JPH0796577B2 - Photocurable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The photocurable resin composition of the present invention is used for producing a resin or hologram for imparting waterproofness to paper or film when a printed or coated article having a three-dimensional pattern is obtained. It is useful as a resin sometimes used and a resin for forming a transfer film.

[Prior art]

(A) A photopolymerizable compound having an ethylenically unsaturated group such as epoxy acrylate or acrylic urethane is diluted with (B) a polymerizable unsaturated monomer such as ethylene glycol diacrylate or trimethylol propane triacrylate. Using (C) a photocurable resin containing a photosensitizer as a binder, and using a photocurable ink containing a pigment, a leveling agent, etc., to print on a resin film or a resin injection molded product. Is being done.

The component (A) of these photocurable resin compositions generally exhibits a liquid state at room temperature (20 to 30 ° C.) and is coated on a substrate such as paper, resin, metal, etc. Has the drawback that paper, film, etc. cannot be wound or stacked. Further, there is a drawback that the paper or film having the photocured resin layer cannot be subjected to post-processing such as patterning such as embossing, printing, painting and resin laminating.

As a photocurable resin that can be post-processed, (A) component is a solid at room temperature, (a) epoxy acrylate obtained by reacting a high molecular weight epoxy resin with acrylic acid, or (b) a special acrylic melamine compound. Known,
A photo-curable resin containing this is used as a resin for imparting a pattern pattern to a release paper used in the production of vinyl chloride leather foam (Japanese Patent Laid-Open Nos. 58-156099 and 59-117537).
issue).

However, the epoxy acrylate (a) is insufficient in the scratch resistance, surface hardness, and chemical resistance to printing ink of the photocurable resin as a resin for producing these transfer papers and holograms. The latter (b) acrylic melamine compound was developed with the intention of using it in the production of process release paper, so the hardness, scratch resistance, water resistance, and chemical resistance of the cured film, especially alcohol resistance such as methanol and ethanol. It has the disadvantage of being inferior in sex.

[Problems and effects to be solved by the invention]

The present invention was made in order to improve the defects of hardness, scratch resistance, water resistance, and alcohol resistance of the latter resin (b), and the photocurable resin composition of the present invention was applied to a substrate. After that, by drying and scattering the organic solvent and providing a solid photocurable resin layer with no tackiness on the substrate, post-processing such as winding, superimposing, embossing, printing, painting, and laminating. And then light irradiation (electron beam,
(UV) completely hardens the solid photo-curing resin layer, making it tough, with hardness, heat resistance, scratch resistance, water resistance, and chemical resistance.
It was possible to manufacture processed products (holograms, transfer paper, embossed decorative products) having a resin layer having excellent adhesion to a substrate.

[Structure of Invention]

The present invention includes (A) component: (a) component: general formula In the formula, R'represents H or a hydrocarbon group having 1 to 4 carbon atoms, and R is a methyl group, a phenyl group, -N (CH ₂ O
R ') ₂ (R' is the same or different from H above)
Or a hydrocarbon group having 1 to 4 carbon atoms) or an organic group represented by the following formula.

(Y is —CH ₂ OR ′ or hydrogen, R ′ is H or a hydrocarbon group having 1 to 4 carbon atoms which is the same as or different from R ′ above) 1 mol (b) Component: 1.5 to 4 equivalents of polyhydric alcohol of 500 or less ((one hydroxyl group is 1 equivalent) (c) component: amide compound selected from acrylamide and α-lower alkyl substituted acrylamide 1 to 4.5 mols (a), Melamine acrylic compound 50 which is solid at 20 ° C. and is obtained by reacting the components (b) and (c) in the above proportions.
To 90% by weight (B) component: Acrylic acid alkyl ester having one or more acryloyloxy groups in the molecule or methacrylic acid alkyl ester having one or more methacryloyloxy groups in the molecule
10 to 50% by weight (C) component: 10 parts by weight based on 100 parts by weight of the total amount of the non-reacting organic solvent (A) and (B) component that dissolves the components (A) and (B).
~ 900 parts by weight Component (D): Photosensitizer 0.05 to 5 relative to the total amount of the above components (A) and (B).
% By Weight It is intended to provide a photocurable resin composition containing the components (A), (B), (C) and (D).

