JPH0527645B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new and useful curable resin composition. It contains as essential components a vinyl polymer that does not contain functional groups such as amino groups and epoxy groups, and a polyepoxy compound.It has particularly good adhesion to plastics, abrasion resistance, plasticizer migration resistance, and workability. Excellent sex,
This invention relates to a curable resin composition suitable for coating on plastic materials. [Prior Art] Plastic coatings include lacquer-based paints that do not participate in crosslinking, and urethane-based paints that participate in crosslinking. Among these, the so-called urethane curing system, which is itself curable, has excellent coating performance, but it cannot be said to be quick drying, and depending on the solvent used, it can be used for plastic materials. This is not preferable because it may cause the coating to deteriorate in appearance. On the other hand, although lacquer-based paints dry quickly and are easy to use, they cannot be said to have sufficient gloss, appearance, or coating performance. For these reasons, there is a strong desire for the emergence of a new paint system that can compensate for the respective deficiencies of lacquer-based paints and urethane-based paint systems. Conventionally, compositions containing a vinyl polymer containing basic nitrogen as a base resin and a polyepoxy compound as a curing agent have been known to cure at room temperature and provide a cured product with excellent appearance and mechanical performance of the coating film. (Japanese Patent Application Laid-open No. 52-76338, Japanese Patent Application Publication No. 57-166795). [Problems to be Solved by the Invention] However, the paint for plastics obtained using such a composition has the serious drawback of being selective to plastic materials in terms of adhesion.
It cannot be said that it is a desirable paint. [Means for Solving the Problem] As a result of intensive research in view of the above situation, the present inventors have found that a specific tertiary amino group-containing vinyl polymer, a tertiary amino group-containing vinyl polymer, and an epoxy group-containing A composition containing a non-containing vinyl polymer and a polyepoxy compound eliminates the above-mentioned drawbacks of the conventional technology, and improves adhesion to plastic materials and scratches on painted surfaces when packaging painted items. A coating with significantly improved resistance to plasticizer migration, such as contamination or softening of the painted surface due to plasticizer migration due to contact between polyvinyl chloride cord, etc. and the painted surface. The present inventors have discovered that the present invention can provide a membrane, and have completed the present invention. That is, the present invention combines (A) a vinyl polymer containing a carboxylic anhydride group, and a tertiary amino group and a group each having an active hydrogen that can react with at least one carboxylic anhydride group in one molecule. (B) a vinyl polymer containing neither a tertiary amino group nor an epoxy group; and (C) a polyepoxy compound. The present invention provides a curable resin composition comprising: Here, the above-mentioned vinyl polymer containing a carboxylic acid anhydride group [hereinafter abbreviated as vinyl polymer (a-1)] refers to a monomer having an acid anhydride group such as maleic anhydride or itaconic anhydride. [hereinafter abbreviated as acid anhydride group-containing monomer (1)]
It refers to a copolymer obtained by copolymerizing these and another vinyl monomer having copolymerizability [hereinafter abbreviated as other vinyl monomer (2)], Usually, the number average molecular weight (n) is
3000 to 30000 is used. Representative examples of such other vinyl monomers (2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate,
(such as iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate meth)acrylic acid esters; dialkyl esters of unsaturated dibasic acids such as itaconic acid, maleic acid, and fumaric acid;
(meth)acrylic acid, crotonic acid, itaconic acid,
fumaric acid, itaconic acid monoalkyl ester,
Carboxyl groups such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, or adducts of hydroxyl group-containing vinyl monomers such as β-hydroxyethyl (meth)acrylate and acid anhydrides such as succinic anhydride or trimellitic anhydride. Aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene, vinyltoluene; or vinyl acetate, (meth)acrylonitrile, (meth)acrylamide, diacetone acrylamide, N,N-dimethyl(meth) ) Acrylamide, N-vinylpyrrolidone, vinyl chloride, β
