JPH0333149A - Weather-resistant curable resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. curable at a low temp., excellent in the weathering resistance and giving an excellent coating film by compounding an epoxy resin with a polymer which is obtd. by reacting an alkyleneimine with a polymer obtd. by copolymerizing a monomer mixture contg. an ultraviolet-stable polymerizable monomer. CONSTITUTION:An epoxy resin is compounded with a polymer obtd. by reacting an alkyleneimine with carboxyl groups of a polymer which is obtd. by copolymerizing a monomer mixture comprising 0.1-10.0wt.% ultraviolet-stable polymerizable monomer, 0.1-30.0wt.% carboxylated polymerizable unsatd. monomer, and 40.0-99.8wt.% other copolymerizable unsatd. monomer (the sum of the monomers being 100wt.%). As the ultraviolet-stable polymerizable monomer, compds. of formula I and/or II (wherein R1 is H or cyano; R2 and R3 are each independently H or 1-2C alkyl; R4 is H or 1-18C alkyl; and X is imino or oxygen) are used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a curable resin composition with excellent weather resistance. More specifically, it relates to a curable resin composition that cures at low temperatures and has excellent weather resistance and is useful for applications such as paints, inks, and adhesives that provide coatings with excellent drying properties, hardness, solvent resistance, and adhesion. It is something.

(Prior Art) Conventionally, in fields where heat treatment is not suitable, such as building materials, ships, railway vehicles, aircraft, and automobile repair, resin compositions with excellent weather resistance have been desired from the viewpoint of corrosion resistance and aesthetics. To meet these demands, room-temperature-drying acrylic lacquers containing nitrocellulose, cellulose acetate butyrate, etc., and room-temperature-curing two-component urethane resin paints have been widely used.

In contrast, the present inventors have proposed
No. 1, which contains an alkyleneimine modified polymer and an epoxy compound as essential components, and whose total aromatic ring weight is 10f.
! We have proposed a curable resin composition with excellent weather resistance.

In recent years, paints using moisture-curable acrylic silicone resins, paints using fluororesin-incyanate resins, etc. have come into use in order to further improve the level of weather resistance.

(Problems to be Solved by the Invention) The above-mentioned acrylic lacquer is low-priced and easy to use, and the two-component urethane resin paint that cures at room temperature has advantages due to the crosslinking reaction between polyol and polyisocyanate compound. Although it has excellent weather resistance, it has the following drawbacks.

In other words, in order to obtain the desired performance, acrylic lacquers have to increase the molecular weight of the polymer and raise the glass transition temperature (
It is necessary to increase the Tg), but for this purpose it is necessary to dilute with a large amount of organic solvent. This does not meet the recent demand for high-solid paints from the viewpoint of resource conservation, environmental pollution, etc. Furthermore, two-component urethane resin paints that cure at room temperature have problems in terms of toxicity and cost due to the polymericyanate compound used.

The present inventors have solved the problems of the above-mentioned acrylic lacquers and room-temperature curing three-component urethane resin paints by using alkyleneimine-modified polymers and epoxy compounds as essential components, and by reducing the weight of fully aromatic rings. We have proposed a curable resin composition with excellent weather resistance that contains 10% indigo or less. (Unexamined Japanese Patent Publication No. 63
-56549) However, although the above method is effective, in recent years,
Development research has been carried out to develop moisture-curing acrylic silicone paint,
Paints with even better weather resistance, such as fluororesin-isocyanate curing paints, have been developed, but moisture-curing acrylic silicone paints have problems in terms of paint storage management and price. Fluororesin-isocyanate-cured coatings are more expensive, and the problem of toxicity remains unsolved because they are inocyanate-cured.

<Means for Solving the Problems> The present invention is the result of intensive studies on the above-mentioned problems based on the inventor's earlier application, JP-A-63-56549.

That is, the present invention General formula (I> and or general formula (II) 1 RI X-C-C=CH 4 1 x-C C=CH CC=CH+ 1 OR2R.