Acrylic melamine compound as component (A): The acrylic melamine compound as component (A) is described in JP-A-59-11.
(A) melamine compound disclosed in Japanese Patent No. 7537,
(B) Polyhydric alcohol and acrylic amide are used as raw materials in the above proportions, and a catalyst is mixed therein, and the mixture is heated at 50 to 150 ° C.
It is preferably obtained by reacting at 80 to 130 ° C for 2 to 20 hours.

Some specific examples of the methylolated melamine compound and the alkyl etherified melamine compound of the component (a) are shown below. Hexamethylol melamine,
Pentamethylolmelamine, tetramethylolmelamine, trimethylolmelamine, dimethylolmelamine,
Hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, trimethoxymethylmelamine, tributoxymethylmelamine, hexaethoxymethylmelamine, pentaethoxymethylmelamine, tetraethoxymethylmelamine, trimethoxymethyl-diethoxymelamine, triethoxy Methyl-dibutoxymethylmelamine, hexapropoxymethylmelamine, tripropoxymethylmelamine, dibutoxymethylmelamine, trimethoxymethylmelamine, dipropoxymine, hexabutoxymethylmelamine, monomethoxymethylmelamine, tetrabutoxymethylmelamine, tetramethoxymethylmelamine , Methyl guanamine, dimethoxymethyl guanamine, dibutoxymethyl guanamine, monomethoxymethyl Anamin, tri propoxymethyl guanamine, tetramethoxy methyl guanamine, benzoguanamine, tetrabutoxymethylated guanamine, di-butoxymethylated - benzoguanamine and mixtures thereof.

Those particularly suitable for the subject in the present invention are those R 'in formula (I) is hydrogen or methyl radical, R is -N (CH ₂ OCH _{3) 2} or phenyl group.

Next, as the polyhydric alcohol having a molecular weight of 500 or less as the component (b), ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4
Aliphatic alkylenediglycols such as -butanediol, 1,5-pentanediol and 1,6-hexanediol; Aliphatic polyhydric alcohols having 3 or more hydroxyl groups such as trimethylolpropane and pentaerythritol; Diethylene glycol, diethylene glycol Polyoxyalkylene glycols such as propylene glycol, polyethylene glycol, polypropylene glycol; ethylene oxide or propylene oxide 2 to 4 mol adduct of bisphenol A; cycloaliphatic structures such as cyclohexanedimethanol, norbornenedimethanol, tricyclodecanedimethanol Examples thereof include dihydric alcohols and the like. When the molecular weight of the polyhydric alcohol exceeds 500, the melting point of the obtained resin is low, and the drying property of the photocurable resin after removing the solvent is not sufficient.

Further, as the acrylamide and the α-lower alkyl-substituted acrylamide as the component (c), acrylamide, methacrylamide, α-propylacrylamide, α-butylacrylamide, and a mixture thereof are generally suitable. As the α-lower alkyl group, those having 1 to 4 carbon atoms are generally suitable.

Mixtures of these can also be used.

Next, the charging ratio of each component will be described.

The charging ratio of the polyhydric alcohol of the component (b) is 1.5 to 4 equivalents (1 equivalent of -OH is 1 equivalent) to 1 mol of the methylolated melamine compound or the alkyl etherified melamine compound or the alkyl etherified melamine compound of the component (a). ), Preferably 2 to 3 equivalents, and the charging ratio of the acrylamide compound as the component (c) is 1 to 4.5 mol, preferably 2 to 4 mol.

When the charged amount of the polyhydric alcohol of the component (b) is less than 1.5 equivalents relative to 1 mol of the melamine compound of the component (a), the resin obtained has a poor solubility in a reaction solvent such as cyclohexanone or dioxane, and the resin reacts. Precipitates inside. On the other hand, when the amount exceeds 4 equivalents, the obtained resin is polymerized too much, and the viscosity of the reaction solution becomes too high, which makes stirring difficult.

