JPH0253880A - Resin composition for coating excellent in low-temperature curability - Google Patents

Abstract

PURPOSE:To obtain a composition, containing a specific carbonate group- containing copolymer, polyamine compound and specified curing assistant as essential components, excellent in low-temperature curability and compatibility with a long pot life and capable of providing excellent appearance with good transparency. CONSTITUTION:The objective composition containing (B) a polyamine compound at 0.5-2 equiv. ratio of carbonate groups/primary amino groups and (C) 0.0001-20wt.% [based the component (A)] at least one curing assistant consisting of the group ot phosphorus and nitrogen-containing compounds in (A) a carbonate group-containing copolymer prepared by copolymerizing (i) 0.2-90wt.% polymerizable monomer expressed by the formula (R is H or methyl; n is 1-4) with (ii) 0.01-30wt.% carboxyl group-containing monomer and (iii) other copolymerizable monoethylenically unsaturated monomer in 100wt.% total amount of the monomers as essential components.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new and useful resin composition for coatings,
More specifically, a specific carnate group-containing copolymer,
A specific carnate group-containing copolymer that contains a polyamine compound and a specific curing aid as essential components, and has particularly excellent low-temperature curability and compatibility with the polyamine compound, as well as a long pot life. Relating to a resin composition for paint using.

[Conventional technology]

In conventional two-component urethane curable acrylic resin compositions, polyisocyanate compounds have been used as crosslinking agents, but the toxicity of free isocyanate monomers contained in such polyisocyanate compounds has become a problem. There is.

Under these circumstances, inocyanate-free two-component urethane curable resin compositions have been developed, which are crosslinked via urethane bonds by combining a polymer having a carbeneto group in the side chain and a polyamine compound. Are known.

However, carbonate group-containing polymers used in conventional isocyanate-free curable resins for paints have extremely poor compatibility with polyamine compounds as curing agents, resulting in turbidity and coating when mixed. Even if a film is formed, the problem is that the clarity is poor.

Furthermore, due to such poor compatibility, the reactivity between the carbonate group and the polyamine compound is also insufficient, resulting in poor physical properties of the cured coating film.

[Problem to be solved by the invention]

However, in view of the various shortcomings in the prior art as described above, the present inventors have conducted intensive studies to develop a new carbonate group-containing copolymer that has good compatibility with polyamine compounds. , by using specific amounts of a carbonate group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer as described below as essential monomer components of such a carbonate group-containing copolymer. First, a carbonate group-containing copolymer having good compatibility with a polyamine compound can be obtained, and furthermore, a composition comprising the carbonate group-containing copolymer and a thiamine compound may further contain a curing aid. The present invention was completed by discovering that a resin composition for coatings with particularly excellent low-temperature curability can be obtained by adding and blending a phosphorus compound and/or a nitrogen-containing compound. Ta.

[Means to solve the problem]

That is, in the present invention, as an essential component, a polymerizable monomer (a-'1) represented by the general formula C is hereinafter abbreviated as a carzenate group-containing polymerizable monomer (a-1). ]00.2～
90 weight and carboxyl group-containing polymerizable monomer (a-2
) and a monoethylenically unsaturated monomer (a-3) copolymerizable with the above polymerizable monomers (a-1) and (a-2). , a carnate group-containing copolymer obtained by copolymerizing so that the total of all monomers is 100% by weight, and a polyamine compound (B)
and 0.0% for the carbonate group-containing copolymer (4).
0001 to 20% by weight of phosphorus-containing compounds (e
-L) and at least one curing aid (C) selected from the group consisting of a nitrogen-containing compound (c-2), and has particularly excellent low-temperature curability. It is something to do.

Here, first, typical examples of the carzenate group-containing polymerizable monomer (a-1) include 2゜3-carbonate propyl (meth)acrylate, 3.4-carnate butyl (meth)acrylate, 4.5-carzenate pentyl (meth)acrylate, 5,6-car?
Examples include natehexyl (meth)acrylate and 6,7-carnatehexyl (meth)acrylate.