(However, in Formulas (I) and CI), R1 is a hydrogen atom or a cyano group, R2 and R3 are each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R4 is a hydrogen atom or a C1-C2 alkyl group. ~18 alkyl groups, X represents an imino group or an oxygen atom) Polymerizable UV-stable monomer (a) 0°1 to 10.0% by weight, polymerizable unsaturated having a carboxyl group Monomer (b) 0.1 to 30.0% by weight
, other copolymerizable polymerizable unsaturated monomers (c) 4O~
Polymerizable monomer component consisting of 99.8% by weight (however, (a
), (b) and (c) components total 100% by weight. ) and a polymer (A) obtained by reacting the carboxyl group of the polymer obtained by copolymerizing with an alkylene imine (d), and a polymer (A) and The present invention relates to a curable fat composition with excellent weather resistance, which is patented in that the weight of aromatic rings contained in the epoxy compound (B) is 101 fL% or less based on the resin content.

More specifically, the monomer (a) used in the production of the polymer (A) of the present invention includes -a formula (I) and/or -numerical formula (If) R3 C-C=CH R1 1 1 X -C-C=C)1 C-C=CH+ 1 2 3 (However, in formulas (I) and (n), R1 is a hydrogen atom or a cyano group, and R and R3 are each independently a hydrogen atom or a carbon A polymerizable ultraviolet stable monomer (with a> Yes, 0.1 to um%, preferably
0.05 to 4.0% by weight is used. These polymerizable UV-stable monomers are commercially available, for example, from Adeka Argus under the trade names MARK LA-87 and MARK LA-82.

Monomer (b) used in the production of the polymer (A) of the present invention
unsaturated monocarboxylic acids such as (meth)acrylic acid, cinnamic acid and crotonic acid; maleic acid,
Examples include unsaturated dicarboxylic acids such as itaconic acid and fumaric acid or their monoesters, and one type or a mixture of two or more types selected from these groups can be used.

Monomer (c) used in the production of the polymer (A) of the present invention
is not particularly limited as long as it can be copolymerized with the monomers (a and b), such as (meth)acrylamide, N-methylol (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 2- Hydroxypropyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,
n-Butyl (meth) acrylate, isobutyl (meth)
Acrylate, t-butyl (meth)acrylate, 2-
Ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, (meth)acrolein, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (
Examples include meth)acrylates, and one type or a mixture of two or more types selected from these groups can be used.

The precursor polymer for obtaining the polymer (A) of the present invention can be obtained by copolymerizing the above-mentioned monomers (a), (b), and (c) according to known procedures. Polymerization methods such as polymerization method and suspension polymerization method can be employed, but in the present invention, it is most preferable to manufacture by solution polymerization method.

When the polymer is produced by a polymerization method other than solution polymerization, a step of dissolving the polymer in an organic solvent that can dissolve the polymer is required.

When employing the solution polymerization method, solvents that can be used include, for example, toluene, xylene, and other high-boiling aromatic solvents; ester solvents such as ethyl acetate, butyl acetate, and cellosolve acetate; methyl alcohol, ethyl alcohol, Alcohol solvents such as n-butyl alcohol and isobutyl alcohol: Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned, and one type or a mixture of two or more types selected from these groups can be used. .

In addition, usable polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, and di-tetra
Examples include rt-butyl peroxide.

The polymerization temperature of monomers (a) and (b) and (c) ranges from room temperature to 200°C, preferably from 0 to 120°C.

The polymer (A) is an aminated product obtained by reacting the carboxyl group contained in the above polymer with an alkylene imine (d).

The amination reaction is achieved, for example, by mixing and stirring the polymer and alkylene imine at a temperature of 40 to 150''C5, preferably 50 to 100C.

As the alkylene imine (d), for example, ethyleneimine, propylene imine, butylene imine, etc. can be used. Also, N-(2-aminoethyl)aziridine, N
N-(aminoalkyl)-substituted alkyleneimines such as -(3-aminopropyl)alidine and N-(2-aminopropyl)propyleneimine can be used as well.

