JPH02142819A - Curable resin composition - Google Patents

Abstract

PURPOSE:To make it possible to form a resin composition improved in nonyellowing property during the drying of a coating film and low-temperature curability by mixing a resin composition comprising a specified vinyl copolymer and a polyepoxy compound with a specified organophosphorus compound and a cure accelerator. CONSTITUTION:This curable resin composition contains a vinyl copolymer (base resin component) (A) having at least one tert. amino group in the molecule, a polyepoxy compound (B) (curing agent component) and 0.01-10wt.%, based on component A, at least one compound (C) as a cure accelerator selected from among an organic trivalent phosphonium salt, an organic trivalent phosphine and an organic trivalent phosphite. As component A, a reaction product of a carboxyl anhydride group-containing vinyl copolymer with a compound having a group having an active hydrogen atom reactive with the carboxyl anhydride group and a tert. amino group can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel and useful curable resin composition. More specifically, the resin composition is composed of a specific base resin component and a curing agent component, and further contains a specific organic phosphorus-containing compound as a curing accelerator component. The present invention relates to an excellent curable resin composition.

The composition of the present invention having the following contents can be mainly applied to a wide range of applications such as paints, adhesives, and sealants.

[Conventional technology]

In recent years, acrylic lacquers and polyisocyanate-curing urethane paints have become widely used as room-temperature drying paints with good weather resistance.In the case of the former acrylic lacquers, although they have the advantage of being low-priced, cross-linked paints In comparison, the physical properties of the coating film are inferior. On the other hand, in the latter case, there are disadvantages in terms of toxicity due to the isocyanate compound and cost, and neither of these can be said to be preferable. Therefore, the development of a new curing system is desired.

As a result of intensive study in view of the above-mentioned actual situation, the inventors of the present invention found that
As announced in the above publication, we have invented a resin composition that is curable at room temperature and has high performance.

Such a resin composition comprises a vinyl polymer (a-
A tertiary amino compound obtained by reacting 1) with a compound (a-2) having both a tertiary amino group and a group having an active hydrogen capable of reacting with one of the above-mentioned caldic acid anhydride groups in one molecule. This is a room temperature curable resin composition comprising a group-containing vinyl copolymer (1) and a polyepoxy compound as essential components.

On the other hand, although the method of introducing the tertiary amino group into the vinyl polymer is different from the above resin composition, a resin composition using a polyepoxy compound as a curing agent is disclosed in JP-A-52-76338.
As disclosed in the above publication, there is a resin composition that is curable at room temperature. Such a resin composition includes (1) a basic nitrogen-containing acrylic mass of 0.2 to 30% by weight, (2+(
Esters of meth)acrylic acid and aliphatic monohydric alcohol or mixtures thereof 35-99.8% by weight 1, (3
1 and other copolymerizable monomers, i.e., a tertiary amino group-containing vinyl copolymer (It), blended with a polyepoxy compound.

As mentioned above, these resin compositions are novel and have room temperature curability. However, when a resin composition crosslinked with such a tertiary amino group and an epoxy compound is used as a paint, when drying,
Among other things, it not only turns yellow when heated and dried, but also
It was found that it had the disadvantage of poor curing properties at low temperatures.

That is, there was a drawback in that the performance of the cured coating film was insufficient at low temperatures, which are the conditions for use in winter and in cold regions.

[Problem to be solved by the invention]

For this reason, in order to suitably use the above-mentioned resin composition as a resin composition for paint, it is necessary to improve the curability at low temperatures.

Therefore, in view of the various drawbacks in the conventional techniques, the present inventors provide a curable resin composition that has improved both thermal yellowing during drying of the coating film and low-temperature curability. As a result of extensive research, we found that by using a specific organic phosphorus compound as a curing accelerator,
A resin composition comprising a tertiary amino group-containing vinyl copolymer and a polyepoxy compound can be made into an excellent low-temperature curable resin composition, and can be easily cured, especially by heating, during drying of the coating film. Freed from yellowing during drying,
The present invention was completed by discovering that a resin composition capable of giving an excellent cured product could be obtained.

[Means to solve the problem]

That is, the present invention uses a vinyl copolymer (A) having at least one tertiary amino group in one molecule as an essential component.
) and, on the other hand, polyepoxy compound (B), each of which contains a base resin component and a curing agent component, further contains an organic trivalent phosphonium salt, an organic At least one compound (C') selected from the group consisting of trivalent phosphines and organic trivalent phosphites is added to the vinyl copolymer (0 to
．． It is an object of the present invention to provide a curable resin composition which contains an amount of 0.01 to 10% by weight, and is particularly excellent in low-temperature curability and resistance to heat yellowing of coating films.

Here, vinyl copolymer ( Examples of A) include the following:

First, one of them is a monomer having an acid anhydride group such as maleic anhydride or itaconic anhydride as disclosed in JP-A-59-56423 and JP-A-59-142220. and, if necessary, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid; monoalkyl maleate, monoalkyl fumarate or monoalkyl itaconate; or β-hydroxyethyl ( A monomer having a calgexyl group such as an adduct of a vinyl monomer having a hydroxyl group such as meth)acrylate and an acid anhydride such as succinic anhydride or trimellitic anhydride, and each of the above-mentioned monomers. Examples include vinyl copolymers obtained by copolymerizing a copolymerizable vinyl monomer with another vinyl monomer having copolymerizability.
It is abbreviated as 1).

Typical examples of other vinyl monomers having such copolymerizability include methyl (meth)acrylate, ethyl (meth)acrylate, n- or tart-butyl (meth)acrylate, and lauryl (meth)acrylate.
(Cyclo)alkyl or aralkyl esters of various (meth)acrylic acids such as meth)acrylate, benzyl (meth)acrylate or cyclohexyl (meth)acrylate; dialkyl of unsaturated dibasic acids such as itaconic acid, maleic acid or fumaric acid. Esters;
Aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene, vinyl toluene; “Viscoat 8F
, 8FM13F, 3FMJ (Fluorine-containing (meth)acrylic monomer manufactured by Osaka Organic Chemical ■) 4L
-) Fluoroalkyl group-containing vinyl monomers; mono[(
Phosphoric acid group-containing vinyl monomers such as meth)acryloyloxyethyl] acid phosphate; vinyl ethoxysilane, α-(meth)acryloyloxyglobyl trimethoxysilane, trimethylsiloxyethyl (meth)acrylate, l'-KR-215J Or l'-X-5
Silicon-based monomers such as 002J (all products from Shin-Etsu Chemical Co., Ltd.); "T-37J or [LA-82J
(Polymerizable ultraviolet absorber monomer or light stabilizer monomer, respectively, manufactured by Adeka Argus Chemical); or vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, (meth)acrylonitrile , (meth)acrylamide, diacetone acrylamide, N,N-dimethylacrylamide or N
-Vinyl pyrrolide y, etc., but polyester resins having copolymerizable unsaturated bonds (including oil-modified Thai f), vinyl copolymers, etc. can also be used in the same way.

The amount of the monomer having an acid anhydride group as mentioned above and the cal-xyl group-containing monomer used if necessary is 1 to 1. Within the range of 20% by weight, the latter is 0 to 15
A suitable amount is within the range of 99 to 65% by weight, while the amount of copolymerizable vinyl monomer, such as suspended, is suitably within the range of 99 to 65% by weight.

Vinyl copolymer (a-1) can be prepared using the various monomers listed above by any known and commonly used method, but solution radical polymerization is the most effective method. Preferred examples include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, hebutane, and cyclohexane; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol, and monomethyl ether acetate; or acetone, methyl ethyl ketone, Polymerization may be carried out by a conventional method using a ketone solvent such as methyl isobutyl ketone or cyclohexanone, and a known and commonly used polymerization initiator such as an azo or peroxide compound.

