JPS5821409A - Water-miscible resin composition - Google Patents

Abstract

PURPOSE:The titled composition that is made by neutralizing a copolymer from ethylenically unsaturated monomers containing tertiary amino groups, carboxyls and dicyclopentadiene derivatives respectively, then mixing with a specific epoxy resin, thus being curable at room temperature or under heating at relatively low temperature. CONSTITUTION:After the copolymerization of (A) 3-20pts.wt. of an ethylenically unsaturated monomer bearing tertiary amino groups such as N,N-dimethylaminoethyl acrylate, (B) 3-20pts. of a carboxyl-containing monomer such as acrylic or methacrylic acid, (C) 5-30pts. of a dicyclopentadiene derivative of the formula (R is H, lower alkyl, halogen; R' is difunctional organic group; n is 0, 1) such as dicyclopentenyl acrylate and (D) 30-89pts. of other monomers copolymerizable with the above monomers such as styrene, the resultant copolymer is neutralized. This copolymer (98-60pts.) is combined with an epoxy compound miscible with water (2-40pts.) such as trimethylolpropane glycidyl ether to give the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that can be cured by heating at room temperature or low temperature.

In the paint, lk packaging and adhesive industries.

Due to the recent rise in oil prices, there is a strong desire for paints and adhesives that are less polluting, as well as resource and energy efficient.

Conventionally, thermosetting acrylic resins have glycidyl groups, N-methylolamide groups, amide groups,
It is used by containing sil groups, hydroxyl groups, etc. in the carboxyl group, blending these with amino resins, epoxy resins, etc., and causing a curing reaction at a high temperature of 130° C. or higher, and in some cases, 150° C. or higher.

On the other hand, for construction materials such as glass, wood, and concrete, and metal materials for automobile repair, which cannot be treated at high temperatures, nitrified cotton, cellulose acetate butyrate, etc. are used in combination with acrylic resins and alkyd resins. An air-drying paint called lacquer is used. Such paints have poor solvent resistance. It has drawbacks such as poor weather resistance, making it unsuitable for fields that require high-performance coatings. Another drawback is that the amount of solvent in the paint is large, making it difficult to paint. Additionally, phthalic acid enamels and urethane paints are used in some applications. Phthalate enamel has problems with coating performance such as dryness and hardness.

Urethane paints offer high coating properties, but
There are problems with the toxicity, ease of handling, and price of incyanate.

On the other hand, water-based paints dry more slowly and have poorer water resistance than organic solvent-based paints. Poor corrosion resistance. Due to problems such as low hardness, various improvements have been made. Adhesives, especially those used to adhere polypropylene films to paper or printing paper, include m-tinated polypropylene, ethylene 7
Examples include those obtained by dissolving resins such as 4m vinyl copolymer, Odine ester, and polyurethane in organic solvents such as toluene and ethyl acetate, and those obtained by adding a polyisocyanate compound as a curing agent to this solution. When these organic solvent type adhesives are normally used, the non-volatile content is adjusted to 15-30% by weight, and after being applied to the object to be coated, 70-850 to 85% by weight is evaporated and dried, and then applied to other adherends. However, since the organic solvents volatilized during the drying process are a major cause of air pollution, which is a serious social problem, there is a strong desire to reduce the amount of organic solvents used as much as possible.

The present invention solves these problems.

In other words, one aspect of the present invention is.

(5) 3 to 20 parts by weight of an ethylenically unsaturated monomer having a tertiary amino group.

(B) 3 to 20 parts by weight of an ethylenically unsaturated monomer having a carboxyl group.

[C) General formula +1) (However, in formula 9, R is hydrogen, a lower alkyl group, or a halogen, z is a divalent organic group, and n is 0 or l). 5-30 parts by weight.

and (■) (AJ, (B) t, obtained by neutralizing a copolymer obtained by copolymerizing 30 to 89 parts by weight of other ethylenically unsaturated monomers copolymerizable with component (C)) Neutralized resin (1) 9
It relates to a water-dilutable resin composition comprising a combination of 8 to 60 parts by weight and 2 to 40 parts by weight of a water-dilutable epoxy resin (if).

