JPS6327522A - Curable resin composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting essentially of a specific polymer and compound having plural epoxy groups in the molecule, having improved preservation stability and low-temperature curability and suitable for coating materials, etc., capable of giving films having excellent drying properties, weather resistance, etc. CONSTITUTION:A composition consisting essentially of (I) a polymer obtained by partially neutralizing carboxyl groups in a polymer prepared by copolymerizing (A) 1-20wt% carboxyl group-containing unsaturated monomer, e.g. (meth)acrylic acid, etc., with (B) 80-99wt% another polymerizable unsaturated monomer, e.g. (meth)acrylamide, etc., [provided that the total of the components (A) and (B) is 100wt%] with a basic compound, e.g. triethylamine, etc., and reacting the residual carboxyl groups with an alkyleneimine, e.g. ethyleneimine, etc., and (II) a compound containing at least 2 epoxy groups in the molecule, preferably ethylene glycol diglycidyl ether, etc. USE:Inks, adhesives, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable resin composition. More specifically, it is suitable for use in paints, inks, adhesives, etc. that have good storage stability and cure at low temperatures to provide coatings with excellent drying properties, hardness, weather resistance, solvent resistance, adhesion, etc. The present invention relates to useful curable resin compositions.

(Prior art and problems to be solved by the invention) Conventionally, in fields where heat treatment is not required, such as plastics, concrete, building materials, and soot replenishment for automobiles, nitrocellulose, cellulose acetate butyrate, etc. have been added. Room-temperature-drying acrylic lacquers and room-temperature-curing two-component urethane resin paints are widely used. The acrylic lacquer on the front fabric is low in price and easy to use, while the latter two-component urethane resin paint has excellent coating performance due to the crosslinking reaction between polyol and polyisocyanate compound. However, it does have the drawbacks mentioned above.

In other words, acrylic lacquer has the desired performance of 1. In order to do this, it is necessary to increase the number of polymer molecules (1) or to increase the glass transition temperature (Tg), which requires dilution with a multi-ω 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 have problems in terms of toxicity and cost due to the polyisocyanate compound used.

Although various research and development efforts have been made to develop new curing systems to solve these problems, the current state of the art is that a paint with performance that can replace conventional technology has not yet been obtained.

(Means and effects for solving the problem) As a result of extensive research, the present inventors have discovered a polymer containing two specific types of functional groups and a compound containing at least two epoxy groups in the molecule. It has been found that a composition containing as an essential component does not have any of the above-mentioned problems and can be cured extremely easily at room temperature. Furthermore, a paint comprising the composition,
We have completed the present invention by discovering that the coating film has excellent drying properties, hardness, weather resistance, solvent resistance, and adhesion, as well as excellent workability.

That is, the present invention provides unsaturated m containing a carboxyl group.
Monomer (a) (hereinafter referred to as monomer (a)). )1~20i1
iffi% and other polymerizable unsaturated monomers (b) (
Hereinafter, it will be referred to as monomer (b). ) 80 to 99% by weight (however, (a) + (b) is 100% by weight), and some of the carboxyl groups of the polymer obtained by copolymerizing the carboxyl groups with a basic compound (
C), and the remaining carboxyl group is reacted with fullkyleneimine (DJ) to form a compound (I), and a compound containing at least two epoxy groups in the molecule (■) (
Hereinafter, it will be referred to as epoxy compound <II). ) The present invention relates to a curable resin composition comprising:

Monomers (a) used in the production of polymer (I) include, for example, unsaturated monocarboxylic acids such as (meth)acrylic acid, Cincin M 13 and crotonic acid; maleic acid, itaconic acid and fumaric acid; unsaturated dicarboxylic acids or monoesters thereof, and one type or a mixture of two or more types selected from these groups can be used. The monomer (a) is a polyepoxy compound (III
) acts as a functional group when reacting with alkyleneimine (D) and becomes a reactive group when reacting with alkylene imine (D) to impart an amino group to polymer (I), and has a concentration of 1 to 20% by weight. Use with. If the amount of monomer (a) used is less than 1% by weight, it will not be a substantially effective amount when reacting with the epoxy compound (If) or alkyleneimine (including).
On the other hand, if it is used in an amount exceeding 20% by weight, it is not preferable because the water resistance and storage stability of the curable resin composition deteriorate.

The monomer (b) used in the production of the polymer (1) is not particularly limited as long as it can be copolymerized with the monomer (a), such as (meth)acrylamide, N-methylol (meth), etc. ) 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 (meth)acrylate, etc. One type or a mixture of two or more types selected from these groups can be used.

The precursor compound for polymer (I) can be obtained by copolymerizing the above monomers (a) and (b) according to known procedures. For example, solution polymerization method, bulk polymerization method, suspension polymerization method, etc. Polymerization methods such as turbidity polymerization can be employed, but in the present invention, it is most preferable to produce by solution polymerization.If the polymer is produced by a polymerization method other than solution polymerization, A step of dissolving into a soluble nFB agent is required.

Solvents that can be used when using the solution polymerization method include:
For example, toluene, xylene and other high boiling aromatic solvents; ester solvents such as ethyl acetate, butyl acetate and cellosolve acetate; alcohol solvents such as methyl alcohol, ethyl alcohol, n-butyl alcohol and isobutyl alcohol; methyl ethyl ketone and ketone solvents such as methyl isobutyl ketone, and one or two selected from these solvents.
Mixtures of more than one species can be used.

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

Polymerization temperature is room temperature to 200°C, preferably 40 to 120°C
is within the range of

The small polymer (I) is obtained by partially neutralizing the carboxyl groups contained in the above polymer with an FA-based compound (C), and adding m or more alkylene (C) to the remaining carboxyl group. A compound with stronger basicity than alkyleneimine (#) is preferable, and for example, a tertiary amine such as triethylamine can be used.

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)aziridine and N-(2-aminopropyl)propyleneimine can be used as well.

The amination reaction is carried out at, for example, 40 to 150°C, preferably 5°C.
This is achieved by mixing and stirring the polymer and fullkylene imine under a temperature condition of 0 to 100°C.

The polymer (I) thus obtained has: - a 2-second functional group in the molecule, which is a carboxyl group formed by forming a salt between the amino group and the basic compound (C) resulting from an amination reaction;

If the amination reaction is carried out without neutralization with a basic compound (C), some of the carboxyl groups contained in the polymerization of the precursor will be modified with aminoalkyl, resulting in poor weather resistance. Only curable resin compositions can be used. On the other hand, when the carboxyl groups contained in the precursor polymer are neutralized with a basic compound (C) having five or more bases, the amination reaction does not proceed, resulting in poor curability. Therefore, in the present invention, it is preferable to use the basic compound (C) in an amount of 0.1 to 0.6 g per carboxyl group contained in the precursor polymer.

The epoxy compound (U) used in the present invention is not particularly limited as long as it has at least two epoxy groups in the molecule, but particularly suitable epoxy compounds (ff) in the present invention include, for example, ethylene glycol diglycidyl ether , propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and copolymers containing glycidyl (meth)acrylate components, etc., and mixtures of one or more of these. can be used.

There are no particular restrictions on the use of epoxy compound (II), but
In order to exhibit necessary and sufficient performance such as drying properties, hardness, weather resistance, and solvent resistance, 0.0.
It is preferable to set it as 5 to 3.0 hits, more preferably 0
．． 7 to 2.0 for now.

The curable resin composition of the present invention contains the above-mentioned polymer (I) and epoxy compound (If) as essential components. The curable resin composition of the present invention can be used as is for paints, inks, adhesives, etc., but if necessary, known fillers, leveling agents, plasticizers, stabilizers, dyes, toners, pigments, and electrostatic charges may be added. Various additives such as inhibitors may be included as appropriate.

(Effects of the Invention) Since the curable resin composition of the present invention has excellent low-temperature curability, it can be suitably used in various applications such as paints and inks.

Further, the curable resin composition of the present invention can easily disperse various inorganic Ni materials and organic pigments by a known pigment dispersion method, and can be used as a vehicle component for colored enamel paints. 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. by spray painting, roll painting, brush painting, etc., and is dried. Forms a coating film with excellent properties, hardness, weather resistance, solvent resistance, and adhesion. In particular, it has excellent low-humidity curing properties and adhesion to various substrates, so it can be applied to substrates that are not suitable for heat treatment, such as plastics and wood products, and to substrates with difficult adhesion, such as chrome plating and stainless steel. .

Furthermore, by using the curable resin composition of the present invention,
There is no concern about toxicity due to isocyanate, which is seen in urethane-based paints, and paints with the above characteristics can be manufactured easily and at low cost, making them suitable for use in large structures, automobile repair, and woodwork such as furniture painting. Can be used for a wide range of purposes.

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

Incidentally, unless otherwise specified, quadruple parts and % indicate parts by weight and fffffi%, respectively.

Reference example 1 5 pieces of isopropyl alcohol in a 4-bottle flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas inlet tube.
0 parts were added and the stomach was warmed to 80°C. While blowing nitrogen gas into the mixture, 6 parts of methacrylic acid, 20 parts of methyl methacrylate, 20 parts of butyl methacrylate, 1-4 parts of butyl acrylate, and 0.5 parts of azobisisobutyronitrile were added.
The mixture was added dropwise from the dropping funnel over 2 hours, kept at 80° C. for 6 hours, and then cooled to room temperature to give 1 q of a solution of the carboxyl group-containing polymer.