The appropriate amount of these to be used is 0.2 to 90% by weight, preferably 2 to 45% by weight.

Next, typical examples of the carboxyl group-containing polymerizable monomer (a-2) include (meth)acrylic acid,
Hydroxyl group-containing vinyl monomers such as crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid monoalkyl ester, maleic acid monoalkyl ester or hafumaric acid monoalkyl ester, or β-hydroxyethyl (meth)acrylate and anhydride. These include adducts with acid anhydrides such as succinic acid or trimellitic anhydride. And such carboxyl group-containing polymerizable monomer (a-2)
The amount of polyamine compound (B
) and the viscosity when mixed with the amine (B), a suitable range is 0.01 to 30% by weight, preferably 0.1 to 10% by weight.

In addition, the copolymerizable monoethylenically unsaturated monomer (a-3) can be copolymerized with the polymerizable monomers (a-1) and (a-2), respectively, as listed above. Any of them can be used, but the most representative ones are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. ) Butyl acrylate, (meth)
2-ethylhexyl acrylate, lauryl (meth)acrylate; styrene, α-methylstyrene, p-te
rt-butylstyrene, dimethylstyrene, vinyltoluene; (meth)acrylamide, N-methylol (meth)acrylamide, butoxy (meth)acrylamide;
2-hydroxyethyl (meth)acrylate, 2-hydroxyprogyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (
meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate, polyethylene glycol mono(meth)acrylate, polyzolo 2-hydroxypropyl mono(meth)acrylate (meth)acrylate, "Plaxel FM or FA monomer" [
Caprolactone addition monomer from Daicel Chemical Co., Ltd.]
; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; further (meth)acrylonitrile, vinyl acetate, diethyl maleate, dibutyl maleate, fumaric acid, sibutyl, diethyl itaconate/I/or dibutyl itaconate, etc. It is.

In order to prepare the above-mentioned nate group-containing copolymer (4) using the various monomers listed above, it is possible to use any known and commonly used method. The simplest method is the polymerization method.

In this case, aromatic hydrocarbon solvents such as toluene or xylene; (cyclo)aliphatic hydrocarbon solvents such as pentane, hexane or cyclohexane; such as ethyl acetate, n-butyl acetate or ethylene glycol monomethyl ether acetate are used. Ester solvent; acetone,
Ketone solvents such as methyl ethyl ketone, methyl imbutyl ketone or cyclohexanone; solvents such as alcohol solvents such as isopro-, n-butanol or isobutanol, and known and commonly used polymerizations such as azo-based and peroxide-based solvents. Polymerization may be carried out in a conventional manner using an initiator.

In addition, during polymerization, tert-dodecyl mercaptan,
Polymerization can also be carried out using mercaptans such as lauryl mercaptan, thioglycolic acid alkyl ester or β-mercaptopropionic acid, and molecular weight regulators such as α-methylstyrene dimer.

Next, the polyamine compound (B) component constituting the coating resin composition of the present invention will be explained.

The paste resin component, which is the carnate group-containing copolymer (4) prepared as described above, is mixed with the polyamine compound (B), which is the curing agent component.

As the polyamine compound (B), at least one kind is appropriately selected from known and commonly used polyamines such as aliphatic polyamines, aromatic polyamines, composite polyamines, modified aliphatic polyamines, and heterocyclic polyamines.