The epoxy compound (B) used in the present invention is a compound containing at least two epoxy groups in the molecule, and examples of the epoxy compound (B) include bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether. Examples include copolymers containing ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and glycidyl (meth)acrylate components. Species or mixtures of two or more species can be used. There is no particular restriction on the amount of the epoxy compound (B) used, but in order to have excellent weather resistance and to fully exhibit the required performance such as drying property, hardness, and solvent resistance, the amount of the polymer (A ) and is preferably 0.5 to 3.0 equivalents, more preferably 7 to 2.0 equivalents of Q.

In carrying out the present invention, it is essential that the weight of the aromatic ring contained in the polymer (A) and the resin content of the epoxy compound (B) is 10% by weight or less. If the weight of the aromatic ring exceeds 10% by weight, the weather resistance will be poor.

The curable resin composition of the present invention can be used as it is in paints, inks, etc.
It is used for applications such as adhesives, but if necessary, known fillers, leveling agents, plasticizers, stabilizers, dyes, toners,
Various additives such as pigments and antistatic agents may be included as appropriate.

(Function) The curable resin composition of the present invention has the function of providing a coating film with excellent weather resistance.

Furthermore, the paint using the curable resin composition of the present invention as a vehicle component can be applied to metals, inorganic materials, plastics, wood products, etc. using coating methods such as spray painting, roll painting, and spacing. , has excellent weather resistance, and has the ability to form a coating film with excellent drying properties, hardness, solvent resistance, and adhesion.

Furthermore, by using the curable resin composition of the present invention, there is no need to worry about toxicity due to isocyanates as seen in other paints, and paints with the above characteristics can be easily produced, making it suitable for use in structures and automobile repair. It has an action that can be used for a wide range of purposes, such as woodworking and furniture painting.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the following Examples.

Note that parts and % in the examples indicate parts by weight and % by weight, respectively, unless otherwise specified.

Reference Example 1 50 parts of propylene glycol monomethyl ether was charged into a four-bottle flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas introduction tube, and the temperature was raised to 80'C. rMARK LA while blowing nitrogen gas into it.
-87 (product of Adeka Argus), 4 parts of methacrylic acid, 20 parts of methyl methacrylate, 20 parts of butyl methacrylate, 5 parts of butyl acrylate, and 0.5 part of azobisisobutyronitrile were heated for 2 hours. Then, 5 parts of ethyleneimine was added dropwise to the above flask over 10 minutes to obtain a solution of the mixture containing carboxyl groups. One hour after finishing the 0 drop, the temperature was raised to 75°C, kept at the same temperature for 5 hours, and then
A distillation device was set in a double-bottomed flask, heated under reduced pressure, and the same amount of propylene glycol monomethyl ether was replenished as the amount that flowed out, while unreacted ethyleneimine was flowed out of the system to completely remove the remaining ethyleneimine. . f
After i, the nonvolatile content was adjusted to 50% to obtain a solution of polymer (1).

Reference Example 2 A solution of polymer (2) was obtained by repeating the same operations as in Reference Example 1, except that the composition amount of the polymerizable monomer was as shown in Table 1. Ta.

Reference Example 3 In Reference Example 1, a solution of polymer (3) was obtained by repeating the same operation as in Reference PAl, except that the amount of the polymerizable monomer composition was as shown in Table 1. .

Comparative Reference Example 1 In Reference Example 1, the same operation as in Reference Example 1 was repeated except that the amount of M of the polymerizable monomer was changed as shown in Table 1 to prepare Comparative Polymer (I). A solution was obtained.

Comparative Reference Example 2 A solution of comparative polymer (n) was prepared by repeating the same operations as in Reference Example 1, except that the amount of the polymerizable monomer composition was as shown in Table 1. I got it.

