JPS5821410A - Resin composition curable at room temperature or under heating at low temperature - Google Patents

Abstract

PURPOSE:The titled composition that is made by combining an epoxy resin with a copolymer from ethylenically unsaturated monomers containing tertiary amino groups, carboxyls and dicyclopentadiene derivatives respectively, thus being suitably used as a paint giving a high-performance coating or as an adhesive. CONSTITUTION:The objective composition is obtained by adding (A) 2-40pts.wt. of an epoxy compound such as sorbitol polyglycidyl ether to (B) 98-60pts.wt. of a copolymer from (a) 3-20pts.wt. of an ethylenically unsaturated monomer bearing tertiary amino groups such as N,N-diethylaminoethyl acrylate, (b) 1-20pts. wt. of a carboxyl-containing monomer such as acrylic or methacrylic acid, (c) 5-30pts.wt. of a compound of the formula (R is H, lower alkyl, halogen; R' is difunctional organic group; n is 0, 1) such as dicyclopenenyl acrylate and (d) 30- 91pts.wt. of monomers copolymerizable with the above monomers such as styrene.

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, coating, and adhesive industries, due to the recent rise in oil prices, paints and adhesives that are pollution-free, resource-saving, and energy-saving are eagerly desired.

Conventionally, thermosetting acrylic resins are made to contain pendant groups such as glycidyl groups, N-methylinyl groups, amide groups, carboxyl groups, and hydroxyl groups to produce amino resins.

It is used by blending an epoxy resin or the like and curing it at a high temperature of 130'IC or higher, and in some cases, 150°C or higher.

On the other hand, in fields such as plastics, wood, concrete, etc., and metal materials such as automobile repair, which cannot be treated at high temperatures, they are used in combination with pipe acrylic resins, alumina resins, etc. .

An air-drying paint called lacquer is used. Such paints have poor solvent resistance. Due to its poor weather resistance, it is unsuitable for fields that require high-performance coatings. Additionally, the amount of organic solvent in the paint is large, making it difficult to paint.

-@oi@Hyophthalic acid enamel and urethane paint are also used appropriately. Phthalate enamel has dryness, hardness, etc. There is a problem with film performance, and although urethane paints can provide high film properties, the polyisocyanate used is toxic.

There are problems with handling and price.

Therefore, as a result of intensive studies, the inventors of the present invention found that it is possible to provide an m film that cures at room temperature or low temperature heating and has ILI+ performance, and can also be used as an adhesive, resulting in low pollution, resource saving, and labor saving. The present invention provides a unique resin composition.

(A) 3 to 20 parts by weight of an ethylenically unsaturated monomer having a tertiary amino group (B) 1 to 20 parts by weight of an ethylenically unsaturated monomer having a carboxy 7L-group (C) General formula (1 ) n ij Q or l. ) Compound 5
~30 parts by weight and ■) A comonomer obtained by copolymerizing 30 to 91 parts of other ethylenically unsaturated monomers copolymerizable with component (A), (B), or (C) ( 1) A resin composition which can be cured by heating at room temperature or low temperature is prepared by combining 98 to 60 parts by weight and 2 to 40 parts by weight of epoxy resin (Otori).

The resin composition related to the INK of the present invention is heated at room temperature or at a low temperature (40
It can be cured by heating up to 80°C and exhibits excellent properties.

Examples of the ethylenically unsaturated monomer having a tertiary akino group, which is the carrier component of the present invention, include N,N-dimethylamineethyl acrylate), N,N-diethylaminoethyl acrylate, N,N- Diethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, vinylpyridine, vinylviroline, vinylquinoline,
Vinylisoquinoline, N,N-dimethylamino vinyl ether, 2-(N,N-dimethylamino)-4-vinylpyridine, trans-1,2-dipyridylethylene,
2-methyA-5-vinylpyridine.

These include 3-cinnamoylpyridine, 2-methyl-5-cinnamoylpyridine, 4,4-diamino-2-vinyl-5-triazine, and the like. The amount used is 3 to 20 parts by weight,
Preferably from 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. 11! The dosage is 1-20 parts by weight, preferably 2-8 parts by weight.