The resin composition according to the present invention F14 can be heated at room temperature or at low temperature (
It can be cured by heating at 40 to 80°C.

Examples of the ethylenically unsaturated monomer having a tertiary amino group, which is the carrier component of the present invention, include N,N-dimethylaminoethyl acrylate), N,N-diethylaminoethyl acrylate, and N,N-diethylaminoethyl acrylate. methacrylate, N, N-diethylaminoethyl methacrylate,
Vinylpyridine, vinylpyrroline, vinylquinoline.

Vinylisoquinoline, N,N-dimethylamino vinyl ether, 2-(N,N-dimethylamino)-4-vinylpyridine, trans-1,2-cyhyridylethylene, 2
-Methyl-5-vinylpyridine, 3-cinnamoylpyridine, 2-methyl-5-cinnamoylpyridine, 44-
Examples include diamino-2-vinyl-5-meliazine.

The amount used is 3 to 20 parts by weight, preferably 5 to 15 parts by weight; too little will result in insufficient curability, while too much will not only reduce water resistance but also shorten pot life.

Examples of the ethylenically unsaturated monomer having a carboxyl group, which is component (B), include acrylic acid, methacrylic acid, maleic acid, fluoric acid, and itaconic acid. Usage amount is 3
~20 parts by weight, preferably 4 to 8 parts by weight. If the amount used is too small, sufficient water dilutability will not be obtained and, furthermore, the curing reaction will be slow, which poses a practical problem. Too much water will result in poor water resistance and short pot life.

The dicyclopentadiene derivative represented by the general formula (1) as the component (C) is obtained by numbering the dicyclopentenyl group carbon atoms in the compound as shown in the following general formula (n).

We are meeting. Here, R is a divalent bridged group having 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms.

In the alkylene group having a prime number of 2 or more, R and R may be the same or true. 9m is an integer of 1 or more.

Component (C) is dicyclopentenyl acrylate.

Dicyclopenes such as dicyclopentenyl methacrylate, dicyclopentenyl-α-chloroacrylate, dicyclopentenoxyethyl acrylate, dicyclopentenoxyethyl methacrylate, dicyclopentenoxyprobyl acrylate, dicyclopentenoxypropyl methacrylate, etc. Tenoxyalkyl acrylate or methacrylate, acrylic ester of polyalkylene glycol dicyclopentenyl monoether such as acrylic ester or methacrylic ester of diethylene glycol dicyclopentenyl monoether, and methacrylic ester. C) The amount of ingredients used is 5. ~30 parts by weight, preferably 7 to 20 parts by weight. If the amount used is too small, drying properties and
Corrosion resistance.

It has poor moisture resistance and has insufficient initial adhesive strength when used as an adhesive. If the amount of stool is too large, the towability will be poor when used as a paint, and the adhesive strength will be reduced when used as an adhesive. moreover,
The viscosity of the resin increases and workability becomes extremely poor.

Component (2) is an ethylenically unsaturated monomer copolymerizable with component (4), (B) or (C), such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate.

n-butyl acrylate, inbutyl acrylate), 2
- Noalkyl acrylate such as ethylhexyl acrylate, methyl methacrylate.

Ethyl methacrylate, n-propyl methacrylate,
Alkyl methacrylates such as inglovir methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, styrene,
- Styrenic monomers such as monomethylstyrene and vinyltoluene; vinyl esters of saturated basic acids such as vinyl acetate, vinyl propionate, and vinyl stearate;

Epoxy group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, vinyl Schiff 7, such as Ac IJ a nitrile and methacrylate trile, acrylamide, and methacrylamide.

Unsaturated amides such as N-methylol acrylamide and N-butoxymethyl acrylamide, hydroxyalkyl acrylates such as 2-hydrodiethyl acrylate and 2-hydroxypropyl acrylate, 2-hydroxydiethyl methacrylate, 2-hydroxypropyl methacrylate, etc. hydroxyalkyl methacrylate.