-Phosphate esters of hydroxyethyl (meth)acrylate, etc. From the viewpoint of curability, the amount of the acid anhydride group-containing monomer (1) and other vinyl monomer (2) to be used is (1)/(2) = 1/99 to 20 in terms of weight ratio. /80 is appropriate. The method for preparing the vinyl polymer (a-1) is not limited to any particular method, and various known and commonly used polymerization methods such as solution polymerization and bulk polymerization can be used. Therefore, it is most preferable to use a solution polymerization method, which is easy to make into a paint and also allows easy control of the molecular weight. Ester solvents such as enyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Polymerization may be carried out by a conventional method using a known and commonly used polymerization initiator such as an oxide type polymerization initiator. Further, at this time, polymerization can be carried out using mercaptans such as tert-dodecyl mercaptan, lauryl mercaptan, thioglycolic acid alkyl ester, and β-mercaptopropionic acid, and a molecular weight regulator such as α-methylstyrene dimer. Next, a compound having both a group having an active hydrogen that can react with at least one carboxylic acid anhydride group and a tertiary amino group in one molecule [hereinafter referred to as an active hydrogen and tertiary amino group-containing compound ( Typical examples of a-2) are amino alcohols such as dimethylaminoethanol; N,N-dimethylethylenediamine;
Dialkylethylenediamines such as N,N-diethylethylenediamine, N,N-dipropylethylenediamine; N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-
N,N-dialkyl- such as propylene diamine
1,3-propylene diamines; N,N-dimethyl-1,4-tetramethylene diamine, N,N-
N,N-dialkyl-1,4-tetramethylenediamines such as diethyl-1,4-tetramethylenediamine; N,N-dimethyl-1,6-hexamethylenediamine, N,N-diethyl-1,6-
N,N-dialkyl-1,6-hexamethylene diamines such as hexamethylene diamine; N-
N-aminoalkylmorpholines such as (2-aminoethyl)morpholine, N-(3-aminopropyl)morpholine, N-(4-aminobutyl)morpholine, N-(6-aminohexyl)morpholine; -aminoethyl)pyrrolidine, N-
Examples include N-aminoalkylpyrrolidines such as (3-aminopropyl)pyrrolidine, and N-aminoalkylpiperidines such as N-(2-aminoethyl)piperidine and N-(3-aminopropyl)piperidine. However, the reactivity with the vinyl polymer (a-1), the weather resistance of the coating film,
From the economic point of view, it is preferable to use N,N-dialkyl-1,3-propylene diamines. In preparing the vinyl polymer (A) used in the present invention, first, the above-mentioned compound is added to 1 equivalent of the carboxylic acid anhydride group in the above-mentioned vinyl polymer (a-1). The group having active hydrogen and active hydrogen capable of reacting with the carboxylic acid anhydride group in the tertiary amino group-containing compound (a-2) is usually 0.4 to 3
These two components are mixed in such a range that they are equivalent, and reacted at a temperature from room temperature to about 120° C. for about 0.5 to 3 hours to obtain an adduct. The adduct obtained in this way can be used as it is, but it is further heated at 70 to 150°C for about 1 to 20 hours to undergo dehydration condensation and imide cyclization to form a tertiary amino group having an imide ring. In carrying out the present invention, it is particularly preferable to convert it into a vinyl polymer containing the above-mentioned components. As a specific example, the vinyl polymer (a-
1) is a maleic anhydride copolymer, and the active hydrogen and tertiary amino group-containing compound (a-
The reaction formula when N,N-dimethylamino-1,3-propylene diamine is used as 2) is as follows. In this way, tertiary amino group-containing vinyl polymer (A)
Although condensation water is produced in obtaining the above, depending on the application, the condensation water may be used as it is without being removed at all. If it is necessary to remove it, it can be dehydrated by adding a known and commonly used drying agent or dehydrating agent or by azeotropically distilling it with a solvent during or after the dehydration condensation reaction. In addition, the vinyl polymer (B) that does not contain either tertiary amino groups or epoxy groups is an essential component for improving adhesion to plastic materials, especially carboxyl groups and hydroxyl groups. A non-functional vinyl polymer containing no functional groups other than tertiary amino groups or epoxy groups, such as
Those that are compatible with the vinyl polymer (A) are preferred from the viewpoint of coating film appearance, gloss, etc. As the vinyl monomer that can be used in preparing such a vinyl polymer (B), the other vinyl monomers (2) mentioned above can be used. Solution polymerization is a simple method for preparing the vinyl polymer (B), and in addition to the above-mentioned solvents, alcohols such as isopropanol, n-butanol, isobutanol, ethyl glycol monoethyl ether, and ethylene glycol monobutyl ether can be used. Solvents can be used. The ratio of the thus obtained vinyl polymer containing tertiary amino groups (A) to the vinyl polymer (B) containing neither tertiary amino groups nor epoxy groups is as follows:
