JPS62101610A - Radiation-curable resin composition - Google Patents

Abstract

PURPOSE:To make it possible to obtain the titled composition having a well- balanced improvement in a curing rate and properties of a cured product, by incorporating a specified hydroxy group-containing (meth)acrylate oligomer as an essential component. CONSTITUTION:A radiation-curable resin composition containing a hydroxyl group-containing (meth)acrylate oligomer of the formula (wherein R groups may be the same or different and are H or methyl and Z groups may be the same or different and are bivalent 2-20C organic groups and n is an integer of 1-100). This resin composition can be obtained from the oligomer of the formula alone or together with a reactive diluent and various a resins which are well-known and common in a conventional radiation-curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a radiation-curable resin composition, and more specifically, it has excellent curing properties and physical properties of cured products, and is suitable for use in inks, paints,
The present invention relates to a novel radiation-curable resin composition useful for various uses such as adhesives.

[Conventional technology]

Resins that are cured by radiation such as ultraviolet rays or electron beams are widely used because they have advantages such as resource saving, non-pollution, and rapid curing compared to thermosetting resins that are cured by heat. In general, radiation-curable resin compositions include prepolymers such as polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate, or unsaturated polyester, and tetrahydrofuran. Mono(meth)acrylates such as furyl(meth)acrylate and phenoxyethyl(meth)acrylate, and polyol poly(meth)acrylates such as 1,6-hexanethiol di(meth)acrylate and trimethylolpropane tri(meth)acrylate. Contains reactive diluent components such as acrylates. Until now, by changing the blending ratio of these components, radiation-curable resin compositions suitable for each use have been obtained.

[Problem that the invention seeks to solve]

However, it is difficult to obtain a resin composition that is well-balanced in both the curing speed and the physical properties of the cured product by simply blending known components. There is a need for the development of a new radiation-curable resin composition with a high temperature.

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 has the following features:
General formula CI) (In the formula, R is a hydrogen atom or a methyl group, and each may be the same or different, and Z is a divalent organic group having 2 to 20 carbon atoms, and each may be the same. The present invention relates to a radiation-curable resin composition containing as an essential component a hydroxyl group-containing (meth)acrylate oligomer represented by (n is an integer of 1 to 100, which may or may not be the same).

The hydroxyl group-containing (meth)acrylate oligomer represented by the general formula (1) used in the present invention is the general formula (I
I) (wherein, R is a hydrogen atom or a methyl group, and Z is a divalent organic group having 2 to 20 carbon atoms) is oligomerized by addition polymerization of a (meth)acrylate containing a hydroxyl group. This is especially true. Specific examples of hydroxyl group-containing (meth)acrylates represented by the general formula [■] include and droxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl Acrylate, hydroxyhexyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, diethylene glycol monoacrylate, dipropylene glycol monomethacrylate, hydroxycyclohexyl acrylate, hydroxycyclohexyl methacrylate, and the like. These alone,
Alternatively, it can be used as a mixture. In order to oligomerize a hydroxyl group-containing (meth)acrylate by addition polymerization, for example, as described in Japanese Patent Application No. 59-256558, a hydroxyl group-containing (meth)acrylate is mixed with a protonic acid such as sulfuric acid or para-toluenesulfonic acid: Lewis acids such as boron trifluoride and tin tetrachloride Oxysulfates such as titanium dioxysulfate: tungstophosphoric acid, tungstosilicic acid,
It may be maintained at a temperature of 10 to 150° C. in the presence of a catalyst such as a heteropolyacid such as molybdophosphoric acid or molybdosilicic acid.

The radiation curable resin composition of the present invention has the general formula (1)
If it contains the hydroxyl group-containing (meth)acrylate oligomer represented by the above as an essential component, the hydroxyl group-containing (meth)acrylate oligomer represented by the above general formula [I]
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.

Reactive diluents that may be used as necessary in the present invention include:
For example, styrene, α-methylstyrene, acrylonitrile, (meth)acrylamide, diacetone acrylamide, N-methyl(meth)acrylamide, N-methylol(meth)acrylamide, N-vinylpyrrolidone, diallylphthalate, allyl glycidyl ether, (meth) Acrylic acid, alkyl (meth)acrylates such as methyl (meth)acrylate, 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'-)(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate (meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trishydroxyethyl isocyanurate tris(meth)acrylate, ethylene oxide bisphenol A di(meth)acrylate ,
Hydrogenated bisphenol A di(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, synchlopentenyl(
Examples include 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.

Examples of resins that can be used as necessary in the present invention include (
``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 epoxy compound, incyanate group-containing compound and Prepolymers such as urethane (meth)acrylate obtained by reaction with hydroxyalkyl (meth)acrylate, carboxyl group-containing (meth)acrylate obtained by reaction of carboxylic acid anhydride and hydroxyalkyl (meth)acrylate, and unsaturated Examples include polyester, epoxy resin, polyamide resin, acrylic resin, polyvinyl alcohol, 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 using electron beams, ultraviolet rays, etc.
In the case of ultraviolet curing, a conventional photopolymerization initiator, and if necessary, a photopolymerization initiator and a sensitizer are added to the composition at a concentration of 0.1 to 10% by weight. Examples of photopolymerization initiators include benzoin, -thyl compounds; benzophenones such as benzophenone, Michler's ketone, and methyl-0-benzoyl benzoate; acetophinione, trichloroacetophenone, 2,2-jethoxyacetophenone, and p-t-butyl. Acetophenones such as trichloroacetophenone, 2.2-”/methoxy-2-phenylacetophenone, p-dimethylaminoacetophenone; xanthone,
Thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-ingrovirthioxanthone; benzyl, 2-ethylanthraquinone, methyl-benzoylformate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Examples include hydroxy-4'-isopropyl-2-methylpropiophenone, 1-hydroxycyclohexylphenyl lactone, tetramethylthiuram monosulfide, and allyldiazonium salt. Examples of sensitizers include amine compounds, sulfur compounds, and phosphorus compounds. etc. These may be used alone or in combination.

Furthermore, ultraviolet curing and thermosetting, or electron beam curing and thermosetting can also be used together. When heat curing is used in combination, 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-amyl peroxide, dicumyl peroxide, t-butylhachenzoate, azobisisobutyronitrile, etc. can be used, and as necessary. Radical polymerization accelerators such as organic metal salts such as cobalt octenoate, cobalt naphthenate, iron octenoate, manganese octenoate, and vanadium octenoate, organic amines such as N,N-dimethylaniline, etc. can be used in combination. .

〔Effect 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, and can be used in paints, adhesives, inks, etc. It can be used in a wide range of applications, including hard coats, resists, protective films for printed wiring boards, sealants, binders, insulation boards, and oat δ-lint varnishes.

〔Example〕

Next, the present invention will be explained by examples, but the present invention is not limited by these examples. Note that parts in the examples are parts by weight.

Reference Example 1 In a reaction vessel equipped with a thermometer and a stirrer, 232 parts of 2-hydroxyethyl acrylate, 0.07 part of hydroquinone monomethyl ether as a polymerization inhibitor, and 12- as a catalyst were placed in a reaction vessel equipped with a thermometer and a stirrer.
After adding 2.3 parts of tungstophosphoric acid, heat to 80℃ to 7.5
Holds time.

After the reaction is completed, adsorbent powdered magnesium silicate 12
After stirring at 40° C. for 30 minutes, purification was performed by pressure filtration, and the reaction product was a colorless transparent liquid (hereinafter referred to as hydroxyl group-containing acrylate oligomer (1)).

) 228 parts (yield 98.3%) were obtained. IR, NMR,
From the GPC analysis results, the reaction product has an average molecular weight of 401.
was found to be a hydroxyl group-containing acrylate oligomer with the following structure.

Reference Example 2 After charging 260 parts of 2-hydroxypropyl acrylate, parts of hydroquinone monomethyl ether O and OS as a polymerization inhibitor, and 26 parts of 12-tungstosilicic acid as a catalyst into the same reaction vessel as in Reference Example 1, the mixture was heated to 100°C for 5 hours. I kept it. After the reaction is complete, 13 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate as an adsorbent is added, stirred at 60°C for 30 minutes, and purified by pressure filtration to form a colorless transparent liquid. 251 parts (yield: 96.5%) of a product (hereinafter referred to as hydroxyl group-containing acrylate oligomer (2)) were obtained.

The reaction product was a hydroxyl group-containing acrylate oligomer having 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, and then heated to 100°C. It lasted for 4 hours. After the reaction was completed, 260 parts of water was added, stirred at room temperature, allowed to stand, and the aqueous layer (upper layer) was removed.
As a result of removing water and a portion of the remaining raw materials by keeping it at 80°C for 30 minutes under a reduced pressure of 1.5 g, a reaction product of a colorless transparent liquid (hereinafter referred to as hydroxyl group-containing methacrylate oligomer (3)) was obtained. 102 parts (yield 39.2
%) was obtained. The reaction product was a hydroxyl group-containing methacrylate oligomer having an average molecular weight of 297 and the following structure.

Examples 1 to 6 Mixture 1 of the hydroxyl group-containing (meth)acrylate oligomers (1) to (3) obtained in Reference Examples 1 to 3 and the prepolymer and/or reactive diluent shown in Table 1
00 parts, hydroquinone monomethyl ether 0.01
1 part and 5 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgacure 651) were added to prepare ultraviolet curable resin compositions (1) to (6) of the present invention. Each of the obtained resin compositions (1) to (6) was applied to a thickness of 15 μm on a steel plate panel, and was applied at a conveyor speed of 6 mph/min from a distance of 10 crn using a high-pressure mercury lamp of 80 W/α. When the panel was irradiated while moving, a tack-free cured coating film was obtained in all cases with one irradiation. The performance of the obtained cured coating film is shown in Table 1.

Comparative Example 1 To 100 parts of the mixture of prepolymer and reactive diluent shown in Table 1 was added 0.0 parts of hydroquinone monomethyl ether.
01 parts and 5 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgacure 651) were added to prepare a comparative ultraviolet curable resin composition (1). Using the obtained comparative resin composition (1), the curability of the coating film was examined in the same manner as in Example 1, and 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.

Example 7 Hydroxyl group-containing (meth)acrylate oligomer obtained in Reference Example 1 (11,100 parts) and benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgacure 651) 5
% to prepare an ultraviolet curable resin composition (7) of the present invention. 1 of the obtained resin composition (7) was placed on a steel plate panel.
When the panel was coated to a thickness of 5 μm and irradiated using a high-pressure mercury lamp of 80 W/crrL from a distance of 10 α height at a conveyor speed of 5 m for 7 minutes, a cured coating was obtained with one irradiation. It was done. When the performance of the obtained cured coating film was examined in the same manner as in Example 1, the pencil hardness was 2B and the adhesion was 100/100.

Claims (1)

[Claims] 1. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R is a hydrogen atom or a methyl group, and they may be the same or different. , Z are divalent organic groups having 2 to 20 carbon atoms, and may be the same or different, and n is an integer of 1 to 100. A radiation-curable resin composition containing an acrylate oligomer as an essential component.