Further, when the charged amount of the component (c) is less than 1 mol per 1 mol of the melamine compound as the component (a), the melting point of the obtained resin cannot be 80 ° C or higher. When the resin is liquid or viscous at room temperature, or the melting point of the resin is 50
When it is as low as ℃ or less, after coating on a substrate, the organic solvent is scattered by drying to obtain a photo-curable resin layer, and then when this layer is post-processed such as embossing, it is applied to an embossing roll or a press plate. Resin adheres and patterning is not performed clearly.

The reaction of components (a), (b) and (c) is carried out in the presence of a suitable solvent. In this case, the solvent must be inert to the reaction. Examples of such a solvent include hydrocarbons such as benzene, toluene, xylene, and tetralin, cyclohexanone, dioxane, methyl ethyl ketone, methyl isobutyl ketone, and the like. Moreover, you may use these mixtures.

Then, as the catalyst, an acid effective for forming an ester from a carboxylic acid and an alkanol is generally suitable, but a particularly preferable one is an organic acid represented by paratoluenesulfonic acid. The amount of catalyst used is, for example, in the case of paratoluenesulfonic acid, about 100 ppm to 1% by weight, preferably 1000 to 5000, relative to the total amount of each component.
It is usually about ppm.

In the reaction system for obtaining the component (A), an acrylamide compound is present as a reactant and an ethylenically unsaturated bond is present in the product, so that it is generally necessary to prevent the polymerization.

Various compounds are known for preventing the polymerization of such ethylenically unsaturated bonds, and any desired compound can be used in the present invention. Specifically, there are, for example, phenol compounds and amine compounds. When a phenol compound is used, air can be blown into the reaction system because it can promote the distillation of the alkanol (R'OH) formed in addition to prolonging the polymerization inhibitory action. Blowing in is preferred.

This reaction can be carried out according to various operating modes. Specifically, for example, the components (a), (b) and (c) and the catalyst are charged into a reactor equipped with a stirrer, a cooler, and an air blowing device, and a small amount of air is added to the reaction system (liquid phase). Part) and gradually raise the temperature. Distillation of water or alkanol (R'OH) starts when the reaction system temperature is around 80 ° C, and the temperature is raised to about 100 to 120 ° C and heating is continued until distillation of alkanol stops, and the reaction is terminated.

The resin of component (A) obtained by this production is a mixture of resins having an ethylenically unsaturated bond represented by the following general formulas (III) to (VI).

[-CH ₂ NHCOCR ¹ = CH ₂ wherein Z ^{_{is, -CH 2 OR 2, R 1}} , R 2 is H
Or an alkyl group having 1 to 4 carbon atoms, R is an alkylene group having 1 to 8 carbon atoms, X is an integer of 10 to 650, and Y is a polyol residue].

When the resin of the component (A) can be used as the composition of the present invention, it may be used as it is without removing the solvent used in the reaction, or it may be used in a poor solvent such as hexane, heptane or cyclohexane (A). The component resin may be precipitated, dried and then isolated into a powder solid for use.

(B) Acrylic acid alkyl ester having one or more acryloyloxy groups in the molecule or methacrylic acid alkyl ester having one or more methacryloyloxy groups in the molecule: (meth) acryloyloxy which is a polymerizable carbon-carbon double bond Acrylic acid alkyl ester or methacrylic acid alkyl ester having one or more, preferably 2 to 6 groups in the molecule [hereinafter, both are represented as (meth) acrylic acid ester. Specific examples of] include benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrafurfuryl (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane. Glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trimethylolpropane tri (meth) acrylate, tri (meth) acrylate of tris-hydroxyethyl isocyanurate, tricyclodecane dimethanol di (meth) acrylate Rate,
Cyclohexanedimethanol di (meth) acrylate and other monofunctional and polyfunctional (meth) acrylates, phenylglycidyl ether (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, trimethylolpropane (Meth) of glycidyl ethers such as (tri) methacrylate of triglycidyl ether, poly (meth) acrylate of phenol novolak polyglycidyl ether, and di (meth) acrylate of bisphenol A diglycidyl ether
(Meth) acrylates and polyurethanes of polyester polyols, which are reaction products of polyhydric alcohols such as acrylate, neopentyl glycol, 1,6-hexanediol, and polybasic acids such as adipic acid, maleic acid, phthalic acid (Meth) acrylates and the like can be mentioned.

