JPS6231006B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition that has excellent curability at room temperature and is useful for applications such as paints, adhesives, and sealants. In recent years, acrylic lacquer or polyisocyanate-curing urethane paints have been widely used as room temperature drying paints with good weather resistance.
While the former lacquer has the advantage of being low-priced, it has inferior coating properties compared to cross-linked coatings, while the latter coating has excellent coating properties but is inferior to isocyanates. There are problems with the resulting toxicity and price, neither of which can be said to be desirable. For this reason, research and development of new curing systems have been actively conducted, but at present no one with satisfactory performance has yet been obtained. However, as a result of intensive research in view of these circumstances, the present inventors have found that a vinyl polymer having a carboxylic acid anhydride group is used as the base polymer, an epoxy compound is used as the curing agent component, and active hydrogen that is reactive with the acid anhydride group is used as the base polymer. and a tertiary amino group as the component for imparting a functional group to the above base polymer, and if necessary, by adding an alcoholic hydroxyl group-containing compound, a compound with excellent curability at room temperature can be obtained. , discovered that an inexpensive resin composition could be obtained, and completed the present invention. That is, the present invention thus provides (A) a vinyl polymer containing a carboxylic acid anhydride group, (B) an epoxy compound, and (C) each capable of reacting with at least one carboxylic acid anhydride group in one molecule. A compound containing a group having an active hydrogen and a tertiary amino group, and optionally (D) a compound having at least one alcoholic hydroxyl group in one molecule, respectively. The ratio of the total number of equivalents of the acid anhydride group in (A) and the number of equivalents of the tertiary amino group in the compound (C) to the number of equivalents of the epoxy group in the compound (B).
The ratio of the number of equivalents of the active hydrogen-containing group in the compound (C) to the number of equivalents of the acid anhydride group in the polymer (A) so that the ratio is in the range of 0.5 to 2.0. from 0.05
The above compound (D) is further added to
is the ratio of the sum of the number of equivalents of active hydrogen-containing groups in the compound (C) and the number of equivalents of hydroxyl groups in the compound (D) to the number of equivalents of acid anhydride groups in the polymer (A). 0.05
The object of the present invention is to provide a room-temperature curable resin composition containing a compound having a content in the range of 1.0 to 1.0. Here, the above-mentioned carboxylic anhydride group-containing vinyl polymer (A) refers to, for example, a monomer having an acid anhydride group such as maleic anhydride or itaconic anhydride, and a vinyl monomer copolymerizable with these monomers. It refers to the product obtained by copolymerizing the polymer and the polymer. Among them, representative examples of the latter copolymerizable vinyl monomer include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, benzyl methacrylate, and cyclohexyl methacrylate; methyl acrylate; Ethyl acrylate, butyl acrylate,
lauryl acrylate, benzyl acrylate,
Acrylic acid esters such as cyclohexyl acrylate; mono- or dialkyl esters such as itaconic acid, fumaric acid or maleic acid; aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene, vinyltoluene; acrylic acid, methacrylic acid, itacon acids, maleic acid, fumaric acid or crotonic acid, or carboxyl group-containing monomers such as adducts of vinyl monomers having hydroxyl groups and polyvalent carboxylic acid anhydrides; furthermore, vinyl acetate, acrylonitrile, methacrylonitrile , acrylamide, methacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, or N-methylpyrrolidone. The amount of the monomer having a carboxylic acid anhydride group used is preferably in the range of 2 to 30% by weight from the viewpoint of curability, water resistance, alkali resistance, etc., and the amount of the other copolymerizable monomer used is It is 98-70% by weight. The acid anhydride group-containing vinyl polymer (A) can be prepared from the above-mentioned monomers by any known method, but solution radical polymerization is the most preferred method. ,
