JPS62184019A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition improved with respect to yellowing, by mixing a specified vinyl polymer with a polyepoxy compound and a saturated aliphatic dicarboxylic acid. CONSTITUTION:A resin composition containing a vinyl polymer (A) having at least one tert. amino group in the molecule, a polyepoxy compound (B) and a saturated aliphatic dicarboxylic acid (C). As said vinyl polymer (A), a vinyl polymer obtained by reacting a vinyl polymer having a carboxylic acid anhydride group with a compound having an active hydrogen group and a tert. amino group and being reactive with the carboxylic acid anhydride group is used, for example. This resin composition may be used as such as a paint or may be used in the form of a paint formed by mixing it with, optionally, a pigment, a solvent, a resin, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a new and useful curable resin composition,
More specifically, the curable resin composition comprises (a) a vinyl polymer having at least one tertiary amino group in one molecule, (b) a polyepoxy compound, and a saturated fatty acid. relating to things.

[Prior art and problems to be solved by the invention] In recent years, acrylic lacquer or acrylic lacquer has been used as a room temperature drying paint with good weather resistance. Liisocyanate-curable urethane paints are becoming widely used, but in the case of the former acrylic lacquers, although they have the advantage of being low in price, they have inferior coating properties compared to crosslinked paints. On the other hand, in the latter case, there are disadvantages in terms of toxicity due to the incyanate compound and cost, and neither of these can be said to be preferable. Therefore, the development of a new curing system is desired.

The inventors of the present invention have made intensive studies in view of the above-mentioned circumstances, and as a result, as disclosed in JP-A-59-56423 and JP-A-59-142220, we have developed a resin composition that is curable at room temperature and has high performance. invented.

Such a resin composition comprises +A) a vinyl polymer (a) containing a carboxylic anhydride group and, if necessary, a carboxyl group.
A tertiary amino group obtained by reacting -1) with a compound (a-2) having a tertiary amino group and a group having an active hydrogen capable of reacting with the above-mentioned carbic acid anhydride group, each in one molecule. Containing vinyl copolymer (1) and (B) 4'
) An epoxy compound as an essential component. On the other hand, although the method of introducing a tertiary amino group into a vinyl polymer is different from that of the above-mentioned resin composition, it was published in JP-A-52-76338 as a resin composition using a polyepoxy compound as a curing agent. As it was done,
There are resin compositions that are curable at room temperature. Such a resin composition includes (1) 0 basic nitrogen-containing acrylic monomers;
．． 2 to 30% by weight, (2) ester of (meth)acrylic acid and aliphatic monovalent anocol or mixture thereof 3
It is made by blending a polyepoxy compound with a vinyl copolymer (n) consisting of 5 to 99.8 weight % and (3) 0 to 60 weight % of other polymerizable monomers. As mentioned above, these resin compositions are novel and have room temperature curability. However, when these resin compositions crosslinked by tertiary amino groups and epoxy compounds were put to practical use as paints, it was found that the cured product had a drawback of yellowing.

That is, when such a composition is heated at a temperature exceeding 100° C. in order to sufficiently cure it in a short period of time, it has the disadvantage of causing significant yellowing. Therefore, in order to suitably use the above-mentioned resin composition as a resin composition for wing materials, it is necessary to improve the yellowing and discoloration.

[Means for solving problems]

The inventors of the present invention conducted further intensive studies to solve the problem, and as a result, they discovered that it was possible to obtain a resin composition that could eliminate the above-mentioned drawbacks and provide an excellent cured product, and thus completed the present invention. .

That is, the present invention comprises as essential components (a) a vinyl polymer having at least one tertiary amino group in one molecule, and (b) 7J? The present invention provides a curable resin composition comprising a recycled poxy compound and a saturated aliphatic dicarboxylic acid.

Here, the vinyl polymers (a) having at least one tertiary amino group in one molecule include the following. One of them is JP-A-59-56423.
No., and Japanese Patent Application Laid-open No. 142220/1983. That is, a monomer having an acid anhydride group such as maleic anhydride or itaconic anhydride, and if necessary acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid: maleic acid monoalkyl ester, fumaric acid. monoalkyl esters or itaconic acid monoalkyl esters, monomers having carboxyl groups such as adducts of vinyl monomers having di- or hydroxyl groups and acid anhydrides such as succinic anhydride or trimellitic anhydride; A polymer obtained by copolymerizing each of the above monomers with another vinyl monomer having copolymerizability is designated as (a-1). Typical examples of other vinyl monomers having the above-mentioned copolymerizability include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, benzyl methacrylate, and cyclohexyl methacrylate; methyl acrylate; Acrylic acid esters such as ethyl acrylate, butyl acrylate, lauryl acrylate, benzyl acrylate, and cyclohexyl acrylate; Dialkyl esters of unsaturated dibasic acids such as itaconic acid, maleic acid, and fumaric acid M: t Tahastyrene, α-methylstyrene, vinyl Aromatic unsaturated hydrocarbons such as toluene; or vinyl acetate, acrylonitrile, methacrylate trile, acrylamide, methacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, N-
Vinyl pyrrolide/vinyl chloride, etc. The above-mentioned monomers having a carboxylic acid anhydride group and monomers having a carboxyl group, which are used as necessary, are used from the viewpoint of curability, water resistance, alkali resistance, etc.
The former is preferably 1 to 20]ii1%, the latter is preferably 0 to 15% by weight, and the amount of the other copolymerizable monomer is preferably 99 to 65% by weight.

The polymer (a-1) can be prepared from each of the above-mentioned monomers by any known and commonly used method, but solution radical polymerization is most preferred. Aromatic hydrocarbons such as xylene; aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol, and monomethyl ether acetate; or acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Polymerization may be carried out by a method using a ketone solvent and a known and commonly used polymerization initiator such as an azo type or a peroxide type polymerization initiator.

In this case, mercaptans such as t-dodecyl mercaptan, lauryl mercaptan, thioglycolic acid alkyl ester, and β-mercagutopropionic acid, and molecular 'i regulators such as α-methylstyrene dimer can also be used. Next, as a method for introducing a tertiary amino group into the vinyl polymer (a-1), the vinyl polymer (&-1
) in which the vinyl polymer (a-1) is reacted with the compound (a-2) having both a group having an active hydrogen that can react with the cardic acid anhydride group and a tertiary amino group to form an amino group-containing vinyl polymer. A polymer (1) is obtained.

A group having an active hydrogen that can react with the carboxyl anhydride group described above (hereinafter abbreviated as an active hydrogen-containing group), and 3
The compound (a-2) having a primary amino group refers to a compound having a hydroxyl group, a primary or secondary amino group, or a thiol group as the active hydrogen-containing group. Among them, the most preferred compounds include alcohols having a tertiary amino group and primary or secondary aminos having a tertiary amino group. Of these, typical examples of the former amino alcohols include adducts of secondary aminos and epoxy compounds; typical secondary aminos used here include dimethylamino, diethylamino, and dipropyl. There are amino, diptylamino, ethyleneimine, morpholine, hyherazine, piperidine, pyrrolidine, etc., and secondary aminos obtained by addition of primary aminos such as methylamino, ethylamino, and butylamino with mono- or polynoxy compounds. On the other hand, typical epoxy compounds include ethylene oxide, propylene oxide, butylene oxide, dodecene oxide, styrene oxide, cyclohexene oxide, butyl glycidyl ether or phenyl glycidyl ether; -t-
Monoepoxy compounds such as butyl benzoic acid glycidyl ester or "Cardura E-10" (glycidyl ester of branched fatty acids manufactured by Shell in the Netherlands); or ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Thiol digly cycloether, bisphenol A
monoglycidyl ethers of polyhydric alcohols, such as diglycidyl ether of glycerine or triglycidyl ether of glycerine; Cal? polyglycidyl esters of phosphoric acid; or diglycidyl ether type epoxy resins of bisphenol A or bisphenol/I/F; There are polyepoxy compounds such as various epoxy resins such as epoxy resins or hydantoin ring-containing epoxy resins, and also glycidyl ester ethers of p-oxybenzoic acid or various vinyl polymers having epoxy groups in the side chains. and so on.

Typical examples of the tertiary amino group-containing alcohols obtained by reacting secondary aminos with epoxy compounds include dimethylaminoethanol, diethylaminoethanol, diisozolylaminoethanol, diisozolobylaminoethanol, and diisozolylaminoethanol. n-butylaminoethanol, dimethylaminobutanol, diethylaminoethanol, N-(2-hydroxyenarunmorpholine, N
-(2-hydroxyethyl)piperidine, N-(2-hydroxyethyl)pyrrolidine, N-(2- and droxyethyl)aziridine, N,N-dimethyl-2-hydroxypropylamino, N,N-diethyl-2-hydroxy Examples of tertiary amino group-containing alcohols include propylamino, triethanolamino, and tripropaturamino, but in addition to those listed above, amino alcohols such as ethanolamino and gropanolamino can also be used. and an adduct with a (meth)acrylate monomer having a tertiary amino group such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate, or a (meth)acrylate monomer containing the tertiary amino group. A vinyl polymer having both a tertiary amino group and a hydroxyl group in its side chain, which is obtained by copolymerizing a polymer with a hydroxyl group-containing monomer such as β-hydroxyethyl (meth)acrylate, can also be used.