Among them, ethylenediamine, 1,2-diaminopropane,
1.3--/aminopronoyan, 1,4-diaminobutane, 1,5-diaminobutane, 1,6. -diaminohexane, ■, 7-diaminehebutane, 1°8-cyamine octane, 1,9-diaminonane, ■, 10-noaminodecane, 1,2-noaminocyclohexane, 1,4-
Bis(3-aminopropyl)bibebutane, 3,9-bis(3-aminopropyl)-2゜4,8.10-tetraoxas, [5,5]undecane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Pentaethylene hexapane, N,N'-bis(2-
aminomethyl)ethylenediamine, N,N'-bis(
2-aminoethyl)-ethylenediamine, N,N'-bis(3-aminopropyl)ethylene cyamine, N,N
'-His(2-aminomethyl)-1,3-zolopanediamine, N,N'-bis(2-aminoethyl)-1,3
-pronocunnnoamine, N,v-bis(3-aminozorobyl) -L3-zolopanediamine, N,N-bis(2
-aminomethyl) -1,4-butanediamine, N,N
'-bis(2-aminoethyl)-1,4-butanediamine, N,N'-bis(3-aminozolopyl)-1
, 4-butanediamine, bis(4-aminocyclohexyl)methane or 1,3-bis(aminomethyl)cyclohexane or [Jeffamine D-230 or D-400J [Mikata Texaco Chemical Co., Ltd. product]
or trisaminoethylamine or 4-aminomethyl-1,8-diaminooctane or "Jeffamine T-403J (
Including trifunctional primary amine compounds such as
Acid group-containing acrylic resin-zolopyreneimine adduct, polyepoxy compound-polyamine adduct,
Alternatively, they are adducts of oligoester (meth)acrylate and various polyamine compounds as listed above.

Of course, polyamide resins can also be used, and any known and commonly used S9 lyamide resins can be used, but the representative one is ``laccamite'' [Inu Nippon Ink Chemical Industry Co., Ltd.
Examples include polyamide amine resins such as "Tomide" (product of Fuji Kasei Kogyo Co., Ltd.) and "Sanmide" (product of Sanwa Kagaku Kogyo Co., Ltd.).

The blending ratio of the polyamine compound (B) and the above-mentioned carnate group-containing copolymer (4) is such that the equivalent ratio of carbonate group/primary amine group is 05 to 2, preferably 0.8 to 1. It is appropriate that it is within the range of ゜2,
Gives good coating performance.

In this case, if it exceeds 2, curing will inevitably be insufficient and the coating performance will deteriorate, while if it is less than 0.5, the carnate group-containing copolymer (A) Both are unfavorable because the compatibility with the polyamine compound (B) becomes poor and the mixture thereof tends to become cloudy.

Further, the above-mentioned phosphorus-containing compound (e-1) is another essential component constituting the coating resin composition of the present invention.
The hardening aid (C), which is a nitrogen-containing compound (e-2), will be explained below.

