JPS6144895B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-dilutable resin composition that can be cured by heating at room temperature or low temperature. In the paint, coating, and adhesive industries, there is a strong desire for resource-saving and energy-saving paints and adhesives as well as pollution-free products due to the recent rise in oil prices. Conventionally, thermosetting acrylic resins contain glycidyl groups, N-methylolamide groups, amide groups, carboxyl groups, hydroxyl groups, etc. as pendant groups, and these are blended with amino resins, epoxy resins, etc. Depending on the temperature, 150℃
It is used by curing reaction at higher temperatures. On the other hand, in fields where high-temperature treatment is not possible for building materials such as plastics, wood, concrete, and metal materials such as those used for automobile repair, so-called lacquers, which are made by using nitrified cotton, cellulose acetate butyrate, etc. in combination with acrylic resins and alkyd resins, are used. A type of paint that dries naturally is used. Such paints have drawbacks such as poor solvent resistance and poor weather resistance, and are unsuitable for fields that require high-performance coatings. Another drawback is that the amount of organic solvent in the paint is large, making it difficult to paint. Additionally, phthalic acid enamels and urethane paints are used in some applications. Phthalic acid enamels have problems with coating performance such as dryness and hardness, while urethane paints can provide high-quality coating properties, but there are problems with the toxicity of the isocyanate used, ease of handling, and price. On the other hand, water-based paints have problems such as slow drying, poor water resistance, poor corrosion resistance, and low hardness compared to organic solvent-based paints, and various improvements are being considered. Adhesives, particularly those used to bond polypropylene films to paper or printing paper, include resins such as chlorinated polypropylene, ethylene-vinyl acetate copolymers, rosin esters, polyurethanes, toluene, Examples include those dissolved in an organic solvent such as ethyl acetate, and those obtained by adding a polyisocyanate compound as a curing agent to this solution. During normal use, these organic solvent-based adhesives have a nonvolatile content of 15 to 30% by weight, and after being applied to an object, 70 to 85% by weight of the organic solvent is evaporated and dried, and then applied to other adherends. However, the organic solvents volatilized during the drying process are a major cause of air pollution, which has become a serious social problem, so there is a strong desire to reduce the amount of organic solvents used as much as possible. The present invention solves these problems. That is, the present invention comprises (a) 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 () (However, in the formula, R is hydrogen, a lower alkyl group, or a halogen, R' is a divalent organic group, and n is 0 or 1.) Dicyclopentadiene derivatives 5-
30 parts by weight, and (D) a copolymer obtained by copolymerizing 30 to 89 parts by weight of another ethylenically unsaturated monomer copolymerizable with component (A), (B) or (C). The present invention relates to a water-dilutable resin composition comprising a combination of 98 to 60 parts by weight of a neutralized resin and 2 to 40 parts by weight of a water-dilutable epoxy resin. The resin composition according to the present invention can be cured by heating at room temperature or low temperature (heating at 40 to 80°C). Examples of the ethylenically unsaturated monomer having a tertiary amino group, which is component (A) of the present invention, include N.N-dimethylaminoethyl acrylate, N.N-diethylaminoethyl acrylate, and N.N-dimethylaminoethyl acrylate. methacrylate, N/N-diethylaminoethyl methacrylate, vinylpyridine,
Vinylpyrroline, vinylquinoline, vinylisoquinoline, N・N-dimethylamino vinyl ether, 2-(N・N-dimethylamino)-4-vinylpyridine, trans-1・2-dipyridylethylene, 2-methyl-5-vinylpyridine , 3-cinnamoylpyridine, 2-methyl-5-cinnamoylpyridine, 4,4-diamino-2-vinyl-5
- Meliazine etc. The amount used is 3 to 20
The amount by weight is preferably 5 to 15 parts by weight; too little amount will result in insufficient curability, while too much amount will not only reduce water resistance but also shorten pot life. Examples of the ethylenically unsaturated monomer having a carboxyl group as component (B) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. The amount used is 3 to 20 parts by weight, preferably 4 to 8 parts by weight.
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. If there is too much, the water resistance will be poor and the pot life will be shortened. The dicyclopentadiene derivative represented by the general formula () as component (C) can be obtained by numbering the dicyclopentenyl group carbon atoms in the compound as shown in the following general formula ().

[Formula] is bonded to the 8th or 9th position. Here, R' is a divalent organic group having 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms. R' is preferably an alkylene group or

It is a group represented by [Formula]. Here, R'' and R are alkylene groups having 2 or more carbon atoms, and R'' and R may be the same or different, and m is an integer of 1 or more. Component (C) includes dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl-α-chloroacrylate, dicyclopentenoxyethyl acrylate, dicyclopentenoxyethyl methacrylate, dicyclopentenoxypropyl acrylate, Dicyclopentenoxyalkyl acrylate or methacrylate such as cyclopentenoxypropyl methacrylate, acrylic ester or methacrylic ester of polyalkylene glycol dicyclopentenyl monoether such as acrylic ester or methacrylic ester of diethylene glycol dicyclopentenyl monoether There is. The amount of component (C) used is 5 to 30 parts by weight, preferably 7 to 20 parts by weight. If the amount used is too small, the drying properties, corrosion resistance, and moisture resistance will be poor when the resin composition according to the present invention is used as a paint, and the initial adhesive strength will be insufficient when used as an adhesive. If the amount used 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. Furthermore, the viscosity of the resin increases, resulting in extremely poor workability. Component (D) includes ethylenically unsaturated monomers copolymerizable with component (A), (B) or (C), such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, Isobutyl acrylate, 2-
Alkyl acrylates such as ethylhexyl acrylate; methyl methacrylate; ethyl methacrylate; n-propyl methacrylate; vinyl esters of saturated monobasic acids such as vinyl acetate, vinyl propionate, vinyl stearate, epoxy group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, cyanation of acrylonitrile, methacrylonitrile, etc. vinyl, acrylamide,
Unsaturated amides such as methacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, 2-hydroxyethyl acrylate,
Hydroxyalkyl acrylates such as 2-hydroxypropyl acrylate, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, phosphoric acid group-containing unsaturated monomers such as ethyl acrylate phosphate and ethyl methacrylate phosphate, acetic acid Examples include vinyl esters of saturated monobasic acids such as vinyl and vinyl propionate, which may be used singly or in combination of two or more. In some cases, it is also possible to use a polyfunctional ethylenically unsaturated monomer such as ethylene glycol diacrylate in an amount of 0 to 2 parts by weight. Among the copolymerizable ethylenically unsaturated monomers used as component (D), alkyl acrylate, alkyl methacrylate,
Styrenic monomers are preferred. Furthermore, the monomer having a reactive functional group other than a double bond is preferably used in a proportion of 0 to 30% by weight, particularly in a proportion of 0 to 10% by weight based on the total amount of components (A) to (D). Preferably used in If there is too much of a monomer having such a reactive functional group, the coating film properties (water resistance, moisture resistance, chemical resistance, etc.) tend to deteriorate when used as a coating material. Further, in order to improve adhesion, it is preferable to use hydroxyalkyl acrylate, hydroxyalkyl methacrylate, unsaturated amide, etc. among monomers having such reactive functional groups.
Furthermore, as component (D), a copolymer of components (A) to (D) has a glass transition point of 30 to 70, which is particularly preferable for paints.
℃, hard monomers (a) such as methyl methacrylate, ethyl methacrylate, and styrene and soft monomers (b) such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are mixed into (a)/ It is particularly preferable to use (b) in a weight ratio of 80/20 to 50/50. Components (A), (B), (C) and (D) can be obtained by copolymerizing by solution polymerization, bulk polymerization, etc., using well-known methods. The polymerization temperature is approximately 50 to 150℃,
As a polymerization catalyst, benzoyl peroxide, t
- Peroxides such as butyl peroxide and cumene hydroperoxide, azobisisobutyronitrile, azobisisobutyl-valeronitrile, etc. can be used, and the amount used is 0.1 to 100 parts by weight of the total monomer amount. 5 parts by weight. Molecular weight regulators such as mercaptan, carbon tetrachloride, and carbon tetrabromide can also be used if necessary. It is preferable to carry out the copolymerization in the presence of a water-soluble organic solvent because after the polymerization, the copolymer can be neutralized without being isolated and used as it is in the resin composition of the present invention. In this case, the water-soluble organic solvent is preferably used so that the copolymer concentration is 30 to 70% by weight. Examples of the water-soluble organic solvent include ethanol, isopropyl alcohol, isobutanol, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyro cellosolve, 3-methyl-3-methoxybutanol, methyl carbitol, ethyl carbitol, butyl carbitol, and the like. Can be used alone or in combination of two or more. The copolymer thus obtained is neutralized with a neutralizing agent to obtain a neutralized resin (). The degree of neutralization is preferably 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. Water may be added during neutralization. As the epoxy resin (), one that can be diluted with water can be used. Here, "water dilutable" means that it is soluble in a mixed solvent of water/water-soluble organic solvent=5/5 to 8/2 (weight ratio). Examples of the epoxy resin () include glycerol polyglycidyl ether, trimethylolethane polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. to alcohol,
It is possible to use an epoxy resin, etc., which are adducted with ethylene oxide or propylene oxide and then epoxidized at the terminal. The epoxy resin of the present invention may partially contain a compound having only one epoxy group per molecule in an amount of 10% by weight or less, preferably 5% by weight or less. Neutralized resin () and epoxy resin () are
The weight ratio of ()/() is 98/2 to 60/40, preferably 95/5 to 80/20.
If ()/() exceeds 98/2, curing will be insufficient and sufficient coating properties or adhesive properties will not be obtained, while if it is less than 60/40, initial drying properties or initial adhesive strength will decrease. In the present invention, it is preferable that the neutralized resin () and the epoxy resin () are mixed for the first time at the time of use to form a resin composition. If mixed in advance, it will harden more easily during storage. It is preferable to mix the neutralized resin () with water and/or a water-soluble organic solvent in advance. In this case, water/
It is preferable that the water-soluble organic solvent is dissolved in a mixed solvent of 80/20 (weight ratio) or less. If the solid content is too high, the viscosity will be high and workability will be reduced, and if the solid content is too low, the resin concentration will be too low. A mixed solvent of water and a water-soluble organic solvent has a ratio of water/water-soluble organic solvent of 80/
If it exceeds 20, it is undesirable because it tends to separate into a solvent phase and a resin phase. Water/water-soluble organic solvent weight ratio 50/50
It is preferable to set the ratio above, particularly preferably 70/30 to 60/40. The epoxy resin (2) is preferably used as it is 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 or less.
It is used after being dissolved in a mixed solvent of 20 to 50/50, particularly preferably 70/30 to 60/40. When the ratio exceeds 80/20, 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 a ratio of 50/50 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 increases and workability decreases, which is not preferable. If it is less than 30% by weight, the resin viscosity will be low, which is not preferred in practice. In the resin composition according to the present invention, lead naphthenate, zinc naphthenate, cobalt naphthenate, zirconium naphthenate, lead octate, cobalt octenoate, zirconium octenoate, etc. are added to the neutralized resin () as a metal dryer. with the amount of metal
Preferably, it is added in an amount of 0.01 to 1% by weight. It is preferable to add the metal dryer to the neutralized resin (2) in advance, or add it at the time of mixing the neutralized resin (2) and the epoxy resin (2). Note that the resin composition according to the present invention exhibits excellent coating film properties and adhesive properties even without the addition of a metal dryer. The resin composition according to the present invention may optionally contain a water-soluble or water-dispersible acrylic resin, a water-soluble or water-dispersible alkyd resin, a water-dispersible vinyl acetate polymer or copolymer, rosin, rosin ester, ceramics, etc. etc. can be combined. The paint obtained using the resin composition of the present invention can be applied by dipping, brushing, spraying, roll coating, etc.
Can be applied to surfaces such as paper, textiles, plastics, ceramics, iron, and non-ferrous metals. Production Example 1 100g of isopropyl alcohol is placed in a 500ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and inert gas inlet, and the temperature of the flask is raised to 80°C under a nitrogen gas stream. Next, 8 g of N.N-dimethylaminoethyl acrylate, 5 g of methacrylic acid, 10 g of dicyclopentenyl acrylate, 10 g of styrene, 37 g of methyl methacrylate, and 30 g of butyl acrylate as unsaturated monomers, and 1.5 g of azobisisobutyronitrile as a catalyst were mixed. The dissolved liquid is uniformly dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was kept at 80° C. for another 3 hours to complete polymerization and synthesize a copolymer. The polymerization rate was 98% by weight or more.
Thereafter, the pH was adjusted to 10 with triethylamine, and 50 g of tap water was added. The resulting neutralized resin solution had a nonvolatile content of 41% by weight and a viscosity of 8 poise at 25°C. Production Example 2 In the same manner as in Example 1, N.
N-dimethylaminoethyl acrylate 15g, methacrylic acid 5g, dicyclopentenyl acrylate 10g, styrene 10g, methyl methacrylate
Using 30g and 30g of butyl acrylate,
A neutralized resin was synthesized. The prepared neutralized resin solution had a nonvolatile content of 40% by weight and a viscosity of 9.5 poise at 25°C. Production Example 3 In the same manner as in Example 1, N.
8 g of N-dimethylaminoethyl acrylate, 10 g of methacrylic acid, 10 g of dicyclopentenyl acrylate, 10 g of styrene, 32 g of methyl methacrylate
A neutralized resin was synthesized using g and 30 g of butyl acrylate. The prepared neutralized resin solution had a nonvolatile content of 40.5% by weight and a viscosity of 9 poise. Production Example 4 In the same manner as in Example 1, N.
N-dimethylaminoethyl acrylate 8g, methacrylic acid 5g, dicyclopentenyl acrylate 20g, styrene 10g, methyl methacrylate 27
A neutralized resin was synthesized using g and 30 g of butyl acrylate. The prepared neutralized resin solution had a nonvolatile content of 41% by weight and a viscosity of 12 poise. Comparative Production Example 1 In the same manner as in Example 1, 10 g of methacrylic acid and dicyclopentenyl acrylate were used as unsaturated monomers.
10g, styrene 10g, methyl methacrylate 40g
and 30 g of butyl acrylate to synthesize a neutralized resin. The prepared neutralized resin solution had a nonvolatile content of 41% by weight and a viscosity of 7 poise. Comparative Production Example 2 In the same manner as in Example 1, N.
A neutralized resin was synthesized using 8 g of N-dimethylaminoethyl acrylate, 5 g of methacrylic acid, 10 g of styrene, 47 g of methyl methacrylate, and 30 g of butyl acrylate. The prepared neutralized resin solution had a nonvolatile content of 40% by weight and a viscosity of 5 poise. Comparative Production Example 3 In the same manner as in Example 1, N.
N-dimethylaminoethyl acrylate 8g, methacrylic acid 2g, dicyclopentenyl acrylate 10g, styrene 10g, methyl methacrylate 40g
A copolymer was synthesized using 30 g of butyl acrylate. This copolymer is triethylamine
Cloudiness occurred when tap water was added after adjusting the pH to 10, and there was no water dilutability. Examples 1 to 4 and Comparative Examples 1 to 2 Trimethylolpropane, a water-dilutable polyfunctional epoxide compound, was added to 85 parts by weight (solid content) of the resin prepared in Production Examples 1 to 4 and Comparative Production Examples 1 to 2. 15 parts by weight of polyglycidyl ether is blended, and cobalt naphthenate is distributed as a metal dryer so that the amount of metal is 0.05 parts per 100 parts by weight (solid content) of the neutralized resin solution, and water dilution according to the present invention is performed. A possible resin composition was obtained. Furthermore, titanium white was blended so that the blended resin (solid content)/titanium white = 60/40 (weight ratio) to create white enamel. The properties of this white enamel are shown in Table 1. In addition,
When testing properties, the base material is Bonderite #1077
Using a treated steel plate, everything except drying is done at room temperature5.
Characteristics were measured after drying in the sun.

[Table] Production Example 5 Charge 100 g of isopropyl alcohol into a 500 ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and inert gas inlet, and heat the flask to 80°C under a nitrogen gas stream. Next, as unsaturated monomers, 15 g of N.N-dimethylaminoethyl acrylate, 5 g of methacrylic acid, 10 g of dicyclopentenyl acrylate, and butyl acrylate were added.