In this case, a molecular weight regulator such as mercaptans such as t-dodecyl mercaptan, lauryl mercaptan, thioglycolic acid alkyl ester, and β-mercagutopropionic acid, and α-methylstyrene dimer may be used.

Next, the vinyl copolymer (a-1) is reacted with a compound (a-2) having both a group having an active hydrogen group capable of reacting with the carboxylic anhydride group in the polymer and a tertiary amino group. The base resin of the composition of the present invention is a vinyl copolymer (~
get.

Cal mentioned above? A compound (a-2) having both a group having an active water (lO) element that can react with an acid anhydride group (hereinafter abbreviated as an active hydrogen-containing group) and a tertiary amino group is:
This active hydrogen-containing group refers to a compound having each group such as a hydroxyl group, a -class or secondary amino group, or a thiol group, but among these, the most preferable compound is a compound having a tertiary amino group. Examples include alcohols and primary or secondary aminos having a tertiary amino group. Typical examples of the former amino alcohols include adducts of secondary aminos and epoxy compounds, while typical secondary aminos used here include dimethylamino, diethylamino,
dipropylamino, dibutylamino, ethyleneimine,
There are morpholine, piperazine, piperidine, pyrrolidine, etc., and there are also secondary amino group-containing amino alcohols obtained by addition of primary aminos such as methylamino, ethylamino, and butylamino with mono- or polyepoxy compounds. On the other hand, typical epoxy compounds include ethylene oxide, zolopyrene oxide, butylene oxide, dodecene oxide, styrene oxide, cyclohexene oxide, butyl glycidyl ether or phenyl glycidyl ether: or p-tert-butylbenzoic acid glycidyl ester. or monoepoxy compounds such as Cardura E-10J (glycidyl ester of branched fatty acids manufactured by Shell, Netherlands); or ethylene glycol diglycinol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol Polyglycidyl ethers of polyhydric alcohols such as diglycidyl ether of -/I/A or triglycidyl ether of glycerin: Polyglycidyl ethers of polyhydric alcohols such as diglycidyl ester of phthalic acid, diglycidyl ester of isophthalic acid or diglycidyl ester of adipic acid. Polyglycidyl esters of carboxylic acids; or polyepoxy compounds such as various epoxy resins such as diglycyl sol ether type epoxy resins of bisphenols or bisphenol F, novolak type epoxy resins, or hydantoin-containing epoxy resins; Examples include glycidyl ester ether of -oxybenzoic acid and various vinyl copolymers having an epoxy group in the side chain.

Typical examples of the tertiary amino group-containing alcohols obtained by reacting secondary aminos with epoxy compounds include dimethylaminoethanol, diethylaminoethanol, di-n-propylaminoethanol, and diisozolobylaminoethanol. , Moro-butylaminoethanol, Dimethylaminobutanol, Dimethylaminohexanol, N-(2-hydroxyethyl)morpholine, N
-(2-hydroxyethyl)hyperidine, N-(2-hydroxyethyl)pyrrolidine, N-(2-hydroxyethyl)aziridine, N,N-dimethyl-2-hydroxyzolobylamino, N,N-diethyl-2- Examples of alcohols containing tertiary amino groups include hydroxyzolobylamino, triethanolamino, and triethanolamino. Adducts of alcohols and (meth)acrylate monomers having a tertiary amino group, such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate, or (meth)acrylate monomers containing the tertiary amino group. A vinyl copolymer having both a tertiary amino group and a hydroxyl group in the side chain, which is obtained by copolymerizing a monomer containing a hydroxyl group 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-dialkylethylene diamino, N, N-dimethyl-1,3-7'ropylene diamino: y, N, N-? N,N-dialkyl-1,3-propylene diamino such as ethyl-1,3-7'ropylene diamino: or N,N
- N-alkylpiperazines such as dimethyl-1,6-hexamethylene diamino, N-methylbiperazine, and N-methylbiperazine; or the above-mentioned tertiary amino group-containing (meth)acrylate monomers and methylenediamino, piperazine/,
Examples include adducts with methylamino, ethylamino, butylamino, or ammonia.