Aromatic hydrocarbons such as xylene; ethyl acetate,
Usually, using an ester solvent such as butyl acetate, ethylene glycol monoethyl ether acetate, or a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and a known and commonly used polymerization initiator such as an azo solvent or a peroxide solvent. It is preferable to polymerize by a method. At this time, mercaptans such as t-dodecyl mercaptan, lauryl mercaptan, thioglycolic acid alkyl ester, and β-mercaptopropionic acid, and molecular weight regulators such as α-methylstyrene dimer can also be used. In addition, examples of the above-mentioned epoxy compound (B) include monoepoxy compounds such as "Cardilla E-10" (glycidyl ester of branched fatty acids manufactured by Siel in the Netherlands), glycidyl ester of t-butylbenzoic acid; ethylene glycol diglycidyl ether;
Neopentyl glycol diglycidyl ether,
Polyglycidyl ethers of polyhydric alcohols such as 1,6-hexanediol diglycidyl ether, glycerin polyglycidyl ether, sorbitol polyglycidyl ether, diglycidyl ether of hydrogenated bisphenol-A; diglycidyl ester of phthalic acid, isophthalic acid Glycidyl esters of polyhydric carboxylic acids such as diglycidyl esters of polyvalent carboxylic acids; diglycidyl ether-type epoxy resins of bisphenol-A or bisphenol-F, novolak-type epoxy resins, hydantoin ring-containing epoxy resins, glycidyl p-oxybenzoic acid Typical examples include ester ethers and vinyl polymers having epoxy groups in their side chains. Furthermore, a compound containing a group having an active hydrogen which can react with at least one carboxylic acid anhydride group and a tertiary amino group in each molecule as described above.
(C) refers to a compound having a group such as a hydroxyl group, a primary or secondary amino group, or a thiol group as a group having an active hydrogen that can react with the acid anhydride group, Among these compounds, the most preferred are the following amino alcohols having a tertiary amino group, such as those obtained by reacting a secondary amine with an epoxy compound. Representative examples of amino alcohols having a tertiary amino group include dimethylaminoethanol, diethylaminoethanol, diisopropylaminoethanol, dibutylaminoethanol, N-(2-hydroxyethyl)morpholine, N-(2-hydroxy ethyl) piperidine,
N-(2-hydroxyethyl)pyrrolidine, N-
(2-hydroxyethyl)aziridine, N,N-
dimethyl-2-hydroxypropylamine, N,
N-diethyl-2-hydroxypropylamine,
Typical secondary amines used to obtain the amino alcohol include dimethylamine, diethylamine, diisopropylamine, dibutylamine, diethanolamine, dipropanolamine, pyrrolidine, These include piperidine, piperazine, morpholine, and ethyleneimine, as well as primary amines such as methylamine, ethylamine, ethylenediamine, and hexamethylenediamine, as well as ethylene oxide, propylene oxide, butylene oxide, hexene oxide, dodecene oxide, styrene oxide, and butyl oxide. Examples include glycidyl ether or adducts with monoepoxy compounds such as the above-mentioned "Cardilla E-10" or glycidyl ester of t-butylbenzoic acid.On the other hand, representative epoxy compounds include the above-mentioned compounds. Includes mono- or polyepoxy compounds such as those mentioned above. Further, as the compound (C), in addition to the amino alcohols having a tertiary amino group exemplified above, amino alcohols such as ethanolamine and propanolamine and tertiary amino groups such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate may be used. It is also possible to use adducts with acrylic monomers that have a . Incidentally, representative examples of the compound (D) having at least one alcoholic hydroxyl group in one molecule include methanol, ethanol, n-
1 such as propanol, i-propanol, n-butanol, octanol, benzyl alcohol, etc.
Alcohol; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol,
Polyhydric alcohols such as polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol; Furthermore, polycaprolactone polyols obtained by reacting these polyhydric alcohols with caprolactone, or polyesters and alkyds having hydroxyl groups. These include resins or vinyl polymers. The composition of the present invention includes the aforementioned acid anhydride group-containing vinyl polymer (A) and the aforementioned epoxy compound, respectively.