These include unsaturated monomers containing phosphoric acid groups such as ethyl acrylate phosphate and ethyl methacrylate phosphate, and vinyl esters of saturated basic acids such as vinyl acetate and vinyl propionate, which may be used singly or in combination of two or more. . Mata f! Depending on rK, it is also possible to use a polyfunctional ethylenically unsaturated monomer such as ethylene glycol diacrylate within a range of 0 to 2 parts by weight. Among the copolymerizable ethylenically unsaturated monomers used as component (D), alkyl acrylates, alkyl methacrylates, and styrenic monomers are preferred.

Also, reactivity other than double bonds is 1g#! The monomer having groups is preferably used in an amount of 0 to 30% by weight, particularly preferably 0 to 10% by weight, based on the total amount of component (D). If there are too many monomers with such warping functional groups, the film properties (water resistance,
moisture resistance, chemical resistance, etc.) tend to decrease. In addition, in order to improve adhesion, a
Among the t-isomers, it is preferable to use hydroxyalkyl acrylate, human hydroxyalkyl methacrylate, unsaturated amide, and the like. moreover.

In order to make the copolymer of components (2) to (3) have a particularly preferable glass transition point of 30 to 70°C for coatings, hard monomers such as methyl methacrylate, ethyl methacrylate, and styrene ( a) and a soft monomer (b) such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. are used in a weight ratio of (a)/(b) of 80/20 to 50150. is particularly preferred.

Components (B), (C) and (D) are obtained by copolymerization by solution 1i&, bulk polymerization, etc. by well-known methods. The polymerization temperature is about 50 to 150
As a polymerization catalyst at ℃1, benzoyl peroxide, t-
Peroxidized products such as butyl peroxide and cumene hydroperoxide, azobisisobutyronitrile, azobisisobutyl-valeronitrile, etc. can be used, and the amount used is o, i based on 100 parts by weight of the total amount of monomers. ~5 parts by weight. For example, mercaptan if necessary.

Molecular weight modifiers such as carbon tetrachloride and carbon tetrabromide can also be used.

Copolymerization is carried out in the presence of a water-soluble organic solvent.9 After polymerization, co-tf! Neutralization without isolating the r-isomer, Part 1
1. It is preferable because it can be used in the resin composition of the present invention. In this case, the water-soluble organic solvent has a copolymer concentration of
It is preferable that the weight is 30 to 70% by weight. Cough water-soluble organic solvents include ethanol, isopropyl alcohol, isobutanol, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, 3-methyl-3-methoxybutanol, methyl calpitol, ethyl calpitol, butyl calpitol, etc.1 It is used either as a species or in combination of two or more species.

The copolymer thus obtained is neutralized with a neutralizing agent to form a neutralized tree@(I). Preferably, the degree of neutralization is such that the pH is about 8-11. Examples of the neutralizing agent include amine compounds such as trimethylamine, triethylamine, and dimethylaminoethanol, and ammonia, with amine compounds being preferred. Upon neutralization.

Water may be added.

As the epoxy resin (on the epoxy resin side), one that can be diluted with water can be used. Here, dilutable with water means water/water-soluble organic solvent = 5
It means that it is soluble in a mixed solvent of 75 to 8/2 (weight ratio).

Epoxy trees (111ml) include glycerol polyglycidyl ether, trimethylolethane polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Polyhydric alcohol, ethylene oxide or probile/
It is also possible to use an epoxy resin that has been adducted with oxide and then epoxidized at the end. The epoxy resin of the present invention contains one compound having only one epoxy group in one molecule.
Less than 0 weight of vomiting.

Preferably, it may be contained in an amount of 5- or less by weight.

Neutralized tree M 1) and epoxy resin (fl) are (1)/
C11) is blended in a weight ratio of 98/2 to 60/40, preferably 9515 to 8 G/20. (
1)/(I[3 exceeds 98/2, curing is insufficient.

60/4 due to insufficient coating properties or adhesion properties.
If it is less than 0, the initial drying property or initial adhesive strength will decrease.