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

And the above-mentioned compound (a-1) and compound (a-2)
In order to obtain the vinyl copolymer (A) which is the base resin component in the composition of the present invention, the activity in compound (a-2) is Both compounds may be mixed at a ratio such that the amount of hydrogen-containing groups is approximately 0.5 to 3 equivalents, and the mixture may be reacted in a temperature range from room temperature to approximately 120°C.

Further, as an alternative method for producing the tertiary amino group-containing vinyl copolymer (A), there is a method as disclosed in JP-A-52-76338. That is, (1) 0.2 to 30% by weight of tertiary amino group-containing acrylamide, and (2)
35-99. Esters of acrylic acid or methacrylic acid and aliphatic monohydric alcohol or mixtures thereof.
8% by weight, and (3) 0 to 0 other copolymerizable vinyl monomers.
60 parts by weight of the vinyl copolymer (A). The tertiary amino group-containing acrylic monomer used here is dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or tar.
Derivatives of acrylic acid and/or methacrylic acid such as t-7'' tylaminoethyl (meth)acrylate are preferably used, but also N-dimethylaminoethyl (meth)acrylamide, N-diethylaminoethyl (meth)acrylamide, etc. Alternatively, derivatives of (meth)acrylamide such as N-zomethylaminoglovir (meth)acrylamide can also be used.The appropriate amount of these used is within the range of 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.

Further, as the respective monomers used in (2) and (3), other vinyl monomers having copolymerizability described in the first method of the production method may be used. Other monomers not listed include hydroxy (meth)acrylates such as β-hydroxyethyl or β-hydroxyzorobyl (meth)acrylate; “FM monomer”
Or "FA monomer" [both manufactured by Daicel Chemical Co., Ltd.]
[epsilon]-caprolactone addition monomers]; methylol compounds of amide bond-containing monomers such as (meth)acrylamide or diacetone acrylamide: or 2
-Vinylpyridine and the like can also be used.

The amount of ingredients (2) and (3) used is 35% each.
Suitable ranges are from 99.8% by weight, preferably from 50 to 80% by weight, and from 0 to 60% by weight, preferably from 20 to 45% by weight.

In order to prepare the vinyl copolymer (A) from various monomers, it is possible to prepare the vinyl copolymer (A) by using a known and commonly used polymerization method as described in the first method of the production method using a known and commonly used solvent and polymerization initiator. The polymerization may be carried out by a method. However, when seeking only the effect of preventing coloring, the amount is not limited to the above range.

Thus, by each method, a vinyl copolymer (A) having at least one tertiary amino group in one molecule can be obtained.

Next, as the polyepoxy compound (B), the polyepoxy compounds disclosed in the above-mentioned JP-A-59-56423 and JP-A-59-142220 may be used.

That is, the various epoxy compounds listed above can be used as they are, except for the monoepoxy compounds.

In the case of method 1 of the production methods for vinyl copolymer (A), the blending ratio of vinyl copolymer (B) and polyepoxy compound (B) is The polyepoxy compound (B) is
The ratio is preferably such that the epoxy group contained therein is 0.5 to 2 equivalents, and when using a method, the blending of the vinyl copolymer (A) and the polyepoxy compound (B) is preferable. The ratio is such that the ratio of the basic nitrogen atom (dulam atom) in the vinyl copolymer (A) to the oxygen atom (dulam atom) of the epoxy group in the polyepoxy compound (BJ) is I: 0.5 to 3. What is necessary is just to mix|blend a polyepoxy compound (B) with.

Further, as the curing accelerator (C), the organic trivalent phosphonium salts, organic trivalent phosphines, and organic Miura bosphites used in the present invention include the following. first.