Normally (A)/(B) = 95/5 ~ solid content weight ratio
The range is 20/80, more preferably 90/10 to 60/40. When the ratio (A)/(B) is greater than 95/5 and the amount of vinyl polymer (A) having tertiary amino groups is increased, the curability and flexibility of the coating film may be affected. Although it is preferable in terms of the following points, it may not be able to meet the purpose of the present invention due to poor adhesion to certain plastic materials, and conversely, if this ratio is smaller than 20/80, tertiary amino groups may not be present. Vinyl polymer with
When the amount of (A) used is small, it becomes difficult to expect good curability and flexibility of the coating film, which also fails to meet the objectives of the present invention, so neither is preferable. The composition of the present invention is obtained by blending the vinyl polymers (A) and (B) thus obtained with a polyepoxy compound (C). Examples of such a polyepoxy compound include ethylene glycol. Polyglycidyl ethers of polyhydric alcohols such as diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of bisphenol A, triglycidyl ether of glycerin; diglycidyl phthalate Polyglycidyl esters of polyhydric carboxylic acids such as esters, diglycidyl esters of isophthalic acid, diglycidyl esters of adipic acid; diglycidyl ether type epoxy resins of bisphenol A or bisphenol F, novolac type epoxy resins, hydantoin rings There are polyepoxy compounds such as various epoxy resins such as epoxy resins containing epoxy resins, glycidyl ester ether of p-oxybenzoic acid, and various vinyl polymers having epoxy groups in side chains. and a vinyl polymer (A) having a tertiary amino group.
From the viewpoint of curability, the proportion of the and polyepoxy compound (C) used is based on the total equivalent of carboxyl groups, tertiary amino groups, and unreacted acid anhydride groups contained in the vinyl polymer (A). The epoxy group contained in the polyepoxy compound (C) is usually 0.3 to 3 equivalents, preferably
The range is 0.5 to 2 equivalents. The composition of the present invention thus obtained may be used as it is as a paint, or may be further added with pigments, solvents, ultraviolet absorbers, antioxidants,
Resins such as cellulose acetate butyrate, nitrocellulose, or ketone resins, chlorinated polyolefins, polyisocyanates, and blocked polyisocyanates may also be blended and used as paints. [Effects of the present invention] The paint obtained from the composition of the present invention is applied to the object to be coated and left at room temperature for 1 to 2 days, or if necessary forced drying at 60 to 100°C for 20 to 40 minutes. It cures well and provides a coating film with excellent adhesion, plasticizer resistance and abrasion resistance. [Example] Next, the present invention will be specifically explained using reference examples, examples, and comparative examples. Unless otherwise specified, all parts and percentages are based on weight. Reference Example 1 [Preparation example of tertiary amino group-containing polymer (A) solution] 700 parts of toluene was charged into a reactor equipped with a thermometer, a stirring device, a dropping funnel, a nitrogen introduction tube, and a cooling tube, and the mixture was heated under a nitrogen atmosphere. Then, 200 parts of styrene, 460 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 40 parts of maleic anhydride, 10 parts of azobisisobutyronitrile (AIBN), and tert-butyl peroxyoctoate were added. (TBPO) 10 parts, tert-butyl peroxybenzoate (TBPB) 5 parts and toluene 300 parts
dropwise over a period of 3 hours and then kept at the same temperature for 15 hours to continue the reaction,
Number average molecular weight (n) at 50% non-volatile content (NV)
A solution of a vinyl polymer containing 10,000 acid anhydride groups was obtained. Hereinafter, this will be referred to as a vinyl polymer (a-
1-1) Abbreviated as solution. Next, the temperature of this vinyl polymer (a-1-1) solution was lowered to 70°C, and 40 parts of N,N-dimethyl-1,3-propylene diamine was added thereto, and the temperature was maintained at the same temperature for 5 hours. Then, 270 parts of n-butanol was further added to obtain a solution of a tertiary amino group-containing vinyl polymer having an NV of 45% and a Gardner color of 1 or less. Hereinafter, this will be abbreviated as the polymer (A-1) solution, and the reaction rate of acid anhydride groups determined by IR spectrum analysis for this polymer (A-1) is 93 mol%.