Table 1 Examples 1 to 6 Comparative Examples 1 to 5 Polymer (1) obtained in Reference Examples 1 to 3 and Comparative Reference Example 1.2
~(3> and comparative polymers (I) and (II) 1
20 parts each and titanium oxide (DuPont product R-90)
0) 40 parts in a sand mill container, 2000r
pm for 30 minutes to obtain a polymer pigment dispersion having a nonvolatile bone pigment weight concentration of 40%. An epoxy compound was added to this pigment dispersion in an amount such that the epoxy group was equivalent to the amino group contained in the polymer in the dispersion, and as shown in Table 2, polymers (1) to ( Example coating 1 consisting of 3) and an epoxy compound! -1<1) to (6), and comparative coatings (1) to (4) consisting of polymer (3), comparative polymers (I) and (n), and an epoxy compound were obtained.

Furthermore, a commercially available acrylic urethane white paint was prepared as a comparative paint (5).

These paints were spray applied to a zinc phosphate-treated steel plate to a dry film thickness of 40 μm, and then dried (for one week at room temperature) to obtain various test paint films. The results of various tests on these coatings are shown in Table 3.

[Method for testing the performance of coating films and their evaluation criteria] (1) Drying property: Evaluated by touch after drying at room temperature for 1 hour.

◎・・・・・・・・・No change O・・・・・・・・・Slight marks Δ・・・・・・
・・・・・・Leaves marks×・・・・・・・・・ Strong adhesiveness (2) Pencil hardness: The scratch hardness of the paint film was examined using a Mitsubishi uni with a weight of 250.

(3) Solvent resistance: The state of the coating film was observed in a spot test using urethane thinner.

◎・・・・・・・・・No change O・・・・・・・・・Slightly softened Δ・・・・・・
・・・・・・・・・Softened×・・・・・・・・・・・・The paint film melted (4) Weather resistance: Gloss and color difference of the paint film after 3000 hours of irradiation with a sunshine-type laser meter , adhesion and appearance were observed.

(1> (2) (3) Specular reflectance was measured at a gloss level of 60 degrees.

Color difference: Color difference ΔE was measured using a color machine.

Adhesion: The remaining coating film was examined by peeling off with 1rNr cellophane tape.

◎・・・・・・・・・100/Zo.

○・−・・−・・−100/Zoo ~95/Zo.

Δ-・---95/100~90/100X・・
...90/100> (Effect of the invention) The curable resin composition of the present invention has excellent weather resistance, and has excellent drying properties, hardness, solvent resistance, and adhesion. T! l!
Forms a film. Furthermore, by using the curable resin composition of the present invention, there is no need to worry about the toxicity caused by incyanate, which is found in urethane-based paints, and there is no need to worry about the toxicity caused by incyanate, which is found in urethane-based paints, and the high cost of acrylic silicone-based paints and fluorine-based paints. Since the paint having the above-mentioned characteristics can be easily produced, it has the effect of being usable in a wide range of applications such as structures, automobile repair, and woodworking such as furniture painting.

Claims (3)

[Claims] (1) Polymerizable UV-stable monomer (a) 0.1-10.
0% by weight, carboxyl group-containing polymerizable unsaturated monomer (b) 0.1 to 30.0% by weight, other copolymerizable polymerizable unsaturated monomers (c) 40 to 99.8% by weight (However, the total of components (a), (b) and (c) is 100% by weight.) The carboxyl group of the polymer obtained by copolymerizing the polymerizable monomer component consisting of ) and a curable resin composition with excellent weather resistance, characterized in that the epoxy compound (B) is an essential component in the molecule. (2) The curable resin composition according to claim (1), wherein the weight of the aromatic ring contained relative to the resin content of the polymer (A) and the epoxy compound (B) is 10% by weight or less. (3) Polymerizable UV-stable monomer (a) has general formula (I) and/or general formula (II) ▲Mathematical formula, chemical formula, table, etc.▼...(I) ▲Mathematical formula, chemical formula, There are tables, etc.▼...(II) (However, in general formulas (I) and (II), R_1 is a hydrogen atom or a cyano group, and R_2 and R_3 are each independently a hydrogen atom or a carbon number of 1 to 2. 2. The curable resin composition according to claim 1, wherein a compound represented by an alkyl group, R_4 is a hydrogen atom is an alkyl group having 1 to 18 carbon atoms, and X is an imino group or an oxygen atom is used.