JPH03185073A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject curable resin composition free from influences of humidity and water, excellent in workability, reactivity, weather resistance, chemical resistance, etc., and suitable for a coating material, an adhesive, etc., by blending a polymer having a grafted primary (secondary) amino group with a specified compound. CONSTITUTION:(A) A polymer having a grafted primary or secondary amino group is blended with (B) a compound, e.g. an alkylacrylamide glycolate alkyl ether represented by formula I (R1 is H or 1-2C alkyl; R2 and R3 are 1-4C alkyl) and having an unsaturated bond capable of Michael addition with an amino group and an active ester group capable of interchange reaction with an amino group or a compound expressed by formula II (R4 is same as R1; R5 is alcohol, phenol, amine or hydroxylamine residue capable of interchange with amino group at ordinary temperature) and having an unsaturated bond capable of Michael addition with an amino group and an active ester group capable of interchange reaction with an amino group or an amide group, e.g. N-(meth) acryloxysuccinamide, thus obtaining the objective curable resin composition.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to (a) a polymer having a grafted primary amino group or a grafted secondary amino group, and (b) a polymer having at least an amino group and a Migel addition in the molecule The present invention relates to a curable resin composition comprising a compound having an unsaturated bond, and an active ester group or amide group that undergoes an exchange reaction with an amino group.

[Prior Art] Conventionally, curable resin compositions include curable resin compositions of polyhydric alcohol compounds such as polyester polyols and acrylic polyols and polyvalent incyanate compounds, and curable resin compositions of polyhydric incyanate compounds such as polyamines and polyamide amines. Curable resin compositions of amine compounds and epoxy resins are used in a wide variety of applications, including paints, adhesives, surface treatment agents, molded products, and foamed resins.

[Problems to be Solved by the Invention] However, although the curable resin composition of a polyhydric alcohol compound and a polyhydric incyanate compound has characteristics such as its reactivity, weather resistance, and versatility, Problems of toxicity, the problem that it cannot be used in aqueous systems because it reacts with water, and management issues to suppress side reactions of isocyanate compounds due to water, moisture, etc. even when used in solvent or non-solvent systems. Although there are some problems in curable resin compositions of polyvalent amine compounds and epoxy resins that have not yet been resolved, they have characteristics such as reactivity, chemical resistance, and versatility, but they do not have good weather resistance. , there were problems with low-temperature curability, etc.

c. Means for Solving Problems] The present inventors have discovered a curable resin composition of a polyhydric alcohol compound and a polyvalent isocyanate compound, and a curable resin composition of a polyvalent amine compound and an epoxy resin. As a result of intensive research into curable resin compositions that do not have the above-mentioned problems, the present invention was achieved.

That is, the present invention provides (a) a polymer having a grafted primary amino group or a grafted secondary amino group, and (b) - Formula (I) 0 0R2 II CH2= C-C-NH-C-C-0 -R31 R10 ... (I) (wherein R1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R2 and R3 are each independently selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms) A metal product having an unsaturated bond that undergoes Michael addition with an amine group and an active ester group that undergoes an exchange reaction with an amino group represented by the formula (II) CI+2 = C-C-R5... - (II) (wherein R4 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R5 is an alcohol, phenol, amine, or hydroxylamine residue that can undergo an exchange reaction with an amino group at room temperature) selected from the group consisting of.

The present invention relates to a curable resin composition characterized by comprising a compound having an unsaturated bond that undergoes a Michael addition with an amino group represented by the following formula, and an active ester group or amide group that undergoes an exchange reaction with the amino group.