Mixing 32 g and 40 g of methyl methacrylate and 2 g of azobisisobutyronitrile as a catalyst,
Pour the dissolved liquid evenly into the flask from the dropping funnel.
Drip for an hour. After the dropwise addition was completed, the mixture was kept at 80° C. for another 3 hours to complete the polymerization and synthesize a copolymer. The polymerization rate was 98% by weight or more. After this, the pH was adjusted to 10 with triethylamine, and 50 g of tap water was added. The resulting neutralized resin solution had a nonvolatile content of 41% and a viscosity of 25%.
It was 3 poise at ℃. Production Example 6 In the same manner as in Example 1, N.
A neutralized resin was synthesized using 15 g of N-dimethylaminoethyl acrylate, 5 g of methacrylic acid, 20 g of dicyclopentenyl acrylate, 30 g of butyl acrylate, and 30 g of methyl methacrylate. The prepared neutralized resin solution has a non-volatile content of
41% by weight, and the viscosity was 5 poise at 25°C. Production Example 7 In the same manner as in Example 1, N.
A neutralized resin was synthesized using 10 g of N-dimethylaminoethyl acrylate, 10 g of methacrylic acid, 10 g of dicyclopentenyl acrylate, 30 g of butyl acrylate, and 40 g of methyl methacrylate. This prepared neutralized resin solution contains non-volatile content.
40.5% by weight, and the viscosity was 3.5 poise at 25°C. Comparative Production Example 3 In the same manner as in Example 1, N.
A neutralized resin was synthesized using 15 g of N-dimethylaminoethyl acrylate, 5 g of methacrylic acid, 40 g of butyl acrylate, and 40 g of methyl methacrylate. The prepared neutralized resin solution had a nonvolatile content of 41% by weight and a viscosity of 1.5 poise at 25°C. Comparative Production Example 4 In the same manner as in Example 1, 10 g of methacrylic acid and dicyclopentenyl acrylate were used as unsaturated monomers.
A neutralized resin was synthesized using 10 g of methacrylate, 40 g of butyl acrylate, and 40 g of methyl methacrylate.
This prepared solution of neutralized resin has a non-volatile content of 41.5
The viscosity in weight percent was 3.8 poise at 25°C. Comparative Production Example 5 A copolymer was synthesized in the same manner as in Example 1 using 10 g of N.N-dimethylaminoethyl acrylate, 10 g of dicyclopentenyl acrylate, 40 g of butyl acrylate, and 40 g of methyl methacrylate. This copolymer becomes cloudy when diluted with tap water after being neutralized with triethylamine.
It was not dilutable with water. Examples 5 to 7 and Comparative Examples 3 to 4 Synthesis in Production Examples 5 to 7 and Comparative Production Examples 3 to 4,
Add 10 parts by weight of epoxy resin (trimethylolpropane triglycidyl ether) to 90 parts by weight (solid content) of the prepared neutralized resin solution, and mix with water/isopropyl alcohol = 1/1 (weight ratio) to make it non-volatile. It was adjusted to 25% by weight. After applying this adjusted adhesive composition to polypropylene film,
The polypropylene film was dried at 0.degree. C., and the polypropylene film was thermocompression bonded to the cardboard using a roller press at that temperature. The test results are shown in Table 2.

[Table] The resin composition of the present invention uses less solvent and can be cured at room temperature or by low-temperature heating. It has excellent coating properties such as hardness, moisture resistance, water resistance, and hardness, and when used as an adhesive, it has excellent adhesive properties such as initial adhesive strength and water-resistant adhesiveness.

Claims (1)

[Scope of Claims] 1 (A) 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 () (However, in the formula, R is hydrogen, a lower alkyl group, or a halogen, R' is a divalent organic group, and n is 0 or 1.) Dicyclopentadiene derivatives 5-
30 parts by weight, and (D) a copolymer obtained by copolymerizing 30 to 89 parts by weight of another ethylenically unsaturated monomer copolymerizable with component (A), (B) or (C). A water-dilutable resin composition comprising a combination of 98 to 60 parts by weight of a neutralized resin () and 2 to 40 parts by weight of a water-dilutable epoxy resin ().