In the present invention, it is preferable that the neutralized resin (fl) and the epoxy resin (set) be mixed for the first time during use to form a resin composition.If they are mixed in advance, they will easily harden during storage.

The neutralized resin (1) is preferably mixed with water and/or a water-soluble organic solvent in advance, in which case the solid content is 30 to 60 ml.

It is preferable that water/water-soluble organic solvent be dissolved in a mixed solvent of 80/20 (weight ratio) or less. If the solid content is too high, the viscosity will increase and workability will decrease.

If the solids content is too low, the resin concentration will be too low. In the mixed solvent of water and water-soluble organic solvent, it is preferable that the water/water organic solvent has a weight ratio of 50150 or more, preferably 9% to 70/30.
Preferably, the ratio is 60/40.

The epoxy resin (1) is preferably used in its 11st form or dissolved in a water-soluble organic solvent.

In the resin composition according to the present invention, the weight ratio of water/water-soluble organic solvent is 80/20 or less, preferably 80/20 to 5.
0150. Particularly preferably, it is used after being dissolved in a mixed solvent of 70/30 to 60/40. When it exceeds 80,720, the resin phase and solvent phase tend to separate. Further, in order to reduce the amount of organic solvent used, it is preferable to use 5075Q or more.

Further, the amount of solvent is adjusted so that the resin solid content is 30 to 60% by weight. If it exceeds 60% by weight, the viscosity is high and the paper-making workability is deteriorated, which is not preferable. If it is less than 310% by weight, the resin concentration will be low, which is not preferred in practice.

Lead naphthenate, zinc naphthenate, cobalt naphthenate, zirconium naphthenate, and lead octenoate are added to the resin composition according to the present invention as metal driers.

Cobalt octenoate, zirconium octenoate, etc.
Preferably, the metal is added in an amount of 0.01 to 1% by weight based on the neutralizing resin tl)K. It is preferable that the metal dryer be added to the neutralized resin (1) in advance, or added at the time of mixing the neutralized resin (1) and the epoxy resin (I[).

The resin composition according to the present invention exhibits excellent coating WX41 properties and adhesive properties even without the addition of a metal dryer.

The resin composition according to the present invention may be used as necessary.

Water-soluble or water-dispersible acrylic resins, water-soluble or water-dispersible alkyd resins, water-dispersible vinyl acetate polymers or copolymers, rosin, rosin esters, shellac, etc. can be blended.

The paint obtained using the resin composition of the present invention can be applied by methods such as dipping, dry coating, spray coating, and A-ru coating.

Wood 9 Paper, fiber, plastic, ceramic, iron.

Can be painted on surfaces such as non-ferrous metals.

Manufacturing example 1 Stirrer, @changed needle, reflux condenser 1, 1 dropping funnel.

100% isopropyl alcohol in a 5004 flask equipped with an inert gas inlet. and heat the flask to 80°C under a nitrogen gas flow. Then, as unsaturated monomers, 8t of N,N-dimethylaminoethyl acrylate, 5F of methacrylic acid, and 10% of dicyclopentenyl acrylate were added.
f, stille/10? , methyl methacrylate 37) and butyl acrylate 30? and azobisisobutyronitrile 1.5? as a catalyst. The mixed and dissolved solution is uniformly dropped into the flask from the dropping funnel over a period of 2 hours. After completion of the dropwise addition, the mixture was kept at 80° C. for another 3 hours to complete 9 polymerizations and synthesize a copolymer. The polymerization rate was 98% by weight or more. After this, adjust the pH to 10KII with triethylamine, and tap water to 50KII. added. The resulting neutralized resin solution had a nonvolatile content of 41% by weight and a viscosity of 8 poise at 25°C.

Manufacturing example 2 N was added as an unsaturated monomer in the same manner as in Example 1.

N-dimethylaminoethyl acrylate 15P.