First of all, typical phosphorus-containing compounds (c-1) include triethylphosphine, triethylphosphine, tributylphosphine, tripentylphosphine, trihexylphosphine, trihebutylphosphine, trioctylphosphine, and trinonyl. phosphine,
Tridecylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dipropylphenylphosphine, dibutylphenylphosphine, cyclohexylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, propyldiphenylphosphine, butyldiphenylphosphine, cyclohexyldiphenyl Phosphine, bis(diphenylphosphine)methane, 1,2-bis(,diphenylphosphino)ethane, 1,2-bis(
diphenylphosphino)ethylene, 1,4-bis(diphenylphosphono)butane, triphenylphosphine,
tri〇-)lylphosphine, tri-m-)lylphosphine, tri-p-)lylphosphine, diphenyl(0-
These include three-coordinated organic phosphorus compounds such as tolyl)phosphine, diphenyl(m-tolyl)phosphine, and diphenyl(p-)lyl)phosphine, as well as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, and tetrabutylphosphonium bromide. 1hydroxide, methyltriphenyl bromide, methyltriphenyl chloride, methyltriphenyl iodide, bromomethyltriphenylphosphonium bromide,
Chloromethyltriphenylphosphonium chloride, vinyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, 2-hydroxyethyl bromide, 2-hydroxyethyl chloride, methoxymethyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, pro/4' sol Triphenylphosphonium bromide, propadyltriphenylphosphonium chloride, calmethoxymethyltriphenylphosphonium bromide, caldemethoxymethyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, cyclozologyltriphenylphosphonium bromide, cyclozologyl triphenyl chloride, acetonyltriphenylphosphonium bromide, acetonyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, brorotriphenylphosphonium chloride, (carbetoxymethyl)triphenylphosphonium bromide, (carbetoxymethyl)triphenylphosphonium chloride, 1.3-・dioxolane-2-
yl-methyltriphenylphosphonium bromide, 1
．． 3-dioxolan-2-yl-methyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium chloride r1 (2-trimethylaminoethyl)triphenylphosphonium bromide, (2-dimethylaminoethyl)
Triphenylphosphonium chloride, (4-carboxybutyl)triphenylphosphonium bromide, (4
-carboxybutyl)triphenylphosphonium chloride, (2-(1,3-dioxan-2-yl)-ethyltriphenylphosphonium bromide, [2-(1,
3-Dioxan-2-yl)-ethyl trinoenylphosphonium chloride)', 2-hydroxybenzyltriphenylphosphonium bromide, 2-hydroxybenzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride , phenacyltriphenylphosphonium bromide, phenacyltriphenylphosphonium chloride, (4-ethoxybenzyl)
Triphenylphosphonium bromide, (4-ethoxybenzyl)triphenylphosphonium chloride, p-
Xylylene bis(triphenylphosphonium bromide>-th) is a four-coordinated organic phosphorus compound such as p-xylylene bis(triphenylphosphonium chloride).

Next, typical examples of the nitrogen-containing compound (c-2) include pyridine/, 2-hydroxypyridine,
1,5-diazabicyclo[3,4,0]nonene-5,1
, 8-diazabicyclo[5,4,O]laurensen-7 or 1,4-diazabicyclo(2,2,2]octane.

The amount of the curing aid (C) which is a phosphorus-containing compound and/or a nitrogen-containing compound that has been submerged is as follows: A suitable range is from 0.0001 to 20% by weight, preferably from o, o oi to 10% by weight, based on the nate group-containing copolymer (4).

If it is less than 0.0001, the effect as a curing aid cannot be expected. On the other hand, if it exceeds 20% by weight, the coating film performance such as yellowing and chemical resistance will inevitably deteriorate. Both are undesirable because they last for a long time.

The coating resin composition of the present invention thus obtained has -
It can be used as a clear paint, or by mixing pigments, it can be used as a enamel paint.

Furthermore, the composition of the present invention may further contain various conventional additives such as leveling agents, ultraviolet absorbers, pigment dispersants, etc., as required, and may also be used to dilute ketone solvents. By using it as a thinner, it is possible to extend the pot life, improve the appearance of the coating film, and also add other resin components such as well-known and commonly used cellulose compounds, plasticizers, and even polyester resins. can also be used together.

The thus obtained coating resin composition of the present invention with excellent low-temperature curability is extremely useful for coating a wide variety of materials or processed products such as Zolastics, metals, wood, building materials, and inorganic base materials. .

In addition, as a coating method, commonly used methods such as brush coating, spray coating, or roll coating can be adopted, and as a curing method, a wide range of methods can be used, from drying at room temperature to drying with heat.
The copolymer component (A
) and crosslinking agent component (B) can be designed to suit the combination.

〔Example〕

Next, the present invention will be explained in detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, unless otherwise specified, all terms, parts, and parts are based on weight.

