JPH0430415B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful curable resin composition containing a specific vinyl polymer containing a tertiary amino group as a base resin component, and more specifically, to a curable resin composition containing a specific vinyl polymer containing a tertiary amino group and a polyepoxy resin composition. The present invention relates to a resin composition comprising a compound as a main component. Conventionally, this type of tertiary amino group-containing vinyl polymer has been used as a paint resin, but in order to prepare such a tertiary amino group-containing vinyl polymer, N,N-dialkyl Tertiary amino group-containing (meth)acrylates such as aminoalkyl (meth)acrylates as monomers (co-)
A method of polymerization is used. However, the polymers obtained by these methods have an amine odor and are significantly colored, so when a cured coating is made from a resin composition obtained by blending such polymers with an epoxy resin, However, it also had the disadvantage that the coating film was markedly colored, impairing its commercial value. However, in view of the above-mentioned shortcomings in the prior art, the present inventors have developed a method of combining a vinyl polymer containing a carboxylic anhydride group, a group having active hydrogen in one molecule that can react with the carboxylic anhydride group, and a vinyl polymer containing a carboxylic anhydride group. 3
It is obtained by reacting the compound with a compound each having at least one amino group. carboxyl group and 3
Japanese Patent Application No. 57-166795 and Japanese Patent Application No. 58-1982 have previously been published regarding compositions composed of a polyepoxy compound and a specific vinyl polymer having both a class amino group and a polyepoxy compound.
No. 17192, but it was subsequently discovered that the compositions related to both of these applications gave only cured products with insufficient stain resistance and alkali resistance,
Further research revealed that a tertiary amino group-containing vinyl polymer obtained by reacting the carboxylic acid anhydride group-containing vinyl polymer with a specific tertiary amino group-containing compound was obtained by reacting the carboxylic acid anhydride group-containing vinyl polymer with a polyepoxy compound. The present inventors have now completed the present invention by discovering that by blending these compounds, a cured product can be obtained that has no amine odor, little coloring, and has excellent stain resistance, alkali resistance, and weather resistance. That is, the present invention comprises a vinyl polymer (a-1) containing a carboxylic acid anhydride group as a main component;
Vinyl containing a tertiary amino group obtained by addition reaction with a compound (a-2) containing one primary amino group and one tertiary amino group in the molecule, followed by dehydration condensation and imide cyclization. Polymer (A)
and a polyepoxy compound (B), and provides a curable resin composition having particularly excellent stain resistance and alkali resistance of the cured product. Here, as the vinyl polymer (a-1) containing the above-mentioned carboxylic acid anhydride group, for example, monomers having an acid anhydride group such as maleic anhydride or itaconic anhydride, and these acid anhydride groups are used. It is obtained by copolymerizing the containing monomer with other copolymerizable vinyl monomers, and typical examples of the above-mentioned copolymerizable vinyl monomers include methyl ( meta) acrylate,
Ethyl (meth)acrylate, propyl (meth)
Acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-
(meth)acrylic acid esters such as butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate or benzyl (meth)acrylate; itaconic acid; Dialkyl esters of unsaturated dibasic acids such as maleic acid or fumaric acid; (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid monoalkyl ester, maleic acid monoalkyl ester or fumaric acid mono alkyl esters,
or a monomer having a carboxyl group such as an adduct obtained by reacting a hydroxyl group-containing vinyl monomer such as β-hydroxyethyl (meth)acrylate with an acid hydrate such as succinic anhydride or trimellitic anhydride; Aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene or vinyltoluene; or vinyl acetate, (meth)acrylonitrile, (meth)acrylamide, diacetone acrylamide, N,N-dimethyl(meth)acrylamide, N-vinylpyrrolid , vinyl chloride or phosphate ester of β-hydroxyethyl (meth)acrylate. The amount of the acid anhydride group-containing monomer listed above is determined based on the curability of the resulting curable resin composition and the stain resistance and alkali resistance of the cured product. 1 in (a-1)
Preferably, it is present in a proportion between 20% and 20% by weight. Furthermore, although it is possible to obtain a resin composition that meets the purpose of the present invention without using the carboxyl group-containing monomers listed above,