(C) Organic solvent: As the organic solvent of the component (C), benzene, toluene,
Examples thereof include aromatic hydrocarbons such as xylene, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, dioxane, and tetrahydrofuran. These organic solvents are preferably cyclohexanone, dioxane, methyl ethyl ketone, and methyl isobutyl ketone, which have a boiling point of 100 to 160 ° C., which facilitates evaporation during drying, and also have hydrophilicity.

(D) Photosensitizer: As the photosensitizer of the component (D), various photosensitizers that have already been used as photosensitizers for UV-curable coatings, for example, benzoin, benzoin methyl ether, benzoin. Ethyl ether, benzoin isopropyl ether, α
-Benzoin compounds such as methylbenzoyl and α-phenylbenzoin; anthraquinone compounds such as anthraquinone and methylanthraquinone; benzyl; diacetyl; phenylketone compounds such as acetophenone and benzophenone; diphenyldisulfide, tetramethylthium sulfide, etc. [Alpha] -chromium methylnaphthalene; halogenated hydrocarbons such as anthracene and hexachlorobutadiene, pentachlorobutadiene, and the like.

Optional components: In addition to the present composition, phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; Storage stability is improved. Furthermore, if necessary, an accelerator, a viscosity modifier, a surfactant,
You may mix | blend various auxiliary agents, such as a defoaming agent. It is also possible to blend a polymer such as styrene / butadiene rubber.

(Composition ratio) The mixing ratio of the (A) component and the (B) component is 50 to 90% by weight of the resin of the (A) component, 10 to 50% by weight of the (B) component, and 10% by weight of the (B) component. If it is less than%, the physical properties of the cured film such as scratch resistance, water resistance and alcohol resistance are insufficient. on the other hand,
When the content of the component (B) exceeds 50% by weight, a coating film having no tackiness cannot be obtained even if it is applied to a substrate and then dried to scatter the organic solvent.

The organic solvent of the component (C) is 10 to 900 parts by weight, preferably 40 to 700 parts by weight, based on 100 parts by weight of the total amount of the resins of the components (A) and (B).

The photosensitizer of the component (D) is 0.01 to 5% by weight, preferably 0.05 to 5% by weight based on the total amount of the resins of the components (A) and (B).
Used in a proportion of 1% by weight.

The accelerator is 0.05 to 5% by weight based on the total amount of the resins of the components (A) and (B).

The composition of the present invention is prepared so that the viscosity at 25 ° C. is 30 to 5,000 centipoise in order to facilitate impregnation or coating on a substrate.

(Production of Processed Product) The photocurable composition of the present invention is applied to or impregnated on a substrate such as a metal plate, paper or polyethylene terephthalate, and then the temperature at which the organic solvent of the component (B) scatters, for example, 100 to 1
A photocurable resin layer is formed on a base material by conducting it for 0.1 to 1 minute in a heating furnace set at 65 ° C. and drying, and the photocurable resin layer is patterned by a stanber, followed by ultraviolet rays, electron beams, etc. Is irradiated to photo-cur the resin, and aluminum is deposited on the photo-cured resin to form a hologram.

In addition, a photocurable resin composition is applied to the surface of the pre-set offset printed coated paper, and after drying, the photocurable resin is embossed and then photocured to form a relief to form a three-dimensional map or Can make posters.