It was hot. Reference Example 2 [Preparation example of tertiary amino group-containing polymer (A) solution] The same procedure as in Reference Example 1 was carried out except that the same amount of itaconic anhydride was used instead of maleic anhydride, and the NV was 45. A solution of a tertiary amino group-containing vinyl polymer having a Gardner color of 1% or less [hereinafter, this will be abbreviated as a polymer (A-2) solution. ]
I got it. The reaction rate of acid anhydride groups in this polymer (A-2) was 95 mol%. Reference Example 3 Vinyl polymer obtained in Reference Example 1 (a-1-
1) 1000 parts of the solution was heated to 80°C under a nitrogen stream, 23 parts of N,N-diethyl-1,3-propylenediamine was added thereto, and the reaction was continued by keeping at the same temperature for 3 hours. After that, 135 parts of n-butanol was added to obtain 3 with NV of 45% and Gardner color of 1 or less.
A solution of a vinyl polymer containing amino groups [hereinafter abbreviated as polymer (A-3)] was obtained. The reaction rate of acid anhydride groups in this polymer (A-3) was 43 mol%
It was hot. Reference Example 4 Into a reactor similar to Reference Example 1, 522 parts of toluene and 500 parts of n-butanol were charged and heated under a nitrogen stream.
The temperature was raised to 110℃. Next, a mixture consisting of 100 parts of styrene, 600 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 2 parts of AIBN, 3 parts of TBPO, 5 parts of TBPB and 200 parts of toluene was added dropwise over 3 hours, and then kept at the same temperature for 15 hours. The reaction was continued to produce a non-functional vinyl polymer with NV of 45% and n of 20,000 [hereinafter referred to as polymer (B-
1)] was obtained. Examples 1 to 3 and Comparative Examples 1 to 2 Each formulation as shown in Table 1 and PWC were
Add titanium oxide separately to 35%,
After kneading in a sand mill for 1 hour, ethyl acetate/iso-butanol/butyl cellosolve = 40/
Dilute with 40/20 (weight ratio) thinner,
Various white enamel paints were prepared. Next, each paint was sprayed onto various plastic materials such as acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), polyphenylene oxide, and polyphenylene ether to a film thickness of 15 μm. Painted separately, 60
Baking was performed at ℃ for 30 minutes. Thereafter, each coated product was left at room temperature for 3 days, and the coating film performance was evaluated. The results are shown in Table 1. It should be noted that "adhesion" is based on a cross-section adhesion test. 【table】

Claims (1)

[Scope of Claims] 1 (A) A vinyl polymer containing a carboxylic anhydride group, a group each having an active hydrogen in one molecule that can react with at least one carboxylic anhydride group, and a tertiary amino group. (B) a vinyl polymer containing neither a tertiary amino group nor an epoxy group, and (C) a polyepoxy compound. A curable resin composition comprising: 2. The solid content weight ratio of the tertiary amino group-containing vinyl polymer (A) and the vinyl polymer (B) containing neither tertiary amino group nor epoxy group is (A)/(B)=
The curable resin composition according to claim 1, which has a hardness of 95/5 to 20/80. 3. The compound having a group having an active hydrogen that can react with at least one carboxylic acid anhydride group and a tertiary amino group in one molecule is N,N-dialkyl-1,3-propylenediamine. A curable resin composition according to claim 1 or 2.