(B), a compound (C) having both an active hydrogen group and a tertiary amino group, and, if necessary, an alcoholic hydroxyl group-containing compound (D). The amount of C) to be blended is such that the ratio of the number of equivalents of active hydrogen-containing groups in the compound (C)/the number of equivalents of acid anhydride groups in the vinyl polymer (A) is 0.05 to
2.0, and the blending amount of the above compound (B) is [number of acid anhydride group equivalents in the vinyl polymer (A) + number of tertiary amino group equivalents in the compound (C)] ]/The ratio of the number of epoxy group equivalents in the compound (B) is
0.5 to 2.0, and when the above compound (D) is further blended, the total blending amount of the above compound (C) and the compound (D) is
The ratio of the number of equivalents of groups having active hydrogen in the compound (D) and the number of equivalents of hydroxyl groups in the compound (D)/the number of equivalents of acid anhydride groups in the vinyl polymer (A) is within the range of 0.05 to 1.0. It is preferable to be selected to enter. The thus obtained composition of the present invention can be used as it is, or if necessary, pigments, solvents,
Paints prepared with additives etc. can be applied to the object to be coated and left at room temperature for about 1 to 2 days, or if necessary, dried at 60 to 100 degrees Celsius for 20 to 30 minutes. By sufficiently curing the coating film, a coating film with excellent mechanical strength can be obtained. Furthermore, the paint obtained from the composition of the present invention is significantly cheaper than urethane paints, and there is no concern about toxicity, which is often a problem with urethane paints. 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 just the paint as described above, but can also be used as an adhesive or a sealant. Next, the present invention will be explained in more detail with reference to Examples, in which all parts are by weight unless otherwise specified. Reference Example 1 (Preparation example of vinyl polymer (A)) Toluene was placed in 3 flasks equipped with a thermometer, a stirring device, a dropping funnel, a nitrogen introduction tube, and a cooling tube.
400 parts and 300 parts of cellosolve acetate were charged, and the temperature was raised to 110°C under a nitrogen stream. Next, 200 parts of styrene and 331 parts of methyl methacrylate were added at the same temperature.
parts, n-butyl methacrylate 200 parts, n-butyl acrylate 200 parts, maleic anhydride 69 parts, azobisisobutyronitrile 10 parts, t-butyl peroxy-2-ethylhexanoate 10 parts, t-butyl peroxy 3 parts oxybenzoate, 200 parts toluene
and 100 parts of cellosolve acetate were added dropwise over 4 hours and then kept at the same temperature for 15 hours to give a non-volatile content of 52.1% and a Gardner viscosity of S.
A polymer solution (A-1) having an acid anhydride group and having a Gardner color of 1 or less was obtained. Reference example 2 (same as above) Reference example 1 except that the amount of methyl methacrylate was changed to 269 parts and the amount of maleic anhydride was changed to 138 parts.
Repeat the same operation to obtain a non-volatile content of 53.0%,
Gardner viscosity W~X and Gardner color 1
The following solution of a polymer having an acid anhydride group (A-
2) was obtained. Reference example 3 (same as above) The amount of methyl methacrylate was changed to 321 parts,
The same procedure as in Reference Example 1 was carried out except that 79 parts of itaconic anhydride was used instead of maleic anhydride, and the nonvolatile content was 51.5% and the Gardner viscosity R.
A solution (A-3) of a polymer having an acid anhydride group and having a Gardner color of 1 or less was obtained. Reference example 4 (same as above) 200 parts of vinyltoluene instead of styrene and n-butyl methacrylate
A polymer solution containing an acid anhydride group (A-4) was prepared in the same manner as in Reference Example 1, except that 200 parts of cyclohexyl methacrylate was used. ) was obtained. Reference Example 5 (Same as above) A mixture consisting of 200 parts of styrene, 300 parts of ethyl methacrylate, 300 parts of isobutyl methacrylate, 50 parts of vinyl acetate, 81 parts of lauryl methacrylate, and 69 parts of maleic anhydride was used as a monomer. The non-volatile content was 51.9%, the Gardner viscosity was U-
A polymer solution (A-5) having an acid anhydride group and having V and a Gardner color of 1 or less was obtained. Reference Example 6 (Same as above) As monomers, 300 parts of styrene, 300 parts of methyl methacrylate, and 100 parts of dibutyl fumarate.
