JPH11302347A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent adhesivity to polyolefin-based resins such as polypropylene and useful for coatings, adhesives, inks, sealants, or the like., by compounding a polyhydric alcohol component, a polyvalent isocyanate component and a (meth)acrylate component. SOLUTION: This curable resin composition comprises (A) a polyhydric alcohol component, (B) a polyvalent isocyanate component containing a hydroxyfatty acid ester (preferably a ricinolic acid ester, a 12-hydroxystearic acid ester, caster oil, hydrogenated caster oil), and (C) a (meth)acrylate component capable of reacting with the isocyanate component. The component A and the component B are preferably compounded so that the molar ratio of the isocyanate groups in the component B to the hydroxyl groups in the component A is (0.01-2.5):1. The component A and the component C are preferably compounded so that the molar ratio of the active hydrogen atoms in the component C to the hydroxyl groups in the component A is (0.01-2.0):1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition which is cured by active energy rays such as ultraviolet rays.
More specifically, the present invention relates to a curable resin composition having excellent adhesion to a polyolefin resin such as polypropylene.

[0002]

2. Description of the Related Art In recent years, active energy ray-curable paints which are cured by irradiation with active energy rays such as ultraviolet rays have been widely used in place of organic solvent-based paints due to environmental pollution problems and energy saving. This is because it contains a resin and a monomer that can be cured by irradiation with active energy rays such as ultraviolet rays, and has an advantage that the solvent does not volatilize during the formation of a coating film because the monomer also functions as a solvent. And the resin composition having this active energy ray-curing property is also used for applications such as adhesives and inks, including the above-mentioned paints.
Plastics such as polyolefin resins are increasing as coated or adherends, and adhesion and adhesion to polyolefin resins have become important properties.

[0003]

Problems to be solved by the invention are as follows.
For example, in a solvent-based resin composition, it has been attempted to mix a chlorinated polyolefin, but at present, there is no definitive measure for the above-described typical curable resin composition.

[0004]

In view of the above situation, the present inventors have conducted intensive studies and have found that (a) a polyhydric alcohol component, (b) a polyhydric isocyanate component, and (c) an isocyanate component. The present inventors have found that a curable resin composition having excellent adhesiveness (adhesion) with a polyolefin resin can be obtained when the resin comprises a reactive (meth) acrylate component and the component (b) contains a hydroxy fatty acid ester. The invention has been completed.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, the (a) polyhydric alcohol component is characterized most by containing a hydroxy fatty acid ester, and the content of the hydroxy fatty acid ester in the component (a) is not particularly limited. The content is preferably 90% by weight or more in the component, and if the content is less than 90% by weight, there is a possibility that the adhesiveness to the polyolefin-based resin may be reduced, which is not preferable.

Specific examples of such hydroxy fatty acid esters include ricinoleic acid ester, 12-hydroxystearic acid ester, castor oil, hydrogenated castor oil and the like. Other polyhydric alcohol components in the component (a) include ethylene glycol, 1,2- or 1,3-propylene glycol, butylene glycol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, dipropylene glycol,
1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methylpentanediol, cyclohexanedimethanol, hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol , Polybutylene glycol, polytetramethylene glycol,
Polyhydric alcohols such as polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythol, sorbitol, mannitol, glycerin, polyglycerin, and the polyhydric alcohols and maleic anhydride, maleic acid , Fumaric acid, itaconic anhydride, itaconic acid,
Adipic acid, phthalic acid, phthalic anhydride, terephthalic acid,
Examples include polyester polyols, caprolactone-modified polyols, polyolefin-based polyols, polycarbonate-based polyols, and polybutadiene-based polyols, which are reactants with polybasic acids such as isophthalic acid, and these can be used in combination with the above-mentioned hydroxy fatty acid esters.

The polyvalent isocyanate component (b) includes aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates or a mixture thereof. 4-tolylene diisocyanate or 2,
6-tolylene diisocyanate (TDI) such as tolylene diisocyanate, and mixtures thereof, diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate ( Aromatic polyisocyanates such as modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), and trimethylhexamethylene diisocyanate (TMXDI); Dimer compound, aliphatic polyisocyanate such as isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), These reaction products of polyisocyanate and polyol and the like, 2,4-tolylene diisocyanate, isophorone diisocyanate (IPDI)
Is preferably used.