Further, a photo-curable resin composition is applied onto a release film of polyethylene terephthalate, dried, a pattern is printed on the photo-curable resin, and then a hot stamping agent is applied on the printed surface, then plywood, ABS. A base material such as a sheet or a zinc plate is attached to the hot stamping agent surface, transferred onto the base material with a thermal transfer roll, the release film is removed, and the exposed photocurable resin layer is photocured to form a pattern A film, a metal plate, etc. transferred to a material can be manufactured.

The embossing is performed by a usual method using, for example, a pair of embossing rolls composed of a metal roll and a paper roll, for example, at 50 to 150 ° C. and a pressure of 10 to 50 kg / cm ² . One-sided embossing is sufficient for embossing, but double-sided embossing is also possible. Since the photo-curable resin coated on the paper is solid at room temperature, setting the temperature of the embossing roll to the softening point of the photo-curing resin or lower prevents the resin from adhering to the embossing roll. The light used to cure the photocurable resin includes high energy ionizing radiation and ultraviolet rays.

As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as Kotskcroft type accelerator, Van de Graaff type accelerator, linear accelerator, petatron, cyclotron is industrially most convenient and economically used. In addition, radiation such as γ-rays, X-rays, α-rays, β-rays, neutron rays, and proton rays emitted from radioactive isotopes and nuclear reactors can also be used.

Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low pressure mercury lamp,
There are high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, and sun lamps.

Hereinafter, the present invention will be described in detail with reference to manufacturing examples and application examples.
The parts and% in the examples are by weight unless otherwise specified.

Production Example of Resin of Component (A) in the Present Invention: Production Example 1 A four-necked flask was equipped with a stirrer, a thermometer, a cooler, and a glass tube for blowing air, and hexamethoxymethylmelamine (Mitsui Higashi) was placed in this flask. Pressure chemical Cymel 303 390
(1 mol), acrylamide 248.5 parts (3.5 mol), ethylene glycol 45 parts (1.5 equivalents), cyclohexanone 751.9 parts, paratoluene sulfonic acid 2 parts and hydroquinone 0.5 part were charged, and air was blown at a rate of 200 ml / min. While gradually raising the temperature to 100 ° C. and maintaining the same temperature for 7 hours, the reaction was terminated.

After completion of the reaction, the mixture was cooled to 70 ° C., 30 g of sodium bicarbonate was added, and this temperature was maintained for 30 minutes. Then, it filtered with the filter paper and obtained the resin solution. The viscosity of this resin solution is 420 cps (25 ° C),
The melting point of the resin obtained by evaporating the solvent was 112 ° C.

Production Examples 2 to 4 Table 1 shows the molar ratios of ethylene glycol and acrylamide charged to 1 mol of hexamethoxymethylmelamine.
A resin solution was obtained in the same manner as in Example 1 except that the resin solution was changed as shown in FIG.

Production Examples 5 to 8 In Production Example 1, the melamine compound as the component (a),
A resin solution having the viscosity shown in Table 1 was obtained in the same manner except that the kind of the polyhydric alcohol as the component (b) and the mixing ratio of each component were changed as shown in Table 1.

Example 1 280 parts of the resin obtained in the above Production Example 1 (cyclohexanone 50%
Solution) and 60 parts of pentaerythritol triacrylate were mixed well, and further 60 parts of cyclohexanone was added to prepare a resin solution having a resin concentration of 50%. To 100 parts of this resin solution,
1.5 parts of 2,2-dimethoxy-2-phenylacetophenone was blended as a photosensitizer to obtain a photocurable resin composition.

Examples 2 to 8 and Comparative Examples 1 to 5 In Application Example 1, the ratio of the resin as the component (A) and the resins obtained in Production Examples 2 to 8 and carbon-carbon in the molecule of the portion (B) were used. A photocurable resin composition was obtained in the same manner except that the ratio and kind of the compound having a double bond were changed.

(1) Application example of formation of relief layer These compositions were applied on the surface of offset printed coated paper at a coating amount of 5 g / m ³ using a Meyer bar and dried at 150 ° C to evaporate the solvent. After that, embossing was carried out, and then ultraviolet rays generated from a mercury lamp were irradiated to photo-cure the surface of the coated paper to form a transparent relief layer. As a result, a printed matter having a three-dimensional effect was obtained.

It can be used for record jackets, posters, works of art, etc.

(II) Application example of formation of hologram layer These compositions were coated on a 75 μm polyethylene terephthalate film with a roll coater in an amount of ² g / m ² and dried at 80 ° C. to evaporate the solvent, and then laser light was applied. A fine stamped layer was formed by hot-pressing at 150 ° C. with a press stamper continuously prepared from the master hologram prepared by using. Then, it was photo-cured by irradiating it with ultraviolet rays generated from a mercury lamp. Further, an Al layer was vapor-deposited thereon by a vacuum vapor deposition method to form a hologram. This can be used for printed matter, a display, and the like that display a three-dimensional image.

(III) Application example of transfer film These compositions were coated on a 25 μm polyethylene terephthalate release film by a gravure printing method, dried at 105 ° C., then a gravure pattern was printed on the composition, and heat sealing was performed. Of acrylic adhesive (hot stamping agent) was applied. After the synthesis, thermal transfer was performed with a heat roll from the film side with the acrylic adhesive side facing down. Then, the peeling film was peeled off, and the resin of the surface layer was cured by irradiating with ultraviolet rays generated from a mercury lamp. This can be used as a wall material.

Table 2 shows the physical properties of these processed products.

The evaluation methods of physical properties are as follows.

Chemical resistance: When the cured surface of this composition is rubbed with a gauze soaked in methyl ethyl ketone 100 times to rub it back and forth, the one with no abnormality on the surface is regarded as good, and the abnormality on the surface causes the surface of the substrate to The exposed one was regarded as defective.

Alcohol resistance and water resistance: When the cured surface of this composition is contacted with methanol, ethanol, and water for 24 hours at room temperature, those with no abnormality on the surface are regarded as good, and the surface shows abnormalities such as peeling and blistering. The one in which the surface of the substrate was exposed was regarded as defective.

Heat resistance: The cured surface of the composition was heated to 200 ° C. with a hot roll and held for 3 minutes, and then discoloration, deformation, etc. were observed. Those with no abnormalities were regarded as good, and those with yellowing or deformation or peeling were regarded as poor.

Scratch resistance: When the cured surface of the present composition was rubbed with # 0000 steel wool 10 times, the surface without any change was evaluated as good, and the surface scratched or whitened was evaluated as poor.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03F 7/027 511 (56) References JP 61-98761 (JP, A) JP 54 -155249 (JP, A) JP-A-58-156099 (JP, A)

Claims (1)

[Claims] 1. Component (A): Component (a): General formula In the formula, R ′ represents H or a hydrocarbon group having 1 to 4 carbon atoms, and R represents a methyl group, a phenyl group, —N (CH ₂ O
R ') ₂ (R' is the same or different H or hydrocarbon group having 1 to 4 carbon atoms) or the organic group represented by the following formula (Y is —CH ₂ OR ′ or hydrogen, R ′ is H or a hydrocarbon group having 1 to 4 carbon atoms which is the same as or different from R ′ above) 1 mol (b) Component: Polyhydric alcohol of 500 or less 1.5 to 4 equivalents (one hydroxyl group is 1 equivalent) (c) component: amide compound selected from acrylamide and α-lower alkyl substituted acrylamide 1 to 4.5 moles (a), ( Melamine acrylic compound 30 solid at 20 ° C. obtained by reacting components b) and (c) in the above proportions
To 90% by weight (B) component: Acrylic acid alkyl ester having one or more acryloyloxy groups in the molecule or methacrylic acid alkyl ester having one or more methacryloyloxy groups in the molecule
10 to 50 wt% Component (C): 1 to 100 parts by weight of the total amount of the non-reactive organic solvents (A) and (B) components that dissolve the above components (A) and (B)
0 to 900 parts by weight of component (D): photosensitizer 0.05 to 5 relative to the total amount of the above components (A) and (B)
Weight% A photocurable resin composition containing the above components (A), (B), (C) and (D) in the above proportions.