Methacrylic acid 5? , dicyclopentenyl acrylate 1
0? , styrene 10P, methyl methacrylate 30)
and butyl acrylate 30? A neutralized resin was synthesized using The prepared neutralized resin solution had a nonvolatile content of 40% by weight and a viscosity of 9.5 poise at 25°C.

Manufacturing example 3 N was added as an unsaturated monomer in the same manner as in Example 1.

N-dimethylaminoethyl acrylate 81F, methacrylic acid top, dicyclopentenyl acrylate) 10)
, styrene 10? , methyl methacrylate 32f and butyl acrylate 30F were used to synthesize a neutralized resin. This prepared neutralized resin solution had a nonvolatile content of 40.5% by weight and a viscosity of 9 poise.

Production example 4 N was added as an unsaturated monomer in the same manner as in Example 1.

N-dimethylaminoethyl acrylate 8? , methacrylic acid 5), dicyclopentenyl acrylate) 20P, styrene 10? , methyl methacrylate 27? and butyl acrylate 30? A neutralized resin was synthesized using

The prepared neutralized resin solution had a non-volatile content of 41 parts by weight and a viscosity of 12 poise.

Comparative Production Example 1 In the same manner as in Example 1, 10% of methacrylic acid was used as the unsaturated monomer. , dicyclope/tail acrylate) 10), styrene 10? A neutralized resin was synthesized using methyl methacrylate 40F and butyl acrylate 30T. The prepared neutralized resin solution had a nonvolatile content of 41% by weight and a viscosity of 7 poise.

Comparative manufacturing example 2 N was used as the unsaturated drug in the same manner as in Example 1.

N-dimethylaminoethyl acrylate 8? , methacrylic acid 5? , styrene 10? , methyl methacrylate 47
? and butyl acrylate 30? A neutralized resin was synthesized using The prepared neutralized resin solution had a nonvolatile content of 400% by weight and a viscosity of 5 poise.

Comparative manufacturing example 3 N was added as an unsaturated monomer in the same manner as in Example 1.

N-dimethylaminoethyl acrylate 8? , methacrylic acid 2? , dicyclopentenyl acrylate) 10F, styrene 10? , methyl methacrylate) 4 Of, butyl acrylate 30? The copolymer was synthesized using

This copolymer has a pH of 10 KISil with triethylamine.
Cloudiness occurred when tap water was added after conditioning, and there was no water dilutability. 15 parts by weight of trimethylolpropane polyglycidyl ether, which is a polyfunctional epoxide compound that can be diluted with water, is added to the weight part (solid content), and cobalt naratenate is added as a metal dryer to 100 parts by weight of the above neutralized resin solution (solid). (min.) to obtain a water-dilutable resin composition according to the present invention. Furthermore, blended resin (solid content) / titanium white = so / 40 (
White enamel was created by blending titanium white so that the weight ratio was as follows. The properties of this white enamel are shown in Table 1.
When testing the 411 properties, a steel plate treated with Bonderite Toner 10 Fufu was used as the base material, and the test was carried out at room temperature except for drying properties, and the properties were measured after being left to dry for 5 days.

The rest below! 21- Manufacturing example 5 Stirrer, temperature needle, reflux condenser, 1 dropping funnel.

100% isopropyl alcohol in a 500d flask equipped with an inert gas inlet. The temperature of the flask was raised to 80°C under a nitrogen gas stream. Then, N as an unsaturated monomer
, N-dimethylaminoethyl acrylate 1st, methacrylic acid 5? , dicyclopentenyl acrylate 10?
, butyl acrylate 32f and methyl methacrylate 40) and azobisisobutyronitrile 2t as a catalyst were mixed and dissolved and uniformly dropped into the flask from a dropping funnel for 2 hours. After completion of the dropwise addition, the mixture was kept at 80° C. for 3 hours to complete polymerization and synthesize a copolymer. The polymerization rate is 9
It was more than 8 weight. After this.

Adjust pH to 11 with triethylamine, tap water to 50
Added P. The resulting neutralized resin solution had a nonvolatile content of 41% and a viscosity of 3 poise at 25°C.

Manufacturing example 6 N was added as an unsaturated monomer in the same manner as in Example 1.