When preparing (A), when it is necessary to shorten the reaction time or when it is necessary to improve the curability of the composition of the present invention, the carboxyl group-containing monomer may be used. It is preferable to copolymerize the vinyl monomer (a-1) in an amount of 0.1 to 15% by weight, preferably 1 to 15% by weight. Although it is possible to prepare the vinyl polymer (a-1) from the various monomers listed above by any known method, solution radical polymerization is particularly preferred. Most preferably, these include aromatic hydrocarbons such as toluene, xylene; (cyclic) aliphatic hydrocarbons such as hexane, heptane, cyclohexane; ester systems such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate; or acetone, methyl ethyl ketone. , methyl-iso-butyl ketone,
It is appropriate to carry out the polymerization by a conventional method using various types of solvents such as ketone type solvents such as cyclohexanone and various known and commonly used polymerization initiators such as azo type or peroxide type. At this time, polymerization can also be carried out using a mercaptan such as tert-dodecyl mercaptan, lauryl mercaptan, thioglycolic acid alkyl ester or β-meltocaptopropionic acid, or a molecular weight regulator such as α-methylstyrene dimer. Next, a compound (a
-2) Representative examples include N,N-dialkylethylenediamines such as N,N-dimethylethylenediamine, N,N-diethylethylenediamine, and N,N-dipropylethylenediamine;
N,N-dialkyl-1,3- such as N,N-dimethyl-1,3-propylene diamine, N,N-diethyl-1,3-propylene diamine, N,N-dipropyl-1,3-propylene diamine; Propylene diamines; N,N-dimethyl-1,4
-tetramethylenediamine, N,N-diethyl-
N,N-dialkyl-1,4-tetramethylene diamines such as 1,4-tetramethylene diamine and N,N-dipropyl-1,4-tetramethylene diamine; N,N-dimethyl-1,6-hexamethylene Diamine, N,N-diethyl-1,6-hexamethylenediamine, N,N-dipropyl-
N,N- such as 1,6-hexamethylene diamine
Dialkyl-1,6-hexamethylene diamines; N-(2-aminoethyl)morpholine, N-
N-aminoalkylmorpholines such as (3-aminopropyl)morpholine, N-(4-aminobutyl)morpholine, N-(6-aminohexyl)morpholine; N-(2-aminoethyl)pyrrolidine;
N such as N-(3-aminopropyl)pyrrolidine
-aminoalkylpyrrolidines; or N-(2
-aminoethyl)piperidine, N-(3-aminopropyl)piperidine, etc. Among them, N,
Preference is given to using N-dialkyl-1,3-propylene diamines. These polymers (a-1) and compound (a
-2) The vinyl polymer (A) described above by reaction with
To prepare, first, 1 equivalent of compound (a-2) is added to 1 equivalent of acid anhydride group in polymer (a-1).
These two compounds are mixed at a ratio such that the amount of amino groups is approximately 0.5 to 3 equivalents, and heated from room temperature to 120°C.
After the adduct is obtained by reacting at a temperature of about 100°C for about 0.5 to 3 hours, the adduct is then heated at 70 to 150°C for about 1 to 20 hours to cause dehydration condensation (imide cyclization reaction) to form an imide. A vinyl polymer (A) having a ring and also having a tertiary amino group can be obtained. Here, when a maleic anhydride copolymer is used as the polymer (a-1) and N,N-dimethyl-1,3-propylene diamine is used as the compound (a-2), Vinyl polymer (A) is obtained according to the reaction formula. As can be seen in these exemplary reaction formulas, condensation water is produced, but depending on the application, such condensation water does not need to be removed and can be used as is. If necessary, dehydration can be carried out during or after the dehydration condensation reaction by adding a known and commonly used dehydrating agent or drying agent, or by performing azeotrope with a solvent. Here, the ring closure rate of the amide carboxylic acid moiety to the imide ring in the polymer having an amide carboxylic acid structure which is the addition reaction product of the polymer (a-1) and the compound (a-2) is as follows: Usually 70%
It is desirable to set the above. This is because if it becomes too high, exceeding 70%, it becomes impossible to ensure the stain resistance, alkali resistance, etc., which are the characteristics of the present invention. The curable resin composition of the present invention is obtained by blending the vinyl polymer (A) thus obtained with a polyepoxy compound (B). To name a few, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether or hydrogenated bisphenol A Polyglycidyl ethers of polyhydric alcohols such as diglycidyl ether; phenols such as diglycidyl ether type epoxy resin of bisphenol A, diglycidyl ether type epoxy resin of bisphenol F, or polyglycidyl ether type epoxy resin of novolac type phenol resin; Polyglycidyl ethers of polyhydric hydroxyl group-containing compounds; Polyglycidyl esters of polyhydric carboxylic acids such as diglycidyl ester of adipic acid, diglycidyl ester of phthalic acid, or diglycidyl ester of isophthalic acid; N, N,
N-glycidyl polyamines such as N',N'-tetraglycidyl-m-xylylene diamine or 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane; or hydantoin ring-containing epoxy resins, p-oxybenzoin Glycidyl ester ether or side chain of acid (β-methyl)