Further, (c) the (meth) acrylate component capable of reacting with isocyanate contains an active hydrogen such as a hydroxyl group or an amino group, and specifically includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol triacrylate, 2-hydroxyethyl acryloyl phosphate, 4-hydroxybutyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate,
(Meth) acrylic acid and the like are mentioned, and among them, 2-hydroxypropyl acrylate and (meth) acrylic acid are preferably used.

Next, a method for obtaining the resin composition of the present invention using the above components (a) to (c) will be described, but the method is not limited thereto. In obtaining the resin composition of the present invention, first, the isocyanate group in the component (b) is 1.01 to 1 mol per mole of the hydroxyl group in the component (a).
(A) is added to (b) in a ratio of 2.5 mol to obtain a terminal isocyanurethane oligomer. The addition (reaction) temperature at this time is preferably 50 to 90 ° C., and usually a catalyst such as a tin compound is coexisted at about 5 to 5000 ppm.
Thereafter, (c) is added to the urethane oligomer. In this case, the amount of active hydrogen in the component (c) is 0.01 to 1 mol per 1 mol of the hydroxyl group in the component (a).
The addition (reaction) temperature is preferably 40 to 60 ° C. at this time, and usually a catalyst such as a tin compound is present in an amount of about 5 to 5000 ppm. .

Thus, the resin composition of the present invention can be obtained. If necessary, a photopolymerization initiator or an ethylenically unsaturated monomer can be added to the resin composition. Examples of the initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, and 2-hydroxy-2.
-Methyl-1-phenylpropan-1-one, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)
-2-hydroxy-2-methylpropan-1-one, 4
-(2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, an allyl ketone-containing compound, 1-hydroxycyclohexyl phenyl ketone,
-Methyl-1- [4- (methylthio) phenyl] -2-
Acetophenone photopolymerization initiators such as morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin photopolymerization initiators such as benzyl dimethyl ketal, benzophenone,
Benzoylbenzoic acid, methyl benzoylbenzoate, 4-
Phenylbenzophenone, hydroxybenzophenone,
Acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4
Benzophenone-based photopolymerization initiators such as -methoxybenzophenone, thioxanthone, 2-chlorothioxanthone,
2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone,
Thioxanthone-based photopolymerization initiators such as 2,4-diisopropylthioxanthone, further α-acyloxime ester-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, methylphenylglyoxylate, benzyl,
9,10-phenanthrenequinone, camphorquinone,
Dibenzosuberone, 2-ethylanthraquinone, 4 ',
4 ″ -diethylisophthalophenone, 3,3 ′, 4
4'-tetra (t-butylperoxycarbonyl) benzophenone and the like can be mentioned.

If necessary, auxiliaries or initiators used in combination therewith include triethanolamine, methyldiethanolamine, triisopropanolamine,
4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone,
-Dimethylaminoethyl benzoic acid, ethyl 4-dimethylaminobenzoate, ethyl (4-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate,
Auxiliary agents such as polymerizable tertiary amines, cobalt octenoate, cobalt naphthenate, manganese octenoate, manganese naphthenate, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t- Initiators such as butyl perbenzoate may be mentioned.

The ethylenically unsaturated monomer is not particularly limited as long as it has an ethylenically unsaturated bond. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2 −
Dicyclopentenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, tetrahydrofurifuri (Meth) acrylate, carbitol acrylate, benzyl acrylate, allyl acrylate, phenoxyethyl acrylate, styrene,
Vinyltoluene, chlorostyrene, α-methylstyrene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, acryloxyethyl phosphate, 2-vinylpyridine, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Acrylate, ethyl carbitol acrylate, polypropylene glycol diacrylate, polyethylene glycol (# 200, # 400, # 600) diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 1,6-hexane Diol diacrylate, trimethylolpropane triacrylate, EO (ethylene oxide) -modified trimethylolpropane triacrylate, methyl triglyco Le, acryloyl morpholine, 1,9-nonanediol diacrylate, 2-n-
Butyl-2-ethyl-1,3-propanediol diacrylate and the like, among which 1,9-nonanediol diacrylate, 2-n-butyl-2-ethyl-1,3
-Propanediol diacrylate and EO (ethylene oxide) -modified trimethylolpropane triacrylate are preferably used.

The amount of the photopolymerization initiator and the ethylenically unsaturated monomer in the present invention is not particularly limited, but the amount of the photopolymerization initiator (including the auxiliary and the initiator when they are used together) is as follows. It is about 1 to 10% by weight based on the total weight of the resin composition of the present invention, and the mixing ratio of the resin composition of the present invention to the ethylenically unsaturated monomer is the weight ratio of the resin composition / ethylenically unsaturated monomer. 95/5 to 15/85
And more preferably 90/10 to 3
At 0/70, if the compounding weight ratio of the resin composition exceeds the above range, the viscosity of the compounding composition becomes high and the workability is remarkably reduced when applied to painting or the like. If the blending weight ratio exceeds the above blending weight ratio, the toughness of the resulting film tends to decrease, and at the same time, the scratch resistance tends to decrease, which is not preferable.

The resin composition of the present invention may contain an organic solvent, if necessary, such as a ketone solvent such as acetone, methyl ethyl ketone and cyclohexanone, methyl acetate, ethyl acetate, and the like. Ethyl solvents such as butyl acetate, ethyl lactate, methoxyethyl acetate, propylene glycol monomethyl ether acetate and ethylene glycol diacetate; ether solvents such as diethyl ether, ethylene glycol dimethyl ether and dioxane; aromatic solvents such as toluene and xylene; pentane , Hexane and the like, aliphatic solvents such as methylene chloride, chlorobenzene and chloroform, and alcohol solvents such as isopropyl alcohol and butanol.

Further, when used as a paint, pigments, fillers, leveling agents, thermoplastic resins and the like are often added as additives. Examples of the pigment include titanium white, cyanine blue, cream yellow, watching red, red bengal, carbon black, and aniline black.

As the thermoplastic resin, cellulose acetate butyrate, nitrocellulose, vinyl chloride resin,
Vinyl acetate resin, acrylic resin and their copolymers,
Butylated melamine, butylated urea and the like can be mentioned. Also, it can be used in combination with a wax type unsaturated polyester resin. Other additives include antioxidants, ultraviolet absorbers, silicone oils, surfactants and the like. In addition, when used as an adhesive, a vinyl acetate resin, a thermoplastic resin such as a vinyl acetate copolymerizable resin, a polyisocyanate, a silane-based cross-linking agent and the like are often used in combination, and in an application such as an ink, it is usually , A pigment, a pigment dispersant, a wetting agent, a viscosity modifier, a (modified) alkyd resin, and the like.

As a method for curing the curable resin composition of the present invention, the curable resin composition can be cured by irradiating an active energy ray, and the energy rays include far ultraviolet, ultraviolet, near ultraviolet, and red. In addition to external light, electromagnetic waves such as X-rays and γ-rays, electron beams, proton beams, neutron beams and the like can be used. However, a curing method using ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of a radiation irradiation device, and price. The ultraviolet light referred to in the present invention is 150 to 450 n.
It mainly emits light in the m wavelength range, and is irradiated using a chemical lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like.

In applying the curable resin composition of the present invention as a paint or an adhesive, known methods such as a curtain coater, a roll coater, a flow rotor, spraying and dipping can be adopted. The thickness of the coating cannot be determined unconditionally depending on the object to be coated or the intended use, but can usually be suitably selected from the range of 5 to 200 μm. In addition, for the ink application, a known dedicated machine such as offset printing, gravure printing, flexographic printing, screen printing, or the like can be used. Further, the object to be coated may be plastics such as vinyl chloride resin, polyethylene terephthalate (PET), polymethacrylate, polycarbonate, nylon (polyamide), and the like.
Wood, metal plate, metal oxide film, glass, ceramics,
Although it can be widely used up to paper and concrete, the curable resin composition of the present invention has excellent adhesiveness (adhesion) with a polyolefin resin, and is particularly suitable for polyolefin resins such as polyethylene and polypropylene. Useful.

[0019]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “parts” means on a weight basis unless otherwise specified.

Example 1 A 5-liter four-necked flask equipped with a thermometer, a reflux condenser and a stirrer was used to prepare (a) 512 parts of castor oil (containing 1.46 mol of hydroxyl groups), and (b) isophorone diisocyanate (I).
PDI) (containing 2.89 mol of isocyanate groups) 321
And 0.1 part of dibutyltin dilaurate, and reacted at 70 to 90 ° C. for 5 hours to obtain a terminal isocyanurethane oligomer. Next, hydroquinone monomethyl ether 0.7 was added to the obtained urethane oligomer.
(C) was added to the reaction solution maintained at 70 to 80 ° C.
167 parts of 2-hydroxyethyl acrylate (containing 1.44 mol of hydroxyl groups) were added dropwise, and after completion of the addition, the mixture was aged for 2 hours by heating (50 ° C.). The curable resin composition of the present invention at a temperature of ° C was obtained.

