JPH0471404B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a radiation-curable resin composition, and more specifically, it has excellent curing properties and physical properties of the cured product,
The present invention relates to a novel radiation-curable resin composition useful for various uses such as inks, paints, and adhesives. [Prior art] Resins that are cured by radiation such as ultraviolet rays or electron beams have advantages over thermosetting resins that are cured by heat, such as resource saving, non-pollution, and rapid curing, so they are widely used. It's being used. In general, radiation-curable resin compositions are made by using a prepolymer such as polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, or polyether (meth)acrylate or unsaturated polyester as a resin component, and using tetrahydrofuranate as a resin component. Mono(meth)acrylates such as furyl(meth)acrylate and phenoxyethyl(meth)acrylate, and polyol poly(meth)acrylates such as 1,6-hexanediol di(meth)acrylate and trimethylolpropane tri(meth)acrylate. It is made by blending reactive diluent components such as. Until now, by changing the blending ratio of these components, radiation-curable resin compositions suitable for each use have been obtained. [Problems to be solved by the invention] However, it is difficult to obtain a resin composition that is well-balanced in terms of curing speed and physical properties of the cured product simply by blending conventionally known components. Therefore, there is a demand for the development of a new radiation-curable resin composition that is well-balanced in both curing speed and physical properties of the cured product. The present inventors conducted various studies in view of the above circumstances, and as a result, arrived at the present invention. Therefore, the present invention provides a radiation-curable resin composition that can be used for various purposes. [Means and effects for solving the problems] The present invention is based on the general formula [] (However, in the formula, R is a hydrogen atom or a methyl group, which may be the same or different, and Z is a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, and (n is an integer from 1 to 100) as an essential component. The present invention relates to a radiation-curable resin composition. The hydroxyl group-containing (meth)acrylate oligomer represented by the general formula [] used in the present invention has the general formula [] (In the formula, R is a hydrogen atom or a methyl group, Z
is a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms and may have an ether bond in the molecule. ) It is obtained by addition polymerizing and oligomerizing a hydroxyl group-containing (meth)acrylate represented by: Specific examples of the hydroxyl group-containing (meth)acrylate represented by the general formula [] include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate,
Hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate,
Examples include dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, hydroxycyclohexyl acrylate, hydroxycyclohexyl methacrylate, and the like. These may be used alone or as a mixture. To oligomerize a hydroxyl group-containing (meth)acrylate by addition polymerizing it, for example, as described in Japanese Patent Application No. 59-256558, the hydroxyl group-containing (meth)acrylate is treated with a protonic acid such as sulfuric acid or para-toluenesulfonic acid; boron trifluoride,
Maintained at a temperature of 10 to 150°C in the presence of catalysts such as Lewis acids such as tin tetrachloride; oxysulfates such as titanium oxysulfate; heteropolyacids such as tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, etc. do it. The radiation-curable resin composition of the present invention contains a hydroxyl group-containing (meth)acrylate oligomer represented by the above general formula [] as an essential component, and contains a hydroxyl group-containing (meth)acrylate oligomer represented by the above general formula []. ) The radiation-curable resin composition of the present invention can be obtained by using the acrylate oligomer alone or by using the oligomer in combination with a conventional radiation-curable resin composition, a known and commonly used reactive diluent, and various resins. Examples of reactive diluents used as necessary in the present invention include styrene, α-methylstyrene,
Acrylonitrile, (meth)acrylamide, diacetone acrylamide, N-methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone, diallyl phthalate, allyl glycidyl ether, (meth)acrylic acid, methyl (meth)acrylate Alkyl (meth)acrylates such as, tetrahydrofurfuryl (meth)acrylate, methoxyethyl (meth)acrylate, phenoxyethyl (meth)
Acrylate, dibromopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate , polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate
Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta Erythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate,
Trishydroxyethyl isocyanurate tri(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, dicyclo Examples include pentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, silicone (meth)acrylate, amide (meth)acrylate, phosphoric acid (meth)acrylate, and the like. These can be used alone or as a mixture. Resins that may be used as necessary in the present invention include:
For example, polyester (meth)acrylate obtained by the reaction of (meth)acrylic acid, glycols, and polybasic acid, epoxy (meth)acrylate obtained by the reaction of (meth)acrylic acid and an epoxy compound, and isocyanate group-containing compounds. Urethane (meth)acrylate obtained by reaction with hydroxyalkyl (meth)acrylate, carboxyl group-containing (meth)acrylate obtained by reaction of carboxylic anhydride and hydroxyalkyl (meth)acrylate
Examples include prepolymers such as acrylates, unsaturated polyesters, epoxy resins, polyamide resins, acrylic resins, polyvinyl alcohols, etc., and these can be used alone or as a mixture. When the above-mentioned reactive diluent or resin is used in the present invention, the amount thereof is not particularly limited, and is appropriately determined depending on the viscosity and curability required of the resulting resin composition or the desired physical properties of the cured product. be able to. The radiation-curable resin composition of the present invention can be applied to or molded onto various substrates by means known to those skilled in the art. Radiation curing can be performed with electron beams, ultraviolet rays, etc. In the case of ultraviolet curing, a normal photopolymerization initiator, and if necessary, a photopolymerization initiator and a sensitizer are used at 0.1
It is incorporated into the composition at a concentration of ~10% by weight. Examples of photopolymerization initiators include benzoin alkyl ethers such as benzoin, benzoin isopropyl ether, and benzoin isobutyl ether;
benzophenone, Michler's ketone, methyl-ο-
Benzophenones such as benzoyl benzoate; acetonephenone, trichloroacetophenone, 2,2-diethoxyacetophenone, p-t
- Acetophenones such as butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone; such as xanthone, thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone Thioxanthone; benzyl, 2-
Ethyl anthraquinone, methyl-benzoylformate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-
Examples of sensitizers include 4'-isopropyl-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, and allyldiazonium salts. Examples of sensitizers include amine compounds, sulfur compounds, and phosphorus compounds. Can be mentioned. These may be used alone or in combination. Furthermore, ultraviolet curing and thermosetting, or electron beam curing can also be used together. When heat curing is used together, common radical polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, di- t
- aluminum peroxide, dicumyl peroxide,
t-butyl perbenzoate, azobisisobutyronitrile, etc. can be used, and if necessary, radical polymerization accelerators such as cobalt octenoate, cobalt naphthenate, iron octenoate, manganese octenoate, vanadium octenoate, etc. can be used. Organic metal salts, organic amines such as N,N-dimethylaniline, etc. can be used in combination. [Effects of the Invention] The radiation-curable resin composition of the present invention has excellent curability and adhesion to substrates, and also has excellent physical properties of the cured product such as hardness of the cured product obtained by curing.
Paints, adhesives, inks, hard coats, resists, protective films for printed wiring boards, encapsulants, binders,
It can be used for a wide range of purposes such as insulating varnish and overprint varnish. [Example] Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.
Note that parts in the examples are parts by weight. Reference Example 1 A reaction vessel equipped with a thermometer and a stirrer was charged with 232 parts of 2-hydroxyethyl acrylate, 0.07 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.3 parts of 12-tungstophosphoric acid as a catalyst, and then heated to 80°C for 7.5 hours. held. After the reaction is complete, add 12 parts of powdered magnesium silicate as an adsorbent and heat at 40°C.
After stirring for 30 minutes, the reaction product was purified by pressure filtration to produce a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing acrylate oligomer (1)).
228 parts (yield 98.3%) were obtained. IR, NMR, GPC
From the analysis results, it was found that the reaction product was a hydroxyl group-containing acrylate oligomer with an average molecular weight of 401 and the following structure. Reference Example 2 After charging 260 parts of 2-hydroxypropyl acrylate, 0.08 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of 12-tungstosilicic acid as a catalyst into the same reaction vessel as in Reference Example 1,
It was kept at 100℃ for 5 hours. After the reaction is complete, 13 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate, which is an adsorbent, is added, stirred at 60°C for 30 minutes, and purified by pressurization to form a colorless transparent liquid. product (hereinafter referred to as
It is called hydroxyl group-containing acrylate oligomer (2). ) 251 parts (yield 96.5%) were obtained. The reaction product was a hydroxyl group-containing acrylate oligomer with an average molecular weight of 510 and the following structure. Reference Example 3 Into a reaction vessel similar to Reference Example 1, 260 parts of 2-hydroxyethyl methacrylate, 0.13 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of tungstophosphoric acid as a catalyst were charged.