There are various vinyl polymers having glycidyl groups, and these may be used alone or in combination of two or more. The blending ratio of the vinyl polymer (A) and the above-mentioned polyepoxy compound (B) is as follows:
From the viewpoint of curability, the compound (B) is
The range is preferably such that the amount of epoxy groups therein is 0.5 to 2 equivalents. In obtaining the composition of the present invention, when an epoxy resin with good weather resistance such as polyglycidyl ether of polyhydric alcohol is used as the polyepoxy compound (B), a cured product with good weather resistance can be obtained. Although a resin composition is provided, ultraviolet absorbers, antioxidants, etc. can be added to the composition of the present invention, and by doing so, weather resistance can be further improved. Typical such ultraviolet absorbers include:
These include benzotriazole compounds, hydroxybenzophenone compounds, and unsaturated nitrile compounds. Typical antioxidants include hindered phenol compounds and hindered amine compounds. As for the amount of the antioxidant and/or the antioxidant, about 0.05 to 5% by weight based on the total solid content of the components (A) and (B) described above is sufficient. The thus obtained curable resin composition of the present invention may be used as it is as a paint, or if necessary, it may be further mixed with a pigment, a solvent, cellulose acetate butyrate, nitrocellulose, chlorinated polyolefins, polyisocyanate, blocking. It may also be used in the form of a paint prepared by blending other synthetic resins such as polyisocyanate or ketone resins. The paint obtained from the composition of the present invention can be applied to a commonly used object and then left at room temperature for 1 to 2 days, or if necessary, dried for 20 to 40 minutes at 60 to 100°C. It is cured to give a cured coating film with excellent physical properties, stain resistance and alkali resistance. In this way, when the paint obtained using the composition of the present invention is used as a clear paint,
There is little discoloration of the paint film, and there are no concerns about toxicity, which is often a problem with urethane paints. Therefore, the composition of the present invention can be applied to various applications in which conventional urethane paints are used, such as automobile repair, woodworking, building materials, and plastics. It can also be applied to applications such as adhesives or sealants. Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. Unless otherwise specified, all parts and percentages are based on weight. Reference Example 1 [Example of Preparation of Polymer (A)] 700 parts of toluene was charged into a reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a condenser, and the mixture was heated to 110°C in a nitrogen atmosphere. The temperature was raised, and then 300 parts of styrene, 200 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, and
- 130 parts of butyl acrylate, 70 parts of maleic anhydride, azobisisobutyronitrile (AIBN)
10 parts of tert-butyl peroxyoctoate (TBPO), 5 parts of tert-butyl peroxybenzoate (TBPB) and 300 parts of toluene.
dropwise over 3 hours and then kept at the same temperature for 15 hours to continue the reaction, producing an acid anhydride with a non-volatile content (NV) of 50% and a number average molecular weight (n) of 9000. A solution of the group-containing vinyl polymer (a-1) was obtained. Hereinafter, this will be abbreviated as vinyl polymer (a-1-1). Next, the temperature of this polymer solution was lowered to 100°C, 72.9 parts of N,N-dimethyl-1,3-propylenediamine was charged therein, and the temperature was maintained at the same temperature for 12 hours for dehydration and ring closure, and then the temperature was lowered under reduced pressure. 100 of toluene
The water of condensation was removed by distillation. Then 100 parts of toluene and 296 parts of n-butanol were added until the Gardner color was 1.
A solution of the objective vinyl polymer having the following properties and an NV of 45% was obtained. Hereinafter, this will be referred to as vinyl polymer (A
-1). The solid acid value of the polymer (A-1) thus obtained was 4.0, and an absorption of 1700 cm ^-1 due to the imide ring was confirmed by IR spectrum analysis. The ring closure rate to the imide ring calculated from this acid value was 89%. Reference Example 2 [Preparation Example of Polymer (A)] The same procedure as in Example 1 was carried out except that 20 parts of 70 parts of maleic anhydride among the monomers to be copolymerized were replaced with acrylic acid. Acid anhydride group-containing vinyl polymer with NV of 50% and n of 9100 (a-
1) was obtained. Hereinafter, this will be abbreviated as vinyl polymer (a-1-2). Next, the temperature of this polymer solution was lowered to 100°C,
After adding 52 parts of N,N-dimethyl-1,3-propylene diamine and holding at the same temperature for 3 hours to cause dehydration and ring closure, 100 parts of toluene was distilled off under reduced pressure to remove condensed water. It was removed. 100 parts of toluene and 275 parts of n-butanol are then added until the Gardner color reaches 1.