In addition, representative examples of the above-mentioned primary or secondary aminos containing a tertiary amino group include N,N-dimethylethylenediamino, N,N-diethylethylenediamino, etc.
, N-dialkylethylenediamino, N,N-dimethyl-1,3-propylenecyamino, N,N-diethyl-
N,N-dialkyl-1,3-propylene diamino such as 1,3-propylene diamino; or N- such as N,N-dimethyl-1,6-hexamethylene diamino, N-methylpiperazine, N-ethylpiperazine Alkylpiperazines; or adducts of the above-mentioned tertiary amino group-containing (meth)acrylate monomers with ethylene diamino, propylene diamino, hexamethylene diamino, piperazine, methylamino, ethylamino, butylamino, ammonia, etc. be.

From the viewpoint of curability, N,N-dialkylaminoethanol and N,N-dialkylaminoglobylamino are particularly preferred compounds (a-2).

And the above-mentioned compound (a-1) and compound (a-2)
In order to obtain the vinyl polymer (1) which is the paste resin component in the composition of the present invention, the active hydrogen in compound (a-2) is Both compounds may be mixed in such a ratio that the number of groups contained is 0.5 to 3 equivalents, and the mixture may be reacted in a temperature range from room temperature to about 120°C.

Another method for producing vinyl polymers containing tertiary amino groups is disclosed in JP-A-52-76338. That is, (1) a basic nitrogen-containing acrylic monomer with 0.2 to 30% weight (2) an ester of acrylic acid or methacrylic acid with an aliphatic monohydric alcohol, or a mixture thereof with 35 to 99.8% weight , (3) A vinyl polymer (n
). As the basic nitrogen-containing acrylic monomer used here, acrylic acid and/or methacrylic acid derivatives such as dimethylaminoethyl acrylate or methacrylate, diethylaminoethyl acrylate or methacrylate, t-butyl acrylate or methacrylate are preferably used. However, other acrylamide or methacrylamide derivatives such as N-dimethylaminoethyl acrylamide or methacrylamide, N-diethylaminoethyl acrylamide or methacrylamide can also be used. The amount used is 0.2 to 30% by weight, but a range of 0.5 to 15% by weight is preferred from the viewpoint of performance and cost.

In addition, the monomers used in 12) and (3) are:
Other vinyl monomers having copolymerizability described in the first manufacturing method may be used. As other monomers not mentioned, 2-hydroxyethyl or propyl acrylate or ethyl acrylamide and methylol compounds, glycidyl acrylate or methacrylate, 2-vinylpyridine, etc. can also be used. The amount used is 35 to 99.8% by weight as components (2) and (3), preferably 50 to 80% by weight.
t and θ~60 weight #, preferably 20 to 45 weight f
It's #chi.

In order to produce 1 gfA of the vinyl polymer (II) from the above monomer, a known and commonly used polymerization method as described in the method 1 of the production method is used, using a known and commonly used solvent and a polymerization initiator. It is better to carry out the polymerization properly. However, if only the effect of preventing coloring is desired, the above range is not necessarily adhered to.

Thus, by each method, a vinyl polymer (a) having one or more tertiary amino groups in one molecule can be obtained. Next, as the polykasaboxy compound (b), the polyepoxy compound (B) published in the above-mentioned publication may be used. That is, the above-mentioned process except for the above-mentioned monoepoxy compound? Oxy compounds can be used.

The blending ratio of the vinyl polymer (a) and the polyepoxy compound (b) is as follows: In the case of the first method of producing a vinyl polymer, the carbon contained in the vinyl polymer (1) is a xyl group and a tertiary amino group. The amount of epoxy groups contained in the polyepoxy compound (b) is 0.5 to 2 for a total of 1 equivalent of 1 and unreacted acid anhydride groups.
In addition, the ratio should be such that I. On the other hand, the vinyl polymer (II) and 4 reprocessing by another method should be used. xy compound (
The blending ratio of (b) is such that the ratio of basic nitrogen atom (dulam atom) in the vinyl polymer to oxygen atom (dulam atom) of the epoxy group in the polyepoxy compound (b) is 0.5 to 3. A polyepoxy compound (b) may be added to each of them.