More specifically, the (a) polymer having a grafted primary amino group or secondary amino group used in the present invention includes, for example, US Pat. No. 3,228,823 and US Pat. No. 3,467.
No. 611, U.S. Patent No. 4,104,230, JP-A-63-
Graft obtained by reacting the carboxyl group of a polymer obtained by copolymerizing an unsaturated monomer containing a carboxyl group described in No. 56549 etc. with other copolymerizable unsaturated monomers with an alkylene imine. A polymer having a primary amino group or a grafted secondary amino group or JP-A No. 6
A polymer having a grafted primary amine group or a grafted secondary amino group obtained by reacting a polymer having an epoxy group in a side chain with ammonia as described in No. 1-136515, etc., or a polymer having a grafted secondary amino group, or US Pat. Homopolymers of polymerizable unsaturated monomers such as acryloxyalkylugetimine or acryloxyalkyloxyalkylugetimine described in U.S. Patent No. 3,497,485, etc., or these ketimine-containing polymerizable unsaturated monomers , a polymer having a grafted primary amino group obtained by hydrolyzing a copolymer with other copolymerizable unsaturated monomers, or Japanese Patent Publication No. 62-17601, Japanese Patent Publication No. 63-61321
The carboxyl group of the polymer obtained by copolymerizing the unsaturated monomer containing a carboxyl group described in the above, and other copolymerizable unsaturated monomers, or the polyamine having an aliphatic amino group, A polymer having a grafted primary amino group obtained by reacting a polyamine having an aliphatic amino group and at least one ether group, or JP-A-54-110248, JP-A-54-1444
No. 32, JP-A-57-3850, JP-A-62-727
A hydrazine derivative having at least two hydrazine residues represented by hydrazine hydrate is reacted with a polymer containing a carbonyl group limited to an aldo group or a keto group as described in No. 42 etc. Polymers with grafted primary amino groups obtained or Japanese Patent Publication No. 1983
A polymer having a grafted primary amino group obtained by reacting a polymer containing an amide group or an ester group with hydrazine hydrate as described in US Pat. No. 4,414,250. A polymer having a grafted primary amino group or a grafted secondary amino group obtained by reacting a polyamine with a polymer containing
It is a polymer having a grafted primary amino group such as vinylamine obtained by various synthesis methods described in JP-A No. 61-51006 and the like.

The compound (b) used in the present invention that has at least an unsaturated bond that undergoes a migel addition with an amino group and an active ester group that exchanges with an amine group in its molecule has the following general formula (I) 0 0R2 II CI+2= C-C-NH-C-C-0-R31 R20... (I> (wherein, R1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R2 and R3 are each independently is selected from the group consisting of lower alkyl groups having 1 to 4 carbon atoms in ) ... (n) (wherein R4 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R5 is an alcohol, phenol, amine, which can undergo an exchange reaction with a primary amino group at room temperature, (I ) Examples of the compound include alkyl acrylamide glycolate alkyl ethers whose manufacturing method is described in U.S. Pat. , butylacrylamide glycolate butyl ether, and the like.

- As a compound represented by formula (II), Po ]
ymer, 13.462-464 (1972), and N-(meth)acryloxysuccinoamide described in J. Polymer Sci., 12,553-559.
(1974) and 1-(meth)acryloylbenzotriazole described in J. Polmer Sc.
i.

12.2453-2452 (1974) 1-(meth)acryloyl imidazole and Makromof
Chem, 172.27-45 (1973; Examples include esters.

The curing mechanism of the present invention is expressed by the following general formula when, for example, methyl acrylamide glycolate methyl ether is used.

0C■3 1 OCH3 That is, the unsaturated bond of methyl acrylamide glycolate methyl ether is a grafted primary amino group or
The active ester part reacts in a Michael addition manner with the active hydrogen of the grafted secondary amino group, and the active ester part has a hardening time of 81 cm, which is three-dimensionally crosslinked by forming an amide bond in the exchange reaction. - The Migel addition reaction rate between the active hydrogen of the amino group and the unsaturated bond is numerically fast and proceeds even at low temperatures, and the bonds formed by this reaction are excellent although they do not contribute much to improving the chemical resistance of the cured product. Provides weather resistance and flexibility. Although the reaction rate of the exchange reaction between the active hydrogen of the amino group and the active ester moiety is not as fast as that of Michael addition, the resulting amide bond gives the cured product excellent chemical resistance and toughness due to its cohesive force. In the curable resin composition, two types of reactions are involved in the curing mechanism as described above, and a cured product that takes advantage of the characteristics of each can be provided.

In order to express the characteristics of the physical properties of the cured product of the curable resin composition of the present invention, as is clear from the above-mentioned curing mechanism, for each two active hydrogens of the amino group, - formula (I) or - formula (n
) is the theoretical equivalent of the unsaturated bond that undergoes Migel addition with the active hydrogen of the amino group, and the compound-molecule having an active ester or active amide moiety that exchange-reacts with the active hydrogen of the amino group. Based on this, the following molar ratios can be used.

(-number of moles of formula (I) or -formula (n))/(number of moles of active amine hydrogen) = 0.1 to 2.0, more preferably a molar ratio of 062 to 1.0. be.