A solution of the objective vinyl polymer having the following properties and an NV of 45% was obtained. Hereinafter, this will be referred to as vinyl polymer (A
-2), the solid acid value of the polymer (A-2) was 16.3, and the ring closure rate to the imide ring calculated from this value was 94%. Reference example 3 [Preparation example of polymer (A)] The monomer composition to be copolymerized was
NV was prepared in the same manner as in Example 1, except that 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 120 parts of n-butyl acrylate, 40 parts of methacrylic acid, and 40 parts of maleic anhydride were used. A solution of an acid anhydride group-containing vinyl polymer (a-1) with a concentration of 50% and n of 9200 was obtained. Hereinafter, this will be abbreviated as vinyl polymer (a-1-3). Next, the temperature of this polymer solution was lowered to 100°C,
41.6 parts of N,N-dimethyl-1,3-propylene diamine was added thereto, kept at the same temperature for 3 hours to cause dehydration and ring closure, and then toluene was added under reduced pressure.
100 parts were distilled off to remove water of condensation. After that, 100 parts of toluene and n
- 264 parts of butanol were added to obtain a solution of the desired vinyl polymer with a Gardner color of 1 or less and an NV of 45%. Hereinafter, this will be abbreviated as vinyl polymer (A-3).
The solid acid value of 3) was 26, and the ring closure rate to the imide ring calculated from this value was 96%. Reference example 4 [Preparation example of polymer (A)] of the polymer (a-1-2) obtained in Example 2
The temperature of 2,000 parts was raised to 100°C, 66.3 parts of N,N-diethyl-1,3-propylene diamine was charged thereto, and the mixture was kept at the same temperature for 3 hours to cause dehydration and ring closure, and then 100 parts of toluene was added under reduced pressure. was distilled off to remove condensed water. After that, 100 parts of toluene and n
- 292 parts of butanol were added to obtain a solution of the objective vinyl polymer with a Gardner color of 1 or less and an NV of 45%. Hereinafter, this will be abbreviated as vinyl polymer (A-4), but the polymer (A-4)
The solid acid value of the compound was 16, and the ring closure rate to the imide ring calculated from this value was 95%. Reference Example 5 (Example of preparation of control polymer solution) of the polymer (a-1-1) obtained in Example 1.
2000 parts were heated to 50°C, 72.9 parts of N,N-dimethyl-1,3-propylenediamine were added thereto, and after keeping at the same temperature for 30 minutes, 311 parts of n-butanol was added. A solution of a tertiary amino group-containing vinyl polymer that is not imidocyclized and has a Gardner color of 1 or less and an NV of 45% was obtained. Hereinafter, this will be abbreviated as vinyl polymer (A'-1), and the solid acid value of this polymer was 37. Examples 1 to 4 and Comparative Example 1 Using each polymer solution obtained in each reference example as a base resin component, a white paint having a PWC of 40% was prepared at the composition ratio shown in Table 1. Next, each paint was mixed with xylene/toluene/n-butanol/cellosolve acetate=
It was diluted to a spray viscosity with a mixed solvent of 30/40/20/10 (weight ratio) and spray-painted on a slate board, and then left at room temperature for 7 days to cure. Performance evaluation was performed on each coating film thus obtained, and the results shown in the table were obtained.

【table】

[Table] As is clear from the results in Table 1, the cured product (coating film) obtained using the curable resin composition of the present invention has excellent alkali resistance, stain resistance, and weather resistance. It was hot.

Claims (1)

[Scope of Claims] 1 (A) A vinyl polymer (a-1) having a carboxylic anhydride group, and a compound (a-1) having one primary amino group and one tertiary amino group in each molecule. −
2), and then dehydration condensation-imide cyclization to obtain a vinyl polymer having a tertiary amino group, and (B) a polyepoxy compound as main components. A curable resin composition containing a tertiary amino group-containing vinyl polymer as a base resin component. 2. The composition according to claim 1, wherein the carboxylic anhydride group-containing vinyl polymer (a-1) has a carboxylic anhydride group and also has a carboxyl group. . 3 Compound (a-2) each having one primary amino group and one tertiary amino group in one molecule as described above
The composition according to claim 1 or 2, wherein is N,N-dialkyl-1,3-propylenediamine. 4. A patent in which the above-described curable resin composition further contains either one of an ultraviolet absorber or an antioxidant, or both the ultraviolet absorber and the antioxidant. A composition according to any one of claims 1 to 3.