Next, is the essential component (c) a saturated aliphatic radical? The general formula H00C(CH2)nCOOH, where n
Saturated dicarboxylic acids represented by = 0 to 8 are most preferred, and specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid and sepacic acid, and the above-mentioned In addition, n is 9 or more or branched, specifically dimethylmalonic acid, methylsuccinic acid, methylmalonic acid, ethylmalonic acid,
Tetramethylsuccinic acid and the like can also be used.

Saturated aliphatic radical? As the acid, one type or a mixture of two or more of these may be used.

The blending amount is 0.1 to 0.1 to the solid content of the vinyl polymer (a) having one or more tertiary amino groups in one molecule.
It is preferably 0.5 to 5% by weight. If the addition value is less than 0.1%, yellowing and coloring will not be improved and 10% by weight.
If used in excess of this amount, it will have an adverse effect on curability.

The composition of the present invention thus obtained may be used as it is as a paint, or if necessary, it may be further added with pigments, solvents, cellulose acetate butyrate, nitrocellulose or ketone resins, chlorinated polyolefins, polyisocyanates, blocked polyesters, etc. It may also be used as a paint in a prepared form by blending resins such as isocyanate.

The paint obtained from the composition of the present invention is sufficiently cured by applying it to the object to be coated and leaving it for 1 to 2 days at room temperature, or if necessary, drying it for 20 to 40 minutes at a temperature exceeding 100°C. and provides a coating film with excellent physical properties.

When the paint obtained from the composition of the present invention is used as a clear paint, there is no yellowing of the paint film, and it is significantly cheaper than urethane paints, which is often a problem with urethane paints. There are no concerns about toxicity.

Therefore, the composition of the present invention can be effectively used in various applications where conventional urethane paints are used, such as automobile repair, woodworking, building materials, and plastics.

Furthermore, the composition of the present invention is not limited to being used merely as a surface coating as described above, but can also be used as an adhesive or a sealant.

Next, the present invention will be specifically explained using reference examples, practical examples, and comparative examples. Unless otherwise specified, all parts and parts are based on weight.

Reference Example 1 [Preparation example of vinyl polymer (1) solution] 300 parts of toluene and 4 parts of butyl acetate were placed in a reactor equipped with a thermometer, a stirring device, a dropping funnel, a nitrogen introduction pipe, and a cooling pipe.
00 parts were charged and the temperature was raised to 110° C. under a nitrogen atmosphere.

Next, 200 parts of styrene, 30 parts of methyl methacrylate
0 parts, 300 parts of le-butyl methacrylate, 130 parts of n-butyl acrylate, 30 parts of acrylic acid, 40 parts of maleic anhydride, azobisisobutyronitrile (AIBN)
10 parts, t-purpurperoxyoctoate (TBP
O) 1 ON, t-butyl/IP-oxypenzoe)
A mixture of 5 parts of TBPB and 300 parts of toluene was added dropwise over 3 hours and then heated to the same temperature for 1 hour.
The reaction was continued for 5 hours until the non-volatile content (NY) reached 5
A solution of a vinyl polymer (a-1) having an acid anhydride group and a carboxyl group with a number average molecular fxt (Mn) of 10,000 at 0% was obtained. Hereinafter, this will be abbreviated as vinyl polymer (a-1-1).

Next, after the temperature of this polymer solution was lowered to 70°C, 40 parts of N,N-dimethylaminoethanol was added thereto, and the same temperature was maintained at RK for 5 hours. Further, 270 parts of n-butanol was added to make NY. A polymer solution having a Gardner color of 1 or less was obtained at 45 cm.

Hereinafter, this will be abbreviated as polymer (1-1), and the reaction rate of acid anhydride groups determined by IR soot 4-cycle analysis for this polymer (1-1) was 88.

Reference Example 2 (same as above) NY was prepared in the same manner as Reference Example 1, except that the same amount of itaconic anhydride was used instead of maleic anhydride.
A polymer having a carboxyl group and a tertiary amino group and having a Gardner color of 45 and a Gardner color of 1 or less [hereinafter abbreviated as polymer (1-2)]. ] was obtained.

Reference Example 3 (same as above) Monomers to be copolymerized include 200 parts of styrene, 250 parts of methyl methacrylate, 340 parts of n-butyl methacrylate, 130 parts of n-butyl acrylate, 50 parts of methacrylic acid, and maleic anhydride. A vinyl polymer having an acid anhydride group and a xyl group (a
-1) solution was obtained.