In 100 parts of the obtained resin composition, 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1 manufactured by Ciba Geigy) was used as a photopolymerization initiator.
173 ") and 60 parts of tripropylene glycol as an ethylenically unsaturated monomer.
Using an applicator with a gap interval of 50 μm, a polypropylene film (corona discharge treated) having a thickness of 20 μm is adhered to each other, and is placed under an 80 W / cm mercury lamp installed at a height of 20 cm at a line speed of 5 m / min. (The accumulated light amount: 161 mj / c
m ² ) and after curing, the adhesive (adhesion) strength was set at 20 ° C. and 65% RH according to the peel test method of JIS Z 0237.
As a result, the material was broken at a rate of 2 kg / inch or more.

Example 2 A curable resin composition was prepared in the same manner as in Example 1, except that 523 parts of hydrogenated castor oil (containing 1.46 mol of hydroxyl groups) was used instead of the castor oil (a). Then, the adhesive strength was measured in the same manner. At 2 kg / inch or more, the material of the polypropylene film was broken.

Example 3 (Production of hydroxy fatty acid ester) A four-necked flask equipped with a packed tower was charged with 350 parts of 12-hydroxystearic acid, 93 parts of ethylene glycol, and 0.1 part of dibutyltin dilaurate. At 4 ° C. for 4 hours and then at a reduced pressure of 50 torr for 3 hours.
The reaction was pursued by also discharging excess ethylene glycol for 0 minute, and the acid value was 0.5 mgKOH / g and the hydroxyl value was 14 mgKOH / g.
7 mg KOH / g of 12-hydroxystearic acid ester was obtained. A curable resin composition was obtained in the same manner as in Example 1 except that 556 parts of the above 12-hydroxystearic acid ester (containing 1.46 mol of hydroxyl groups) was used in combination as the component (a) to obtain a curable resin composition. The adhesive strength was measured. When the adhesive strength was 2 kg / inch or more, the material of the polypropylene film was broken.

Example 4 Example 1 was repeated except that 461 parts of castor oil (same as above) and 73 parts of polytetramethylene glycol (molecular weight: 1,000, containing 1.46 mol of hydroxyl groups) were used as the components (a). A curable resin composition was obtained, and the adhesive strength was measured in the same manner. At 2 kg / inch or more, the material of the polypropylene film was broken.

Comparative Example 1 A curable resin composition was obtained in the same manner as in Example 1 except that 730 parts of polytetramethylene glycol (same as above) was used instead of castor oil to obtain a curable resin composition, and the adhesive strength was measured in the same manner. However, at 82 g / inch, interfacial peeling was observed.

[0026]

The curable resin composition of the present invention is excellent in adhesiveness (adhesion) to a polyolefin resin because it uses a hydroxy fatty acid ester as a constituent component thereof, and can be used for various materials (particularly polyolefin plastics). (1) It is very useful for applications such as paints, adhesives, inks, sealants, etc.

Claims (4)

[Claims] 1. A composition comprising (a) a polyhydric alcohol component, (b) a polyvalent isocyanate component and (c) a (meth) acrylate component capable of reacting with isocyanate, and (b)
A curable resin composition wherein the component contains a hydroxy fatty acid ester. 2. The method of claim 1, wherein the hydroxy fatty acid ester is at least one selected from ricinoleate, 12-hydroxystearate, castor oil and hydrogenated castor oil.
The curable resin composition according to claim 1, which is a seed. 3. The ratio of (a) to (b) is such that the isocyanate group in (b) is 1.0 to 1 mol of the hydroxyl group in (a).
3. The curable resin composition according to claim 1, wherein the amount is from 1 to 2.5 mol. 4. The ratio of (a) to (c) is such that the amount of active hydrogen in (c) is from 0.01 to 2.0 mol per mole of hydroxyl group in (a).
The curable resin composition according to any one of claims 1 to 3, wherein the amount is 0 mol.