[Function] The present invention provides (a) a polymer having a grafted primary amino group or a grafted secondary amino group, and (b) a polymer having the formula (
I) 0 0R2 1 0H2 = C-C-NH-C-C-0-R31 R40...<I) (wherein R1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms) , R2 and R3 are each independently selected from the group consisting of lower alkyl groups having 1 to 4 carbon atoms. or a compound having the general formula (n) 1 CH2= C-C-R5... (n) (wherein R4 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R5 is (selected from the group consisting of alcohol, phenol, amine, and hydroxylamine residues that can undergo an exchange reaction with a primary amino group.) An unsaturated bond that forms a Michael addition with an amino group represented by By providing a curable resin composition characterized by comprising a compound having an ester group or an amide group, it is not affected by humidity etc.
It is possible to provide a curable resin composition that has excellent workability and reactivity, and has characteristics such as chemical resistance, weather resistance, and versatility. Furthermore, this curable resin composition can be used in a wide variety of applications such as paints, adhesives, surface treatment agents, molded products, and foamed resins.

[Examples] Hereinafter, nine embodiments of the present invention will be specifically illustrated and explained using Examples.The present invention is not limited to these Examples in any way.

In the examples, parts indicate parts by weight, and percentages (%
) indicates weight %.

Reference Example 1 After charging 336 parts of isopropyl alcohol and 224 parts of toluene into an IJ flask equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube, and dropping funnel, the temperature was raised to 80°C while introducing nitrogen. .

72 parts of methacrylic acid, 120 parts of butyl acrylate, 48 parts of styrene, and 9.6 parts of azobisisobutyronitrile.
After dropping a polymerizable monomer mixture consisting of 30% and 50% over 2 hours, the copolymer was further aged at 80°C for 6 hours and cooled to obtain an acrylic copolymer with a non-volatile content of 30%. 36 parts of ethyleneimine was added to the mixture at 25°C, and after stirring for 1 hour, the temperature was raised to 75°C and reacted for 5 hours.
After the reaction was completed, the flask was equipped with a distillation device, and while heating under reduced pressure, the effluent was replenished with toluene, and Inglovil alcohol was flowed out of the system together with unreacted ethyleneimine. After completely removing the remaining ethyleneimine,
Methyl isobutyl getone was added to adjust the nonvolatile content to 30% to obtain a grafted amine-containing acrylic copolymer.

Reference Example 2 In a flask similar to Reference Example 1, add 2 isopropyl alcohol.
After charging 80 parts and 124.6 parts of n-butoxyshetanol, the temperature was raised to 80°C while nitrogen was introduced. A polymerizable monomer mixture consisting of 980.5 parts of methacrylate, 63 parts of methyl methacrylate, 136.5 parts of butyl acrylate, 70 parts of styrene and 9 parts of azobisisobutyronitrile was added dropwise over 2 hours. 80℃
The mixture was aged for 6 hours and cooled to obtain a polymer with a non-volatile content of 46.4%. After adding 33 parts of triethylamine to this polymer and mixing uniformly, 61 parts of a 37% ethyleneimine aqueous solution was added.
After dropping 6 parts of the mixture and reacting at 80° C. for 4 hours, 8.4 parts of triethylamine and 75 parts of deionized water were further added to obtain a grafted amine-containing water-soluble acrylic copolymer with a nonvolatile content of 401%.

Reference Example 3 After charging 400 parts of deionized water and 40 parts of an anionic activator (25% aqueous solution) into a flask similar to Reference Example 1,
The temperature was raised to 68° C. while introducing nitrogen. After adding 40 parts of a polymerizable monomer mixture consisting of 48 parts of acrylic acid, 160 parts of 2-ethylhexyl acrylate, and 192 parts of styrene into a flask and stirring for 15 minutes, 1.75% hydrogen peroxide solution was added. 4.6 parts and 3% L-ascorbine'fllyk
15 minutes after the start of polymerization by adding 4.2 parts of Solution J, the remaining polymerizable monomer mixture was uniformly added dropwise over 90 minutes. During this time, 41 parts of 1.75% hydrogen peroxide solution and 37 parts of 3% L-ascorbic acid aqueous solution were added dropwise into the flask every 10 minutes until the dropwise addition of the polymerizable mixture was completed. 40.6 parts of deionized water was added to 150 parts of this emulsion and uniformly mixed.

Add 47.8 parts of 10% ethyleneimine aqueous solution and heat to 50°C.
The mixture was reacted for 2 hours to obtain a grafted amine-containing emulsion with a non-volatile content of 30%.