Examples of the organic trivalent phosphonium salt include triethylbenzylphosphonium chloride, tri')-n-butylallylphosphonium chloride, tri-n-butylallylphosphonium bromide, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, or A typical example is tetra-n-butylphosphonium iodite. Examples of organic trivalent phosphine include trimethylphosphine, triethylphosphine, triethylphosphine, triphenylphosphine, tri(p-methylphenyl)phosphine,
Typical examples include tri(norylphenyl)phosphine, methyldiphenylphosphine, dibutylphenylphosphine, tricyclohexylphosphine, idl, and 2-bis(diphenylphosphine)methane. Representative examples of organic trivalent phosphites include triphenyl phosphite. Each of the above-mentioned compounds may be used alone or in combination of two or more, and the amount added should be determined based on the low-temperature curability of the resulting resin composition and the effect on heat-resistant yellowing of the cured coating film. A range of 0.01 to 10% by weight of the solid content of the coalescence is sufficient.

If the amount added is less than 0.01 weight factor, the desired low-temperature curability cannot be obtained, while if it exceeds 10 layers, the pot life will be extremely short, which is not preferable. Especially, 0.0
A range of 9 to 5% is preferred.

The curable resin composition of the present invention obtained in this way may be used as a paint as it is, or may be further added with pigments, solvents, cellulose compounds such as cellulose acetate butyrate, chlorinated polyolefins,
polyisocyanate, blocked polyisocyanate,
Other synthetic resins such as polyester resins, alkyd resins or ketone resins, as well as UV absorbers such as benzotriazoles, hydroxybenzophenones or unsaturated nitrile compounds, or furthermore hy/tert phenolic compounds or hindered amino acids. Antioxidants such as type compounds or light stabilizers may also be used.

The paint obtained using the composition of the present invention can be used in the form of clear paint or enamel paint for automobile repair, woodwork, building exteriors, building materials, or various 762 Stix m products. Furthermore, it can also be used as a sealant or adhesive.

〔Example〕

Next, the present invention will be explained by reference examples, examples, and comparative examples.
This will be explained in more detail, but unless otherwise specified, all divisions and sections are based on the same criteria.

Reference Example 1 [Example of preparation of tertiary amino group-containing vinyl copolymer] 392 parts of toluene and 408 parts of inbutanol were charged into a reactor equipped with a stirring device, a thermometer, a nitrogen inlet tube, and a reflux condenser. , 900 parts of methyl methacrylate, 100 parts of dimethylaminoethyl methacrylate, 5 parts of azobisisoputiloni (ATBN), tert-butyl peroxyoctoate ( A mixture of 5 parts of TBPO) and 200 parts of toluene was added dropwise over 3 hours. After maintaining the same temperature for 2 hours, a mixture consisting of 5 parts of ATBN, 448 parts of toluene, and 37 parts of isobutanol was added dropwise over 1 hour. Next, it was kept at the same temperature for 12 hours to obtain a solution of the tertiary amino group-containing vinyl copolymer (A) with a nonvolatile content (NY) of 40 cm and a number average molecular weight (Mn) of 12,000. Ta. Hereinafter, this polymer solution will be abbreviated as polymer (A-1).

Reference Examples 2 and 3 (same as above) Same as Reference Example 1 except that the monomers shown in Table 1 were used instead of 900 parts of methyl methacrylate and 100 parts of dimethylaminoethyl methacrylate. , NY was 4 (l) to obtain solutions of tertiary amino group-containing vinyl copolymers (A-2) and (A-3).Hereinafter, these polymer solutions were mixed with polymers (A-2) and (A
-3).

Table 1 Reference Example 4 (same as above) Into a reactor similar to Reference Example 1, 300 parts of toluene and 400 parts of butyl acetate were charged, and the mixture was heated for 11 hours under a nitrogen atmosphere.
The temperature was raised to 0°C. Next, 100 parts of styrene, 400 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 130 parts of n-butyl acrylate, 30 parts of acrylic acid, 40 parts of maleic anhydride, 10 parts of AIBN, 5 parts of TBPO A mixture of 5 parts of -7'' chill peroxybenzoate (TBPB) and 300 parts of toluene was added dropwise over a period of 3 hours and then kept at the same temperature for 15 hours to continue the reaction. Vinyl copolymer (a-1) having an acid anhydride group and a xyl group with Mn of 50 and Mn of 10,000
A solution of was obtained. Hereinafter, this solution was mixed with vinyl copolymer (a-
It is abbreviated as 1-1).