100 parts of n-butyl methacrylate, 121 parts of n-butyl acrylate, and 79 parts of itaconic anhydride. R and Gardner color 1 or less,
A polymer solution (A-6) having acid anhydride groups was obtained. Reference Example 7 (Same as above) As monomers, 200 parts of styrene, 200 parts of methyl methacrylate, 340 parts of n-butyl methacrylate, 100 parts of isobutyl acrylate, 50 parts of acrylonitrile, 10 parts of methacrylic acid, and maleic anhydride. A solution of a polymer having an acid anhydride group (A-
7) was obtained. Reference Example 8 [Preparation example of epoxy compound (B)] A mixture consisting of 200 parts of styrene, 300 parts of methyl methacrylate, 200 parts of n-butyl methacrylate, and 300 parts of glycidyl methacrylate was used as the monomer. A polymer solution containing an average of 19.0 epoxy groups per molecule (B-1) was prepared in the same manner as in Reference Example 1 except for the following: nonvolatile content 51.0%, Gardner viscosity R, Gardner color 1 or less, and number average molecular weight 9000. ) was prepared. Reference Example 9 [Preparation example of compound (D) containing alcoholic hydroxyl group] As monomers, 200 parts of styrene, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, and 200 parts of β-hydroxyethyl methacrylate The non-volatile content was 51.5% in the same manner as in Reference Example 1, except that a mixture consisting of
A vinyl polymer solution (D-1) having a Gardner viscosity S, a Gardner color of 1 or less, and a number average molecular weight of 9000 and containing an average of 13.8 alcoholic hydroxyl groups per molecule was obtained. Examples 1 to 4 A clear paint was prepared according to the prescribed formulation in Table 1, and this was applied to a zinc phosphate-treated steel plate with a doctor blade to a film thickness of about 60μ, and then dried at 23°C for 2 days. did. The results of performance tests on these various coating films are shown in Table 1. Examples 5 to 9 In addition to using each of the polymers obtained in Reference Examples 4 to 9, various components (B), (C), and (D) were also used to create the formulations shown in Table 2. A clear paint was prepared according to the above ratio, and thereafter applied in the same manner as in Example 1 to obtain a paint film. The results of performance tests on these various coating films are summarized in the same table. Comparative Example 1 A control paint was prepared and applied in the same manner as in Examples 1 to 4, except that the use of dimethylaminopropylamine was changed to completely omit the use of dimethylaminopropylamine. I got it. The results of the performance tests on this coating are shown in Table 2.

【table】

[Table] As is clear from the results in Tables 1 and 2, when the component (C) is not used (in the case of Comparative Example 1), the curability at room temperature is poor, and therefore the coating film However, the paint obtained from the resin composition of the present invention has excellent curing properties at room temperature.
It is known to have excellent coating film properties.

Claims (1)

[Scope of Claims] 1. (A) A vinyl polymer containing a carboxylic acid anhydride group, (B) an epoxy compound, and (C) each of which reacts with at least one carboxylic acid anhydride group in one molecule. The above compound (B) contains a compound containing a group having an active hydrogen and a tertiary amino group, and optionally (D) a compound containing at least one alcoholic hydroxyl group in one molecule. The ratio of the total number of equivalents of acid anhydride groups in the polymer (A) and the number of equivalents of the tertiary amino group in the above compound (C) to the number of equivalents of the epoxy group in the compound (B) is 0.5 to 2.0. The ratio of the number of equivalents of the active hydrogen-containing group in the compound (C) to the number of equivalents of the acid anhydride group in the polymer (A) is 0.05 so that the number of equivalents of the acid anhydride group in the polymer (A) is within the range of 2.0, the above compound (D) is further combined with the sum of the number of equivalents of the group containing active hydrogen in the above compound (C) and the number of equivalents of hydroxyl groups in the compound (D) and the above polymer. A room temperature curable resin composition comprising acid anhydride groups in (A) in a ratio of 0.05 to 1.0.