Reference Example 4 After 520 parts of isopropyl alcohol was charged into the same flask as in Example 1, the temperature was raised to 80° C. while introducing nitrogen. A polymerizable monomer mixture consisting of 50 parts of 2-((1,3-dimethylbutyl)imino)ethyl methacrylate, 108 parts of 2-ethylhexyl acrylate, 147 parts of styrene, and 12.2 parts of azobisisobutyronitrile was prepared. After 0 drops of water were added over 2 hours, it was further aged at 80°C for 6 hours, cooled, and 4.3 parts of water was added to reduce the non-volatile content to 3.
An acrylic copolymer containing 4% grafted amine was obtained.

Example 1 Using the grafted amine-containing acrylic copolymer obtained in Reference Example 1 as a main ingredient, MAGME (trade name:
30.2 parts of a 30% butanol solution of methyl acrylamide glycolate methyl ether (manufactured by American Cyanamid, Inc.) was added and mixed uniformly. The following tests were conducted using this mixture. The results are shown in Table-1.

[Coating film curing test and evaluation criteria] (1) Drying property: The above mixture was applied onto a glass plate using a 75 μm applicator, and dried to the touch using an RCC drying meter at 25°C and 60% relative humidity. Evaluation was made based on curing and drying time.

(2) Pencil hardness: After applying the above mixture and curing it for 7 days in the same manner as in (1), the pencil scratch hardness at a load of 250 gr was measured using a pencil scratch tester according to JIS K-540 0. It was measured using

(3) Gel Fraction 2 An appropriate amount of the above mixture was applied onto a Teflon plate, and after 7 days of aging, the coating was peeled off and extracted with acetone using a Soxhlet extractor for 4 hours to measure the gel fraction.

In addition, 14 parts of titanium oxide and appropriate amounts of glass beads were added to 100 parts of the above base material, and 2 parts were added using a paint shaker.
After time-dispersed mixing, the mixture was diluted to 700 cps. Add MAGME to this in the same way as the above mixture,
A paint formulation was obtained by uniformly mixing. The following tests were conducted using this formulation. The results are shown in Table-1.

[Performance test and evaluation criteria for coating film] (4) Weather resistance: The above formulation was applied to a stainless steel plate at 75%
The coating was applied with a μm applicator, cured for 7 days at 25° C. and 60% relative humidity, and then irradiated for 240 hours with a sunshine weather meter according to JIS K-5 400. The state of the coating film was then observed.

[Color difference] ◎；No change ○: Slight discoloration Δ: Slight discoloration ×: Discoloration [Gloss retention rate] Gloss retention rate from initial gloss Display in .

(5) Solvent resistance: After coating in the same manner as in (1), the coating film was lapped using methyl ethyl getone, and the number of times of rubbing until the coating film deteriorated was measured.

Example 2 Using the grafted amine-containing water-soluble acrylic copolymer obtained in Reference Example 2 as a main ingredient, 3 parts of MAGME were added to 100 parts of the main ingredient.
17.4 parts of a 0% aqueous solution was added and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table-1.

Further, a coating composition was obtained in the same manner as in Example 1 by adding 16 parts of titanium oxide and appropriate amounts of glass beads to 100 parts of the above base resin. The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

Example 3 Using the grafted amine-containing emulsion obtained in Reference Example 3 as a main ingredient, 14.4 parts of a 30% aqueous solution of MAGME was added to 100 parts of the main ingredient and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. Display the results -
Shown in 1.

In addition, 100 parts of the above base agent and 18 parts of titanium oxide were mixed,
Further, 14.4 parts of a 30% aqueous solution of MAGME was added and mixed uniformly to obtain a paint formulation.

The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

Example 4 Same as Example 1 except that 35.4 parts of a 30% ethyl acetate solution of 1-methacryloyloxybenzotriazole was added to 100 parts of the grafted amine-containing acrylic copolymer obtained in Reference Example 1. Mixtures and paint formulations were prepared and tested.

The results are shown in Table-1.

Example 5 Using the grafted amine-containing acrylic copolymer obtained in Reference Example 4 as a main ingredient, 8.4 parts of a 30% isopropyl alcohol solution of MAGME was added to 100 parts of the main ingredient and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table-1.

Further, a coating composition was obtained in the same manner as in Example 1 by adding 16 parts of titanium oxide and appropriate amounts of glass beads to 100 parts of the above base resin. The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

Example 6 A hydrazine derivative-modified graft amine-containing acrylic copolymer (Acronal YJ-2715D; Yuka Badish) was used as the main ingredient, and 30 parts of MAGME was added to 100 parts of the main ingredient.
% aqueous solution was added and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table-1.