It was kept at ℃ for 4 hours. After the reaction is complete, add 260 parts of water, stir at room temperature, leave to stand, remove the aqueous layer (upper layer), and keep the resulting residual liquid at 80°C for 30 minutes under a reduced pressure of 3 mmHg to remove water and residual liquid. As a result of removing a portion of the raw materials, 102 parts (yield: 39.2%) of a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing methacrylate oligomer (3)) was obtained. The reaction product was a hydroxyl group-containing methacrylate oligomer with an average molecular weight of 297 and the following structure. Examples 1 to 6 100 parts of a mixture of the hydroxyl group-containing (meth)acrylate oligomers (1) to (3) obtained in Reference Examples 1 to 3 and the prepolymers and/or reactive diluents shown in Table 1 , 0.01 part of hydroquinone monomethyl ether and benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgakiure 651) 5
UV curable resin composition (1) of the present invention
(6) was prepared. Each of the obtained resin compositions (1) to (6) was applied to a thickness of 15μ on a steel plate panel,
When the panel was irradiated using a high-pressure mercury lamp of 80 W/cm from a distance of 10 cm while moving the panel at a conveyor speed of 6 m/min, a tack-free cured coating film was obtained in each case with a single irradiation. The performance of the obtained cured coating film is shown in Table 1. Comparative Example 1 0.01 part of hydroquinone monomethyl ether and 5 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgakiure 651) were added to 100 parts of the mixture of the prepolymer and reactive diluent shown in Table 1, and a UV-curable type for comparison was prepared. A resin composition (1) was prepared. Using the obtained comparative resin composition (1), the curability of the coating film was examined in the same manner as in Example 1, and it was found that two irradiations were required to obtain a tack-free cured coating film. The performance of the obtained cured coating film is shown in Table 1. Comparative Example 2 CH ₂ =CH-COO (-CH ₂ -CH ₂ -COO) - 30 parts of _1.4 H acrylic acid oligomer, 60 parts of the same prepolymer PA used in Example 1, and the same prepolymer PA used in Example 1. A comparative ultraviolet curable resin composition (2) was prepared by adding 0.01 part of hydroquinone monomethyl ether and 5 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgakiure 651) to a mixture of 10 parts of the same reactive diluent TMPTA. Using the obtained comparative resin composition (2), the radiation curability of the coating film was investigated in the same manner as in Example 1.
Two irradiations were required to obtain a tack-free cured coating. Furthermore, the obtained cured coating film had poor smoothness, a pencil hardness of H, and an adhesion of 90/100, and the physical properties of the cured product were inferior to those of the cured coating film obtained in Example 1. Example 7 5 parts of benzyl methyl ketal (manufactured by Ciba Geigy, Irgakiure 651) was added to 100 parts of the hydroxyl group-containing (meth)acrylate oligomer (1) obtained in Reference Example 1 to prepare the ultraviolet curable resin composition of the present invention ( 7) was prepared. The obtained resin composition (7) was applied to a thickness of 15 μm on a steel plate panel, and irradiated with an 80 W/cm high-pressure mercury lamp from a distance of 10 cm while moving the panel at a conveyor speed of 6 m/min. However, a cured coating film was obtained with one irradiation. The performance of the obtained cured coating film was examined in the same manner as in Example 1, and the pencil hardness was 2B and the adhesion was 100/100.

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Claims (1)

[Claims] 1. General formula [] (However, in the formula, R is a hydrogen atom or a methyl group, which may be the same or different,
Z is a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, and may have an ether bond in the molecule, and may be the same or different, and n
is an integer from 1 to 100. ) A radiation-curable resin composition containing as an essential component a hydroxyl group-containing (meth)acrylate oligomer.