Next, 2 parts of triethylamine was charged into the flask and stirred for 10 minutes, and then 4 parts of ethyleneimine was added dropwise over a period of 10 minutes. One hour after finishing the dropping, the temperature was raised to 75°C and held at the same temperature for 5 hours, then a distillation device was set in a four-bottle flask, heated under reduced pressure, and the effluent and toluene from the same tank were replenished. Isopropyl alcohol was flowed out of the system together with unreacted ethyleneimine, and the remaining ethyleneimine was completely removed. Finally, the nonvolatile content was adjusted to 50% to obtain a solution of polymer (1).

Reference Examples 2 to 3, Comparative Reference Examples 1 to 2 In Reference Example 1, the same procedure as in Reference Example 1 was performed except that the composition of the polymerizable material and the ratio of triethylamine and ethyleneimine were as shown in Table 1. Repeat polymer (2) ~
(3) and the solutions of comparative polymers (1) and (2) were 19.

Table 1 Examples 1 to 3, Comparative Examples 1 to 2 Polymers obtained in Reference Examples 1 to 3 and Comparative Reference Examples 1 to 2 (1
) to (3) and 120 parts of comparative polymers (1) to (2) and 40 parts of titanium oxide (Tie Bake R-820 manufactured by Ishihara-san IT Co., Ltd.) were placed in a sand mill container, and 200 parts of
The mixture was stirred at high speed for 30 minutes using llffl to obtain a pigment dispersion of a polymer having a pigment weight density of 40% in nonvolatile matter. To this pigment dispersion, an epoxy compound (Sorbitol polyglycidyl ether, Nagase Sangyo Co., Ltd. ￥J) whose epoxy groups are equivalent to the total of amine groups and carboxyl groups contained in the polymer in the dispersion is blended. , curable resin compositions (1) to (3) consisting of polymers (1) to (3) and epoxy compounds
) and comparative compositions (1) to (2) consisting of comparative polymers (1) to (2) and epoxy compounds as binders (1) to (3) and comparative paints (1) to ( 2)
(q.

These paints were spray applied to a zinc phosphate-treated steel plate to a dry film thickness of 40 μm, and dried at 60° C. for 30 minutes to obtain various test paint films. The results of various tests on these coatings are shown in Table 2.

[Paint film performance test method and its evaluation 1iIli standard] (
1) Drying property 2. Immediately after forced drying, the product was rated at 7F by touch.

◎・・・・・・No change ○・・・・・・Leaves a little mark △・・・・・・Leaves a mark ×・・・・・・strong adhesiveness (2) Gloss = 60' Specular reflectance was measured.

◎...85 O...85~75 △...75~65 X...65〉 (3)! Adhesion: Remaining of the coating film was examined by peeling off with cellophane tape for 1 s+goban.

◎・・・・・・100/100 0・・・・・・100/100～95/100Δ・・・
...95/100~90/, 100X...9
0/100> (4) Pencil hardness: The scratch hardness of the paint film was examined using a Mitsubishi uni with a load of 250a.

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

◎・・・No change ○・・・Slightly softened Δ・・・Softened×・・・Coating film dissolved (6) Chemical resistance: 5% NaOH The condition of the coating film was observed after immersing it in an aqueous solution for 24 hours.

◎・・・No change ○・・・Slight blister occurred △・・・・・・
- Blisters were generated ×... Blisters were generated in the coating film. (7) Weather resistance: The state of the coating film was observed after 400 hours of irradiation with a Sancitoin type weatherometer. □ ◎...No change O...Slight loss of luster △...Fixed luster ×...Cracks occurred in the coating (8) Water resistance : The condition of the coating film was observed after immersing it in dry water at 50°C for 30 hours.

◎・・・No change ○・・・Slight blistering Δ・・・・・・
・Blisters occurred×・・・41 rips occurred in the paint film 2nd
Representative patent applicant Nippon Shokubai Chemical Co., Ltd.
Tsuyoshi Yamaguchi Man! :, 5 (C. Procedural amendment written spontaneously) July IO date, 1985.

Claims (1)

[Claims] 1. Carboxyl group-containing unsaturated monomer (a) 1-
20% by weight and other polymerizable unsaturated monomers (b) 8
The carboxyl groups of the polymer obtained by copolymerizing 0 to 99% by weight (however, (a) + (b) is 100% by weight) are partially neutralized with a basic compound (C), and the remaining A curable resin composition comprising as essential components a polymer (I) formed by reacting an alkylene imine (D) with a carboxyl group and a compound (II) containing at least two epoxy groups in the molecule.