In addition, 100 parts of the above base agent and 18 parts of titanium oxide were mixed,
Furthermore, 11.9 parts of a 30% aqueous solution of MAGME was added and mixed uniformly to obtain a coating composition.

The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

Comparative Example 1 Bisphenol A diglycidyl ether, Epicoat 828 (trade name: Yuka Shell Co., Ltd.) was added to 100 parts of the grafted amine-containing acrylic copolymer obtained in Reference Example 1.
Mixtures and coating formulations were prepared and tested in the same manner as in Example 1, except that 19.9 parts of epoxy compound) was added. The results are shown in Table-1.

Comparative Example 2 Using commercially available polyamide amine as the main ingredient, 122 parts of Epikote 828 was added to 100 parts of the main ingredient and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used.

The results are shown in Table-1.

Further, a coating composition was obtained in the same manner as in Example 1 by adding 18 parts of titanium oxide and appropriate amounts of glass beads to 100 parts of the above base resin. The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

Comparative Example 3 Commercially available acrylic polyol (hydroxyl value 80 mgKOH/g
r, 5solid, non-volatile content 50%, toluene, acetic acid n-
Butyl solution? Trimer of 1,6-hexamethylene diisocyanate (NGO content 16.5
%, nonvolatile content 75%, ethyl acetate solution) were added thereto, mixed uniformly, and diluted with toluene. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table 1.

Further, 30 parts of titanium oxide and appropriate amounts of glass beads were added to 100 parts of the above acrylic polyol with a non-volatile content of 40% in toluene, and mixed in the same manner as in Example 1. This was added to a trimer of 1.6-hexamethylene diisocyanate (NGO content 16.5%, non-volatile content 75%,
9.6 parts of ethyl acetate solution) were added and mixed uniformly to obtain a paint formulation.

Same as Example 1 except that this formulation was used. A similar test was conducted.

The results are shown in Table-1.

Example 7 Grafted amine-containing emulsion 1 obtained in Example 3
00 parts at 25℃, the viscosity of a 1% aqueous solution is 10.0OOcp
CMC (sodium cellulose glycolate)
20 parts of a 2% aqueous solution of MAGMH, 14 parts of a 30% aqueous solution of MAGMH.
4 parts were added and mixed uniformly to obtain an adhesive. This adhesive was applied to an adherend made of birch material in a coating amount of 150 g/aJ and bonded together under conditions of 25° C., a pressing pressure of 10 g/cd, and a pressing time of 1 hour. Furthermore,
After curing for 3 days at 25°C and 60% relative humidity, J
In accordance with IS K-6852, the normal state adhesive strength and the boiling resistant adhesive strength after repeated boiling treatment are calculated as compressive shear adhesive strength (ktr
f/d). The results are shown in Table-2.

Comparative Example 4 Grafted amine-containing emulsion 1 obtained in Reference Example 3
CMC was added to 00 parts in the same manner as in Example 7, and 5.8 parts of ethylene glycol diglycidyl ethyl was added thereto and mixed uniformly to obtain an adhesive.

The same procedure as in Example 7 was carried out except that this adhesive was used. The results are shown in Table-2.

Comparative Example 5 Comparative Example 5 was a water-based vinyl urethane adhesive with a non-volatile content of 46.8% prepared in a two-component type, and the same procedure as in Example 7 was conducted except that this adhesive was used. The results are shown in Table-2.

[Effects of the Invention] As is clear from the examples, the curable resin composition of the present invention is not affected by humidity, water, etc., has excellent workability and reactivity, and has excellent chemical resistance and weather resistance. Characterized by its versatility and versatility,
Taking advantage of these characteristics, it can be used in a wide variety of applications such as paints, adhesives, surface treatment agents, molded products, and foamed resins.

Claims (1)

[Claims] (1) (a) A polymer with a grafted primary amino group or a grafted secondary amino group, and (b) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...(I) (in the formula , R_1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R_2 and R_3 are each independently selected from the group consisting of lower alkyl groups having 1 to 4 carbon atoms.) A compound or general formula (II) that has an unsaturated bond that undergoes a Michael addition with a group and an active ester group that exchanges with an amino group ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...(II) (R_5 is selected from the group consisting of hydrogen and lower alkyl groups having 1 to 2 carbon atoms, and R_5 is selected from the group consisting of alcohol, phenol, amine, and hydroxylamine residues that can undergo exchange reactions with amino groups at room temperature.) 1. A curable resin composition comprising a compound having an unsaturated bond that undergoes a Michael addition with an amino group, and an active ester group or amide group that undergoes an exchange reaction with the amino group.