Next, this vinyl copolymer (a-1-1) f 70
After the temperature was lowered to ℃, 40 parts of N,N-dimethylaminoethanol was added thereto, and the temperature was maintained at the same temperature for 5 hours.
In addition to 270 parts of butanol, NV is 4
A solution of polymer (A) containing 5% tertiary amino groups and carboxyl groups was obtained. Hereinafter, this polymer solution will be abbreviated as polymer (A-4).

Reference Example 5 (same as above) 1,000 parts of the vinyl copolymer (a-1-1) having an acid anhydride group and a carboxyl group obtained in Reference Example 4,
The temperature was raised to 90°C under a nitrogen stream, and N,N-dimethyl-1
, 3-f robylene diamino were added thereto, and the mixture was maintained at the same temperature for 6 hours to carry out a dehydration reaction. During this time,
The acid value at the beginning of the reaction was 22.7, but it decreased to 12.5 at the end of the reaction. From this, it is clear that about 90 moles of the amide bond formed was converted into an imide ring.

In addition, according to IR spectrum analysis, the absorption of the amide bond disappeared, and instead, the absorption of 1700α due to the imide ring
absorption was confirmed.

To the imide ring-containing polymer solution thus obtained, 135 parts of n-sitanol was added to obtain a solution of the polymer (A) having an NV of 45% and a Gardner color of 1 or less. Hereinafter, this polymer solution will be abbreviated as polymer (A-5).

Examples 1 to 6 and Comparative Example 1 Using each polymer solution (A) obtained in each reference example as a base resin component, a white paint with a pwc of 40 cm was prepared using the compounding composition ratio as shown in Table 2. was prepared.

Next, each paint was mixed with xylene/toluene/n-butaseal/cellosol acetate 30/40/20/
Dilute with a mixed solvent of 10 (weight ratio) until it reaches a spray viscosity, and apply slate & o! The coating was applied to a HiP-P board and then allowed to stand at room temperature and 0° C. for 7 days to cure.

Performance evaluation was performed on each of the coating films thus obtained, and the results shown in Table 3 were obtained.

〔Effect of the invention〕

The paint obtained from the composition of the present invention is sufficiently cured by drying at room temperature for several hours after application, or for 10 to 60 minutes at 40 to 100°C, and moreover, it can be cured sufficiently at temperatures of about 0 to 10°C. It has excellent curing properties at low temperatures, excellent resistance to heat yellowing when drying, and provides cured coatings with good physical properties, stain resistance, and alkali resistance.

Claims (1)

[Claims] 1. A vinyl copolymer (A) having at least one tertiary amino group in one molecule as a base resin component and a polyepoxy compound (B) as a curing agent component, respectively. In addition, as a curing accelerator component,
At least one compound (C) selected from the group consisting of organic trivalent phosphonium salts, organic trivalent phosphines, and organic trivalent phosphites is added to the vinyl copolymer (A).
A curable resin composition containing particularly excellent low-temperature curability. 2. The above vinyl copolymer (A) having at least one tertiary amino group in one molecule reacts with the carboxylic anhydride group-containing vinyl copolymer (a-1) and the carboxylic anhydride group. The curable composition according to claim 1, which is a reaction product with a compound having both a group having an active hydrogen and a tertiary amino group. 3. The above vinyl copolymer (A) having at least one tertiary amino group in one molecule is a vinyl monomer containing a tertiary amino group-containing vinyl monomer as an essential monomer component. The curable resin composition according to claim 1, which is a copolymer of a mixture.