Reference Example 1 [Example of Preparation of Carnate Group-Containing Copolymer (4)] 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 in a nitrogen atmosphere. The temperature was raised to 110°C, and then the styrene was heated to 300°C.
parts, 200 parts of methyl methacrylate, 95 parts of n-butyl acrylate, 5 parts of acrylic acid, 400 parts of 2,3-carzenatopropyl methacrylate, 10 parts of azobisisobutyronide IJ/l/(ATBN), tert- 10 parts of butyl peroxyoctoate (TBPO), t
art-butyl peroxybenzoate (TBPB)
A mixture consisting of 5 parts of and 300 parts of toluene was added dropwise over 3 hours, and the reaction was then maintained at the same temperature for 15 hours to allow the reaction to proceed. This results in a non-volatile content (NV) of 50
．． A solution of a vinyl copolymer having carbonate groups with a concentration of 2% and a number average molecular weight (diameter) of 13,700 was obtained. Hereinafter, this will be abbreviated as vinyl copolymer (A-1).

Reference Examples 2 to 4 (same as above) Except for using a monomer mixture as shown in Table 1,
The same operation as in Reference Example 1 was repeated to obtain various vinyl copolymer solutions (A-2) to (A-4).

Reference example 5 (preparation example of vinyl copolymer for comparison) 1st
A control vinyl copolymer solution was obtained in the same manner as in Reference Example 1, except that a monomer mixture as shown in the table was used. Hereinafter, this will be referred to as vinyl copolymer (A'-1
).

Properties of each resin solution (non-volatile content, viscosity and M
n) are summarized in Table 1.

Examples 1 to 5 and Comparative Examples 1 to 9 Each vinyl copolymer solution obtained in each reference example was used as a paste resin component, and a clear paint was prepared at the compounding ratio shown in Table 2 (1). I got it.

However, the abbreviations for each solvent in the column of diluting solvent in the same table are as follows.

MEK...methyl ethyl ketone, n-BuOH
... n-Butanol Each paint was then diluted to spray viscosity using a diluting solvent. In addition to evaluating the storage stability of each diluted paint, we also evaluated the low-temperature curability by measuring the dull fraction of each dry-cured film obtained from each diluted paint over time. The results of both performances are summarized in the same table.

Subsequently, each of the above-mentioned diluted paints was spray-coated on a glass plate and a polypropylene plate, respectively, and then dried and cured at room temperature (25°C) for 7 days.

Performance evaluation was performed on each cured coating film thus obtained, and the results shown in Table 2 (2) were obtained.

/ / As is clear from the results in Table 2 (2), the carbonate group-containing copolymer used in the present invention is a curing agent. 3
9 It is known that it has good compatibility with lyamine compounds and provides an excellent cured product. In particular, it is known that the composition of the present invention not only has excellent low-temperature curability, but also provides a coating film with good transparency and excellent appearance.

〔Effect of the invention〕

The coating resin composition of the present invention has a carbonate group-containing polymerizable monomer and a carbonate group-containing polymerizable monomer, which are used as base resin components, respectively. This favorable result is due to the fact that the carbonate group-containing copolymer resin itself, prepared with a xyl group-containing polymerizable monomer as an essential copolymerization component, exhibits extremely good compatibility with the polyamine compound as a curing agent. Due to their excellent compatibility, they can provide excellent cured products.

In the present invention, since the composition itself consisting of a carbonate group-containing copolymer resin and a polyamine curing agent has excellent low-temperature curability, it can be applied to various substrates with excellent physical properties by such low-temperature curing. A composition that not only can form a cured film but also contains a curing aid exhibits particularly excellent low-temperature curability.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] However, R in the formula represents a hydrogen atom or a methyl group, and n is an integer from 1 to 4. shall be. 0.2 to 90% by weight of the polymerizable monomer (a-1) represented by
．． 01 to 30% by weight and another monoethylenically unsaturated monomer (a-3) copolymerizable with the polymerizable monomers (a-1) and (a-2), based on the total monomer content. A carbonate group-containing copolymer (A) obtained by copolymerizing so that the total amount of the carbonate group-containing copolymer (A) is 100% by weight, and a polyamine compound (B). 0001 to 20% by weight of phosphorus-containing compound (c-1) and nitrogen-containing compound (c-
2) A resin composition for coatings with excellent low temperature curability, which comprises as an essential component at least one curing aid (C) selected from the group consisting of: