above, monocarboxylic acid vinyl esters other than the vinyl ester (ii) such as vinyl acetate and vinyl propionate;
Ethyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or cyclohexyl (
(meth)acrylic acid esters such as meth)acrylate; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, ethyl vinyl ether, n
Typical examples include vinyl ethers such as butyl vinyl ether or cyclohexyl vinyl ether; or vinyl chloride or (meth)acrylonitrile.

The vinyl monomer (1v) of C1 should be 85T11 parts or less.

Monomers (i), (ii), (i
In order to obtain the copolymer (Δ) which is the base resin component of the composition of the present invention from ii) and (iv), conventionally known polymerization methods can be employed, but solution radical polymerization is particularly preferred.

The copolymer (A) thus obtained may be used as it is as a lacquer-type material, or the above-mentioned functional hole-containing vinyl monomer (iii) may be copolymerized into the copolymer (B). When a functional group is introduced and tightened, a curing agent (
It is also possible to mix component B) and use it as a crosslinked type.

Typical examples of such curing agents (B) include amino resins such as alkyl etherified medyllol melamine, alkyl etherified benzoguanamine, and alkyl etherified medyllol urea! 1; Adducts of diisocyanate compounds such as hexamethylene diisocyanate, lysine diisocyanate, and xylylene diisocyanate with polyhydric alcohols such as trimethylolpropane, polyisocyanates having a biuret bond, or polyisocyanates containing an isocyanurate ring. Polyisocyanates: Polyisocyanates such as those mentioned above are reacted with a blocking agent such as oximes or lactams.
Blocked isocyanates obtained by polyepoxy compounds such as neopendel glycol diglycidyl ether, glycerin polyglycidyl ether, sorbitol polyglycidyl ether, diglycidyl phthalate, or epoxy resins containing hydantoin rings; or polyesters containing carboxyl groups. Alternatively, there are polycarboxylic compounds such as acrylic resins having carboxyl groups.

When such a curing agent (B) is used in combination, the usage amount of the curing agent component (number of equivalents of functional groups in the curing agent)/(number of equivalents of functional groups in the base resin) = 0.5 to 2 , 0 is particularly preferable.

The composition of the present invention thus obtained can be used as a clear paint, or can be further mixed with a coloring agent such as a pigment and used as a colored paint.

The h-composition of the present invention may further contain various known and commonly used additives such as leveling agents and ultraviolet absorbers, if necessary.

Next, the present invention will be specifically explained with reference to Reference Examples and Examples. All parts and percentages are based on weight unless otherwise specified. Reference Example 1 [Copolymer ( Preparation example of A)] In a stainless steel autoclave, add
00 parts of toluene, 500 parts of ethyl isobutylene, and 500 parts of ethyl isobutylene, heated to 60°C, and blown to form 406 parts of vinyl berritate, 2 (l 013 and azobis) of methyl methacrylate. A mixture consisting of 20 parts of isovaleronitrile was added dropwise over 4 hours, and the temperature was kept at the same temperature for 15 hours. It is abbreviated as copolymer (A-1).

Reference Example 2 [H] The same procedure as Example 1 was used, except that the use of chlorotrifluoroethylene and megol methacrylate in 9 was changed to 200 parts and 400 parts, respectively, and the non-volatile content was 50%. A solution of copolymer 111 was prepared. Below, this will be abbreviated as copolymer (Δ-2).

Reference Example 3 (same as above) 200 parts of tetrafluoroethylene, 500 parts of toluene, and 500 parts of methyl isobutyl ketone were placed in a stainless steel autoclave and heated to 60°C, and then 400 parts of vinyl persatate was added thereto. A mixture consisting of 350 parts of methyl methacrylate, 50 parts of β-hydroxyedyl methacrylate, and 20 parts of azobisisovaleronitrile was added dropwise over 4 hours and then maintained at the same temperature for 15 hours (after tightening, the nonvolatile content was 50 parts). A copolymer solution of % was obtained.
).

Reference example 4 [same as above] The monomer charging composition was 4 of chlorotrifluoroethylene.
00 parts of vinyl persate, 250 parts of methyl methacrylate and 50 parts of allylglycidyl.
The same procedure as Reference Example 3 was carried out except that the nonvolatile content was 5%.
A solution of 0% copolymer was obtained. Hereinafter, this will be abbreviated as copolymer (A-4).

Examples 1 to 4 Weigh out each component in the proportions listed in Table 1, then add glass peas and mix in a paint shaker to make a white color with a non-volatile content of 50% and a PWC of 40%. A paint was prepared.

Next, this white paint was diluted to a spray viscosity with a mixed solvent of xylene/methyl isobutyl ketone -70/30 (weight ratio), and then sprayed onto a zinc phosphate treated steel plate and cured under the conditions listed in the table. Film thickness is approximately 40μ
A coating film of m was obtained.

However, when we investigated the various properties of each coating film, similar results were obtained.

Table 1 Notes 1) Polyisocyanate resin manufactured by Dainippon Ink & Chemicals, NGO content = 12.5% 2) Adduct of trimellitic acid and ε-caprolactone in a molar ratio of 1:6 3) Ishiya Sangyo Rudil-type titanium oxide manufactured by ■4) Xylene/methyl isobutyl ketone-70/30
(weight ratio) 5) [Sunshine Weatherometer j 3000 hour irradiation As is clear from Table 1, the paint obtained using the composition of the present invention has good weather resistance in terms of appearance and flexibility. It turns out that it's something that is out of character.

Patent applicant Oguchi Hon Ink Kagaku Kogyo Co., Ltd. Procedural amendment (spontaneous) 1. Indication of the case Showa [J57 Patent Application No. 211893] 2. Name of the invention: Resin composition for paint 3. Amendment! Relationship with the case of a person who engages in illegal activities Patent applicant: 35-58 Sakashita, Itabashi-ku, Tokyo
88) Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Kuni Mura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Telephone: Tokyo (03) 272-4511 (Dainippon Ink & Chemicals Co., Ltd.) representative)"
"General" should be corrected to "General."

(2) Description on page 3, line 21 1-Curing agent (△)” rCuring agent (B) Add +1 to J.

t: (+ The statement "allyl glycidyl" in lines 408 to 9 is corrected to "7°lyl glycidyl ether."

(4) Description of “page 5, line 13 r” 1 Kyoelectric combination (13) J, "Revised to copolymer (△) J.

(5) Description in the 810th line ° 1 allylglycidyl-), Corrected to "allyl glycidyl ether."

that's all

Claims (1)

[Claims] (A) (i) Fluoroolefin 5-70IT
[In total, (ii) 10 to 95 parts by weight of vinyl ester of monocarboxylic acid having a 'fulkyl group of C6 to C77, (iii) Vinyl monomer having a functional group O to 40
and (iv) 0 to 85 parts by weight of other vinyl monomers copolymerizable with each monomer listed in Ix in a total amount of 10 parts. With copolymer as an essential component,
and (B) a curing agent if necessary, a resin composition for a solution-type coating.