If it is too small, the curing reaction will be slow, which is a practical problem. If the amount is too high, the water resistance will be poor and the pot life will be shortened.

The dicyclopentadiene derivative represented by the general formula (1) as the component (C) is bonded to the position shown in the following general formula (I) when the dicyclopentenyl base atoms in the compound are numbered. There is. Here, R' is a divalent organic group with a carbon number of 1 to 18. Preferably it is 2-12. R
' is preferably an alkylev group or 1,000BIN-〇+1
It is a group represented by li-Bllll-.

Therefore, 8' and rcn'' are alkylene groups having a leg prime number of 2 or more, and R# and R1 may be the same or different.

m is an integer of 1 or more.

Specific examples of component (C) include dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl-α-chloroacrylate, dicyclopentenoxyethyl acrylate, dicyclopentenoxyethyl methacrylate, and dicyclopentenyl methacrylate. Polyalkylene glycol dicyclopentenyl monoethers such as ethyl acrylate, dicyclopentenoxyethyl acrylate, etc., dicyclotetrapentenyl acrylates or methacrylates, diethylene glycol dicyclobentenyl monoether acrylic acid esters, or methacrylic acid esters. There are acrylic esters and methacrylic esters.

The amount of component (C) used is 5 to 30 parts by weight, preferably 7 to 30 parts by weight.
The amount is 201L parts. If the amount is too small, the resin composition of the present invention will have poor drying properties, and will also have poor corrosion resistance and moisture resistance. On the other hand, if the amount is too large, the viscosity of the resin will increase, resulting in extremely poor workability and poor coatability of the coating film. ■) Convict which is an ingredient.

Ethylenically unsaturated monomers copolymerizable with components (B) and (C) include methyl acrylate, ethyl acrylate, and n-propyl acrylate.

inglovir acrylate, n-butyl acrylate,
Alkyl acrylates such as inbutyl acrylate and 2-ethylhexyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, inglovir methacrylate, n-butyl methacrylate, inbutyl methacrylate, and 2-ethylhexyl methacrylate; Styrene monomers such as styrene, vinyltoluene, α-methylstyrene, and vinyl acetate.

- Vinyl esters of saturated basic acids such as vinyl propionate and vinyl stearate; unsaturated monomers containing polyamide groups such as glycidyl acrylate and glycidyl methacrylate; and acrylic nitriles.

Vinyl cyanide, acrylamide, methacrylamide, N-methyl p-lylacrylamide, such as methacrylate trile. Unsaturated amides such as N-butoxymethylacryland; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydocarbonate xyglobyl methacrylate; Examples include phosphoric acid group-containing unsaturated monomers such as acid ethyl acrylate and phosphoric acid ethyl methacrylate, and these may be used alone or in combination of two or more.

Optionally, 0 to 2 parts by weight of polyfunctional ethylenically unsaturated monomers such as ethylene glycol diacrylate may be used.

Q)) Among the copolymerizable ethylenically unsaturated monomers used as the component, alkyl acrylates, alkyl methacrylates, and styrenic monomers are preferred. Monomer is a prison~Q))
It is preferably used in a proportion of 0 to 30 weight sO in the total amount of components.

In particular, it is preferably used in a proportion of 0 to 10% by weight.
If there is too much of a monomer having such a reactive functional group, there is a tendency for the chemical resistance of the paint to deteriorate. ″
*9. For rounding to improve adhesion? Among monomers having reactive functional groups such as -, it is preferable to use hydroxyalkyl acrylates, hydroxyalkyl methacrylates, unsaturated amides, and the like.

Furthermore, as component (1), hard monomers such as methyl methacrylate, ethyl methacrylate, and styrene are used so that the copolymer (1) has a glass transition point of 30 to 70°C, which is ideal for paints. (51)/(b) of monomer (1) and soft monomer (b) such as ethyl acrylate, butyl acrylate (9v-), 2-ethylhexyl acrylate, etc.
It is particularly preferable to use it in a weight ratio of 80/20 to 5015G.

Components (B1. (C) and ■) are obtained by copolymerization by solution polymerization, bulk polymerization, etc., using well-known methods. The polymerization temperature is about 50-150°C.

Benzoyl peroxide is used as a polymerization catalyst.

Peroxides such as t-butyl peroxide and cumenocarbonate peroxide, azobisisobutyronitrile, and azobisisobutylvaleronitrile can be used, and the amount used is 0.0% per 100 parts by weight of the total monomers. It is 1 to 5 parts by weight. Must-Jl! Depending on the mercaptan, carbon tetrachloride, li! A molecular weight regulator such as W carbon bromide may be used.

Preferably, the copolymerization is carried out in an organic solvent.

Examples of the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, and methyl ethyl ketone.

Examples include methyl isobutyl ketone, isopropyl alcohol, and ethyl cellosolve. As the amount of organic solvent used,
It is preferable that the concentration of the resulting copolymer be 30 to 70 times -.

The epoxy resin of the present invention is an epoxy compound having two or more epoxy groups in the molecule.

A portion of the compound may contain a compound having only one epoxy group in one molecule. For example, glycerol diglycidyl ether, glycerol triglycidyl ether,
Polyglycidyl ethers of aliphatic polyhydric alcohols such as pandiglycidyl ether, trimethylolpropane triclycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triclycidyl ether, diglycerol glycidyl ether, sorbitol tetraglycidyl ether, bisphenol Polyglycidyl ethers of polyhydric phenols such as bisphenol glycidyl ether obtained by the reaction of humans and epichlorohydrin, phenol novolac-rich polyglycidyl ether, polyglycidyl esters of aromatic polybasic acids such as phthalic acid diglycidyl ester, and alicyclic polyesters. Examples include epoxy compounds, copolymers of glycidyl group-containing unsaturated monomers such as glycidyl acrylate, and glycidyl methacrylate. The thick poxy resin (1) may contain a compound having only one epoxy group in the molecule in an amount of 10 parts by weight or less, preferably 5 parts by weight or less.

Copolymer (11) and epoxy resin (compounding ratio of the group is (I)
/(I) is 98/2 to 60/40 (weight ratio), preferably 9515 to 80/20. (1)/(When the ratio exceeds 98/2, curing is insufficient. Furthermore, the resin composition according to the present invention can be used as a paint to obtain a coating film with solvent resistance and corrosion resistance. Metal dryers, such as lead naphthenate, zinc naphthenate, cobalt naphthenate.

When naphthenic zirconium, lead octenoate, zinc octenoate, zirconium octenoate, cobalt octenoate, etc. are appropriately selected and added to the copolymer (1) in a metal amount of approximately α01 to 1 part by weight. , can produce very advanced characteristics.

The resin composition according to the present invention further includes Kll# material, plasticizer 1
It is also possible to add a coloring agent or to mix a wide range of resins such as modified amino resins, polyester resins, and alkali resins.

When the resin composition according to the present invention is used as a paint.

It can be painted using methods such as dipping, buffing, spray molding, and roll painting.

It can be applied to the surfaces of paper, textiles, plastics, ceramics, iron, and non-ferrous metal rings. The resin composition according to the present invention can also be used as an adhesive.

Preferably, it is a human fat composition. If mixed in advance, it will harden more easily during storage. In that case, it is preferable that the copolymer f1) and the epoxy resin (1) are each dissolved in an organic solvent in advance.

As the organic solvent, those mentioned above can be used.

Manufacturing example 1 Stirrer, temperature needle, reflux condenser, 1 dropping funnel.

Toluene 100 in a 9500-flask equipped with an inert gas inlet? The flask was heated to 100 mL under a nitrogen gas stream.
Increase temperature to ℃.

Next, as an unsaturated monomer, N,N-dimethylaminoethyl acrylate 16? , methacrylic acid 6? .

Dicyclopentenyl acrylate 20? , styrene 11
8t and butyl acrylate 40? and azobisisobutyronitrile 2? as a catalyst. A mixed solution of tertiary-butyl peroxide IP and tertiary-butyl peroxide IP is uniformly dropped into the flask from the dropping funnel over a period of 2 hours. 0 After the completion of dropping 1
The temperature was raised to 10°C and kept for 3 hours to complete polymerization. The polymerization rate was 98 kg upwind, and then toluene was 100 kg.
Dilute with F and mourn.

The resulting copolymer solution had a nonvolatile content of 50% by weight and a viscosity of 7 boads at 25°C.

Production Example 2 In the same manner as in Example 1, N,N-dimethylaminoethyl acrylate 30? , methacrylic acid 6
A copolymer was synthesized using F, dicyclopentenyl acrylate) 20f, styrene 104t and butyl acrylate) 40f, and then diluted with toluene. The nonvolatile content of the copolymer solution was 51% by weight. The viscosity at this time was 11 poise at 25°C.

Production Example 3 In the same manner as in Example 1, the unsaturated monomers were N,N-dimethylaminoethyl acrylate (16) e 6t methacrylic acid, dicyclopentenyl acrylate (40)? ,
Styrene 9B? A copolymer was synthesized using Pt- and butyl acrylate). This was followed by dilution with toluene. The copolymer solution had a nonvolatile content of 49% by weight and a viscosity of 15 poise at 25°C.

Comparative Production Example 1 In the same manner as in Example 1, methacrylic acid 6? was used as the unsaturated monomer. , dicyclopentenyl acrylate 20f, styrene 134? A copolymer was synthesized using 40t of butyl acrylate. After this, it was diluted with toluene.

Copolymer Solution Company.

The nonvolatile content is 50% by weight, and the viscosity is 3 poise at 25°C.

Comparative Production Example 2 Copolymerization was carried out in the same manner as in Example 1 using N,N-dimethylaminoethyl acrylate 16F, dicyclopentenyl acrylate 20), styrene 12tP, and butyl acrylate 40F as unsaturated monomers. Combine the union and make a circle. After this, it was diluted with toluene. The copolymer solution is mixed with non-volatile matter of 4&5% by weight, and the viscosity at this time is 25°C.
It was 4.5 poise.

Comparative Production Example 3 In the same manner as in Example 1, N,N-dimethylaminoethyl acrylate 16? was used as the unsaturated monomer. , methacrylic acid 6
f, styrene 138t and butyl acrylate) 4(l
Synthesize copolymerization using 9.

After this, it was diluted with toluene. The copolymer solution has a nonvolatile content of 49% by weight, and the viscosity at 25°C is &
5 poise and nine.

Examples 1 to 3 and Comparative Examples 1 to 3 Prepared in Production Examples 1 to 3 and Comparative Production Examples 1 to 3, 10 parts of sorbitol polyglycidyl ether, which is an aliphatic polyepoxide compound, was added to 90 parts by weight of the resin solid mass. As a metal dryer, cobalt naphthenate was added to 100 parts by weight of the resin 1iIWi so that the metal amount was α05 parts by weight. Further, white enamel was prepared by blending titanium white so that the blended resin (It DAIBU)/titanium white = 60/40 Th (weight ratio). After this, the characteristics were tested and the results are shown in Table 1. In addition, in the test, a steel plate treated with Acid Blast Donna 144 was used as the base material, and the test was performed after being left to dry at room temperature for 3 days except for drying properties.

The resin composition according to the present invention can be cured by heating at room temperature or low temperature, and when it is applied to a coating, the resulting coating film has excellent solvent resistance, corrosion resistance, moisture resistance, and hardness.

Claims (1)

[Claims] L(A) 3 to 20 parts by weight of an ethylenically unsaturated monomer having a tertiary aono group (Bl 1 to 20 parts by weight of an ethylenically unsaturated monomer having a carboxyl group (C) General formula + 11 General formula
5 to 30 parts by weight of a compound to be removed by (9) and (B) and 30 to 91 parts by weight of another ethylenically unsaturated monomer copolymerizable with component (C). A resin composition which can be cured by heating at room temperature or low temperature, which is made by combining a copolymer obtained by polymerization (floss ~ 60 parts by weight) and epoxy resin (1) 2 to 40 parts by weight.