Next, the temperature of this polymer solution was lowered to 70°C.
- After adding 40 parts of diethylaminoethanol, the mixture was maintained at the same temperature for 5 hours, and 270 parts of n-butanol was further added to obtain a polymer solution with NY of 45 inches and Gardner color of 1 or less. Hereinafter, this will be referred to as polymer (1-3
), but the reaction rate of acid anhydride groups determined by IR spectrum analysis for this polymer (1-3) was 85%0 Reference Example 4 (same as above) Acid anhydride groups obtained in Reference Example 1 1000 parts of a solution of a vinyl polymer (a-1-1) having a carboxyl group and a carboxyl group were heated to 80°C under a nitrogen stream, 20 parts of N,N-dimethylaminopropylamine was added, and the solution was heated at the same temperature. After the reaction was continued for 3 hours, 135 parts of n-butanol was added to obtain a solution of a polymer having a NY of 45 and a Gardner color of 1 or less. Hereinafter, this will be referred to as polymer (1-4).
It is abbreviated as

Reference Example 5 (same as above) The vinyl monomer mixture and polymerization initiator used in Reference Example 1 were each mixed with 200 parts of styrene, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 160 parts of n-butyl acrylate, 40 parts of maleic anhydride and 10 parts of azobisin butyronitrile, 1n parts of t-butyl peroctoate - 3 parts of t-butylno-4-benzoate
The same operation as in Reference Example 1 was repeated except that the solution was used as a substitute, to obtain a solution of a vinyl polymer having 45 qb of NY and a Kugardner color of 1 or less.

Hereinafter, this will be abbreviated as polymer (1-5).

Reference Example 6 [Example of Preparation of Vinyl Polymer (II) Solution] In a reactor similar to Reference Example 1, 800 parts of toluene, 200 parts of inbutanol, and 12 parts of dimethylaminoethyl methacrylate were added.
0 parts, 580 parts of methyl methacrylate, 300 parts of n-butyl acrylate, 10 parts of n-dodecyl mercaptan,
Add 10 parts of azobisin butyronitrile and heat at 80℃ for 2 hours.
After stirring for a while, 0.2 part of azobisisobutyronitrile was added three times every 2 hours, and the polymerization was completed in 12 hours to obtain a vinyl polymer (hereinafter abbreviated as It-1).

It was NV50.3 Chigardna Color-1.

A clear paint was prepared using the polymer solution obtained in each reference example, a polyepoxy compound, and a saturated dicarboxylic acid in the composition ratio shown in the table, and toluene/n-butanol = 7
The mixture was diluted with a mixed solvent of 0/30 (weight ratio) to a sprayable viscosity K, and sprayed onto a zinc phosphate-treated steel plate to a film thickness of 40 μm.

The painted steel plate was baked at 120°C for 10 minutes to obtain a cured coating.

1. / [Effects of the Invention] As is clear from the results in Table 1, the paint prepared from the composition of the present invention provides excellent physical properties and a paint film with almost no yellowing or coloring.

Here, the degree of coloration (Δb value) of the coating film is determined by applying each of the above-mentioned clear paints on a pre-applied white urethane coating film in the same manner as above, and then
The yellowing degree of the coating film was measured after being force-dried for a minute, and the difference in yellowing degree (Δb value) from that of the urethane coating alone was examined. This means that the coating film is less colored.

Agent Patent Attorney Katsutoshi Takahashi Procedural Amendment 1i: (Voluntary) October 1986? 1) Mr. Akihiro 1, Indication of the case, Patent Application No. 24025 of 1988 2, Name of the invention: Curable resin composition 3, Person making the amendment Relationship with the case Patent applicant: 174 3-35-58 Sakashita, Itabashi-ku, Tokyo (28B
) Dainippon Ink & Chemicals Co., Ltd. Representative Shigekuni Kawamura 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Phone: Tokyo (03) 272-4511 (Main representative) 5. Detailed explanation of the invention subject to amendment 6. Contents of amendment (1) F! A11AX! )' Table 1 on page 24 is amended as shown in the attached sheet.

(that's all)

Claims (1)

[Scope of Claims] 1. Comprising (a) a vinyl polymer having at least one tertiary amino group in one molecule, (b) a polyepoxy compound, and (c) a saturated aliphatic dicarboxylic acid. Curable resin composition. 2. As a vinyl polymer having at least one tertiary amino group in one molecule, a vinyl polymer containing a carboxylic acid anhydride group, a group having an active hydrogen that can react with the carboxylic acid anhydride group, and a tertiary The curable resin composition according to claim 1, characterized in that a vinyl polymer obtained by reacting with a compound having an amino group is used. 3. Use a vinyl polymer obtained by reacting a monomer mixture containing a basic nitrogen-containing vinyl monomer as a vinyl polymer having at least one tertiary amino group in one molecule. The curable resin composition according to claim 1, characterized in that: