JPH04161414A - Vinyl ester resin composition, its production and coating material containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject resin applicable to metal, wood, plastics, etc., and having excellent curability with ultraviolet ray, etc., adhesiveness heat- resistance and hardness by reacting a hydroxyl-containing vinyl ester resin with an unsaturated isocyanate in air at a temperature below a specific level. CONSTITUTION:A vinyl ester resin modified with an unsaturated isocyanate [preferably modified with an unsaturated isocyanate of formula (R1 is H or CH3; R2 is alkylene or diisocyanate residue)] is produced by reacting a hydroxyl- containing vinyl ester resin (preferably having a hydroxyl value of 22-99) with an unsaturated isocyanate (preferably isocyanatoethyl acrylate) preferably at a weight ratio of (95-80):(5-20) in air at <=170 deg.C (preferably 60 deg.C). A resin composition is obtained by compounding a polymerization initiator to the above resin.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a vinyl ester resin composition that can be applied to metals, wood, plastics, etc. and has excellent UV curability, adhesiveness, heat resistance, and hardness, and its production. The present invention relates to a method and a paint using the same.

(Prior Art) Various methods have been proposed for obtaining a cured film having functions such as hardness, heat resistance, and workability by irradiation with ultraviolet rays, etc., and are now entering the stage of practical use.

Unsaturated polyester resins have traditionally been used as UV-curable paints for wooden furniture.

The UV-curable unsaturated polyester resin that has been commonly used for wooden furniture has slow photo-curing properties, and at practical speeds tends to be insufficiently cured, meaning the three-dimensional structure is incomplete, resulting in poor heat resistance, adhesive properties, etc. It had some disadvantages.

(Problems to be Solved by the Invention) The present invention aims to solve the drawbacks of these conventionally known ultraviolet curable unsaturated polyester resins, that is, to provide a resin composition that has improved curability, adhesiveness, and heat resistance. be.

(Means for Solving the Problems) In order to solve the above problems, the present inventor has completed the present invention as a result of intensive research.

That is, the present invention provides a vinyl ester resin composition characterized by comprising an unsaturated isocyanate-modified vinyl ester resin and a polymerization initiator; A vinyl ester resin composition modified with an isocyanate compound, R.

CH, =C-C-0-R, -NCO However, R,:H,CH.

R2: represents an alkyl group, a diisocyanate residue.

Further, a method for producing an unsaturated isocyanate-modified vinyl ester resin, which is characterized by reacting a vinyl ester having a hydroxyl group with an unsaturated isocyanate in air at a temperature of 170°C or lower, preferably a method for producing a vinyl ester resin having a hydroxyl group, preferably a hydroxyl value of the vinyl ester having a hydroxyl group. The object of the present invention is to provide a manufacturing method characterized in that the number is 22 to 99, and a paint characterized in that a vinyl ester resin composition is used.

(Structure) The unsaturated isocyanate-modified vinyl ester resin of the present invention is modified by addition-reacting the unsaturated isocyanate compound represented by the above structural formula with the terminal and side chain hydroxyl groups of the vinyl ester resin.

The vinyl ester resin used in the present invention is produced by a known method, and specifically, an epoxy acrylate resin obtained by using an epoxy resin and acrylic acid or methacrylic as components, or a saturated dicarboxylic acid and an epoxy acrylate resin. Unsaturated polyester obtained by using an unsaturated dicarboxylic acid or either dicarboxylic acid and a polyhydric alcohol as a component, unsaturated polyester obtained by using a saturated polyester and an epoxy compound containing an α,β-unsaturated carboxylic acid ester group as a component. Saturated polyester acrylate, saturated polyester acrylate.

Examples of saturated dicarboxylic acids that do not have active unsaturated groups include orthophthalic acid, isophthalic acid, terephthalic acid,
Examples include tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples of the unsaturated dicarboxylic acid having an active unsaturated group include fumaric acid, maleic acid, and itaconic acid.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, 1,5
-bentanediol, 1,3-butanediol, 1.
Polyhydric alcohols such as 6-hebosanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol, propylene oxide adduct of bisphenol A, and ethylene oxide adduct of bisphenol A are used as alcohol components. That's what you get.

Typical examples of the epoxy resin include bisphenol A diglycidyl ether, its high molecular weight homologues, and novolac type polyglycidyl ethers. α
, glycidyl methacrylate is a typical example of the epoxy compound containing a β-unsaturated carboxylic acid ester group.

The unsaturated group equivalent of the vinyl ester resin is preferably 100 to 600. If the unsaturated group equivalent is less than 100, it cannot be synthesized, and if it is more than 600, the coating film becomes too hard and cracks occur. In addition, in the case of saturated polyester acrylate and unsaturated polyester acrylate,
The acid value of the saturated polyester and unsaturated polyester used is preferably 17 to 85.

In the present invention, polymerizable monomers such as styrene are generally used, but are not limited to styrene, and include vinyltoluene, α-methylstyrene, chlorostyrene, hydrarylyl cyanurate, etc. Vinyl monomers or vinyl oligomers capable of crosslinking with the above resins, such as allyl compounds, may be used alone or in combination.

The use of a polymerizable monomer such as styrene in the present invention is important in terms of workability and hardness of the cured coating film, and the amount is 0 to 60 parts by weight, preferably 20 to 50 parts by weight.

Vinyl ester resins require hydroxyl groups to add isocyanate groups. The content of hydroxyl groups may be determined by the hydroxyl value. The hydroxyl value is preferably 22 to 99. A resin with a hydroxyl value lower than 22 will have poor ultraviolet curability, and a resin with a hydroxyl value higher than 99 will not have a sufficient value to strengthen the coating film.

When producing the resin of the present invention, the above vinyl ester resin and an unsaturated isocyanate compound are mixed in an air atmosphere for 1
It is obtained by heating to 70°C or less, preferably about 60°C to carry out a urethanization reaction, and adding the compound to the resin. Completion of the reaction is determined by the NCO content, and the reaction is terminated when the NGO content becomes 1% by weight or less.

In order to accelerate this urethanization reaction, for example, tertiary amines such as triethylamine or tributylamine,
Alternatively, there is no hindrance to the use of known and commonly used catalysts such as dibutyltin dilaurate or dibutyntin acetate.

The charging ratio of the vinyl ester resin and the unsaturated isocyanate compound is determined by the hydroxyl value of the vinyl ester resin and the NCO equivalent of the unsaturated isocyanate. All you have to do is determine the number of moles of .

The amount of vinyl ester resin and unsaturated isocyanate compound to be charged is preferably 95 to 80 parts by weight of resin and 5 parts by weight of compound.
~20 parts by weight.

Due to operational problems, the resin of the present invention may contain other compounds having (meth)acryloyl groups within a range of 50% by weight or less based on the solid content of the resin. Particularly preferred as this compound are bisphenol A or
Bisphenol-based epoxy di(meth)acrylates such as dioxydiethylene glycol di(meth)acrylate of bisphenol F. In addition, trimethylolpropane tri(meth)acrylate, hentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. may be used. Furthermore, if the ratio of the above-mentioned (meth)acryloyl group-containing compound to the resin solid content is too large, the heat resistance and mechanical strength of the cured product will decrease, which is not preferable.

Note that in the present specification, the term "(meth)acrylate group" is an abbreviation for "acrylate and/or methacrylate group."

A particularly preferred polymerization initiator used in this invention is a photopolymerization initiator.

Further, if necessary, a thermal polymerization initiator may be used alone or in a mixed system with a photopolymerization initiator.

Examples of photopolymerization initiators include benzoin ethers such as benzoin alkyether, benzophenone, benzyl,
Benzophenones such as methyl orthobenzoyl benzoate, benzyl dimethyl ketal, 2,2-jethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2
Examples include acetophenone types such as -methylpropiophenone and 1,1-dichloroacetophenone, and thioxanthone types such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.

The amount used is usually 0 per 100 parts by weight of resin solid content.
．． The amount is preferably 1 to 10 parts by weight, preferably 1 to 5 parts by weight.

The thermal polymerization initiator used in the present invention is a compound belonging to organic peroxides, such as ketone peroxide, which is described in the technical material "Organic Peroxides" 3rd edition published by NOF Corporation. Hydroperoxides, dialkyl peroxides, diacyl peroxides, or peroxy esters, and diazo compounds such as azobisisobutyronitrile or azobisvaleronitrile.

In addition, when used in general paints, various additives such as organic and/or inorganic extender pigments, fillers, adhesion agents such as silane coupling agents and titanium coupling agents, leveling agents, and sotrobic agent,
Flow improvers such as slip agents, non-radical polymerizable modifying resins such as acrylic resins, epoxy resins, urethane resins, ketone resins, alkyd resins or melamine resins or rubbers, polymerization inhibitors, ultraviolet absorbers, antistatic agents Alternatively, dyeability imparting agents can also be used.

Representative examples of the unsaturated isocyanate compounds used in the present invention include the following compounds.

(1) 2-Methacroyloxyethyl isocyanate (
Isocyanate ethyl acrylate is hereinafter abbreviated as Mol. ) Isocyanate ethyl methacrylate, isocyanate probyl methacrylate, and the like. Preferred is isocyanate ethyl acrylate from the viewpoint of UV curability.

(2) An unsaturated alcohol compound obtained by reacting acrylic acid or methacrylic acid with a monoepoxy compound is reacted with a polyisocyanate compound to form one molecule of (meth)acryloyl group and isocyanate group via a urethane bond. unsaturated isocyanate covalently contained within.

For example, 2-hydroxyethyl acrylate and 2.4-
) Compounds obtained by reaction with lylene diisocyanate can be mentioned.

Examples of unsaturated alcohol compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (
meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxy-2-methobov dipropyl (
meth)acrylate, 2-hydro-cow-3-etho-cow dipropoxy (meth)acrylate, 2-hydro-cow-3-
Butoxy(meth)acrylate, Propylene glycol mono(meth)acrylate, Butanediol mono(
meth)acrylate, hexanediol mono(meth)
Acrylate or neopentyl glycol mono(
Dihydric alcohol mono(meth)acrylate etc.
Examples include meth)acrylates.

Typical polyisocyanate compounds are 2.
4-tolylene diisocyanate, 2.6-tolylene diisocyanate, 1.3-xylene diisocyanate, 1
．． 4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyl-diphenylmethane diisocyanate, inphorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4-diisocyanate, dicyclohexylmethane-2°4'-diisocyanate, or Lylene diisocyanate or a diisocyanate compound obtained by hydrogenating aromatic isocyanates among the diisocyanate compounds described above (for example, hydrogenated xylylene diisocyanate or hydrogenated diphenylmethane-4,4
These are diisocyanates such as '-diisocyanate, and divalent or trivalent polyisocyanate compounds such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate.

The present invention will be explained below with reference examples, examples, and comparative examples. Unless otherwise specified, "parts" and "%" are based on weight.

(Example) Reference Example 1 [Example of Preparation of Vinyl Ester Resin] 51.2 parts of adipic acid, 43.5 parts of ethylene glycol, and 0.0 parts of adipic acid were prepared according to a conventional method. After charging 1 part of butyl titanate (ethylene glycol solution) into the reactor and purging with nitrogen,
Heated to 0°C. The reaction was stirred for 1 hour, during which time 1O
cc water was distilled off. Next, start reducing the pressure and raise the reactor temperature to 19
After warming to 0°C, the nitrogen purge was turned off. 45 minutes later,
The degree of vacuum was 10 mmHg, 20 cc of ethylene glycol was distilled off, the acid value was 29, and the intrinsic viscosity was 0.18. Next, the reduced pressure was released and the reaction temperature was raised to 220"C, during which time nitrogen purge was started. 3.
Two parts of succinic anhydride were added and the polyester and anhydride reaction was carried out for 20 minutes, giving an acid number of 27.6. This carboxyl group-containing polyester was cooled to 160° C. and 1 part of MEHQ was added thereto while stirring. The nitrogen supply was stopped and air purging was started. 4.8 parts of glycidyl methacrylate was added, stirred for 30 minutes, and taken out. The final acid value is 2. It is 0. This synthesized resin solid 60
40 parts of styrene was dissolved in 40 parts of styrene to obtain an unsaturated polyester/acrylate resin (B-1). The hydroxyl value is
It was 60 or so.

Reference Example 2 [Same as above] According to the usual method, 380 parts of epoxy resin Evicron 850 (product of Inu Nippon Ink Chemical Co., Ltd.), 144 parts of acrylic acid, and 1 part of MEHQ were added, and 80 parts of epoxy resin was added in an air atmosphere.
C. and stirred for 2 hours. The acid value was measured to be 2°O. A vinyl ester resin was obtained by dissolving 40 parts of styrene in 60 parts of this synthesized resin solid. Hydroxyl value is 214
Met.

Implementation flJ1 [Example of preparation of unsaturated isocyanate-modified vinyl ester resin] 100 parts of vinyl ester resin (A-1) prepared in a flask equipped with a stirrer, thermometer, and condenser, MOI
16.57 parts were added and heated to 80°C under a stream of air. After 5 hours of reaction, an unsaturated isocyanate-modified vinyl ester resin (C-1) having an isocyanate concentration of 0% was obtained.

Example 2 [Same as above] Under the above conditions, an unsaturated isocyanate-modified vinyl ester resin (C-2) was obtained from tOO parts of vinyl ester I resin (A-2) and MOI of 59.16 parts.

Example 3 [Example of preparation of unsaturated isocyanate-modified vinyl ester resin] 130 g of 2-hydrocyanethyl methacrylate was added to 174 g of 2.4-tolylene diisocyanate at 50°C under a nitrogen atmosphere over about 1 hour. did. After 1 hour, the isocyanate equivalent weight reached 152. This was designated as a modifier (D-1).

In a flask equipped with a stirrer, a thermometer, and a condenser, 100 parts of vinyl ester resin (A-1) and a modifier (
16.57 parts of D-1) was added and heated to 80°C under a stream of air. After 5 hours, an unsaturated isocyanate-modified vinyl ester resin (C-3) having an isocyanate concentration of 0% was obtained.

Comparative example 1 Vinyl ester resin (A-1) is used.

Comparative example 2 Vinylnystyl resin (A-2) is used.

Irgacure 651 (Bhonf Bageigy Co., Ltd.) was used as a photocuring agent in the curable resin compositions of the above Examples and Comparative Examples.
After adding 2.0 parts of the product), apply it to a thickness of 254 μm on a glass plate, and use a high-pressure mercury lamp of 120 ')'/Cl11 to place it on a conveyor at a distance of 15 cI11, 1 m.
The cured film was irradiated with light at a rate of 1/min, and the curing properties and other properties of the obtained cured film were examined using the following method.

<Curability> Under the above conditions, the photocuring state is examined. If the inside is uniformly and completely cured, it is marked as (○), and if it is partially uncured, it is marked as (
△), and cases where almost no curing was evaluated as (x).

<Adhesion> After cross-cutting the cured film into 2m squares and pasting adhesive tape, the number of pieces peeled off rapidly was examined and 5 out of 100 pieces were peeled off.
Less than or equal to 30 pieces (○), 6 to 30 pieces (△), 31 or more pieces (
×).

Heat resistance> The cured film was heat treated at 100℃ for 20 hours and the condition of the cured film at this time was examined. No change was observed (○), there was no noticeable gloss (△), and the strength of the cured film was It was evaluated as a product with no cracks (x).

The above test results were as shown in Table 1 below.

It is clear from Table 1 above that the resin composition of the present invention can form a cured film with extremely good photocurability and excellent properties such as adhesiveness and heat resistance. did it.

On the other hand, the mixed composition of the comparative example could not satisfy heat resistance and other curing properties.

(Effects of the Invention) In the present invention, a vinyl ester resin modified with an unsaturated isocyanate compound and a polymerization initiator can be photocured well by irradiation with light, and the curing speed is extremely high. As a curable material, it can greatly improve the curing process. Furthermore, the composition cured in this manner has excellent heat resistance and adhesive properties.

The cured coating film obtained from the resin composition of the present invention has excellent weather resistance and is therefore suitable for coating construction materials as a paint, for example, for surface protection or for coating roof tiles, slates, tiles, etc. It is also useful for improving aesthetic appearance.

Claims (1)

[Claims] 1. A vinyl ester resin composition comprising an unsaturated isocyanate-modified vinyl ester resin and a polymerization initiator. 2. The unsaturated isocyanate-modified vinyl ester resin is
The vinyl ester resin composition according to claim 1, which is modified with an unsaturated isocyanate compound represented by the following structural formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R_1: H, CH_3 R_2: Alkylene group, diisocyanate residue. 3. A method for producing an unsaturated isocyanate-modified vinyl ester resin, which comprises reacting a vinyl ester resin having a hydroxyl group with an unsaturated isocyanate in air at a temperature of 170° C. or lower. 4. The hydroxyl value of the vinyl ester resin having a hydroxyl group is 2.
4. The manufacturing method according to claim 3, wherein the number is 2 to 99. 5. A paint characterized by using the vinyl ester resin composition according to claim 1.