N-dimethylaminoethyl acrylate 15? .

Methacrylic acid 5? , dicyclopentenyl acrylate 2
Neutralized resins were synthesized using Of, butyl acrylate 30) and methyl methacrylate 30). The prepared neutralized resin solution had a nonvolatile content of 41% by weight and a viscosity of 5 poise at 25°C.

Manufacturing example 7 N was added as an unsaturated monomer in the same manner as in Example 1.

N-dimethylaidiethyl acrylate 1o? .

Methacrylic acid 10P, dicyclopentenyl acrylate 10T, butyl acrylate 30P and methyl methacrylate 40? A neutralized resin was synthesized using The prepared neutralized resin solution had a nonvolatile content of 4α5 by weight and a viscosity of 15 poise at 25°C.

Comparative manufacturing example 3 N was added as an unsaturated monomer in the same manner as in Example 1.

N-dimethylaminoethyl acrylate 15? .

Methacrylic acid 5f, butyl acrylate 407 and methyl methacrylate 40? A neutralized resin was synthesized using The solution of this neutralized resin, which was rated as g*, had a non-volatile content of 41 parts by weight and a viscosity of 1.5 poise at 25°C.

Comparative Production Example 4 In the same manner as in Example 1, 10t of methacrylic acid, 10P of dicyclopentenyl acrylate, 40f of butyl acrylate, and 40% of methyl methacrylate were used as unsaturated monomers.
? A neutralized resin was synthesized using The solution of this neutralized resin adjusted to ij4 has a non-volatile content of 41.5% and a viscosity of 2%.
It was 18 poise at 5°C.

Comparative Production Example 5 N,N-dimethylaminoethyl acrylate 10f, dicyclopentenyl acrylate) 1 in the same manner as in Example 1
(1, co-produced using butyl acrylate 407 □ and methyl methacrylate 40? □ffi&$t
*5! l, &. e,o#! t＆'tlEu)'J
After neutralization with zps7'min, K residue occurred when it was diluted with tap water, and there was no water dilutability.

Examples 5-7 and Comparative Examples 3-4 Synthesized in Production Examples 5 to 7 and Comparative Production Examples 3 to 4.

Prepared neutralized resin solution 90 parts by weight (solid content) K epoxy resin (trimethylolproban trig 1) p) s
, ether) was added thereto, and water/inocvir alcohol = 171 (weight ratio) was blended to adjust the nonvolatile content to 25 parts by weight. The prepared adhesive composition was coated on a polypropylene film, dried at 80° C., and the polypropylene film was thermocompression bonded to cardboard using a roller press at that temperature.

Table 2 shows the test results.

Table 2. [ evaluation 0: G and polypropylene film are sufficiently adhered.

Δ: Paper and polypropylene film peel off when pulled off strongly.

×: There is almost no adhesion between the paper and the polypropylene film.

The resin composition according to the present invention uses less solvent.

It can be cured at room temperature or by low-temperature heating, and the coating film obtained when the cough resin composition is used as a coating has excellent coating properties such as solvent resistance, corrosion resistance, moisture resistance, water resistance, and hardness, and has excellent adhesive properties. Initial adhesive strength when used as an agent.

Excellent adhesive properties such as water resistance.

Claims (1)

[Claims] 1. (A) *3 to 20 parts by weight of an ethylenically unsaturated monomer having a tertiary amino group. (B) 3 to 20,111 parts of an ethylenically unsaturated monomer having a carboxyl group. (C) General formula m (in formula 1, R is hydrogen, lower alkyl group, or...
5 to 30 parts by weight of a dicyclopentadiene derivative represented by the following formula: R' is a divalent organic group, and n is 0 or 1. and ■) (4), a copolymer obtained by copolymerizing 30 to 89 parts by weight of another ethylenically unsaturated monomer copolymerizable with component (B) or (C). Neutralized resin (I) 9
8-60 parts by weight. and a water-dilutable epoxy resin + 1) 2 to 40 parts by weight of a water-dilutable resin composition.