JPH0796578B2 - 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 of (a) is insufficient in 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 for the production of process release paper, so the hardness of the cured film, scratch resistance, water resistance, physical chemical resistance, especially alcohol resistance such as methanol and ethanol. It has the disadvantage of being inferior in sex.

[Problems 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 H or a hydrocarbon group having 1 to 4 carbon atoms which is the same as or different from R '), (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 (1 equivalent of one hydroxyl group) (c) component: amide compound selected from acrylamide and α-lower alkyl substituted acrylamide 1 to 4.5 mol (d) component: molecule 0.01 to 2 equivalents of acrylic acid alkyl ester or methacrylic acid alkyl ester having at least one hydroxyl group and at least two acryloyloxy groups or methacryloyloxy groups therein (one hydroxyl group is 1 equivalent), (a), ( 10 to 90% by weight of a melamine acrylic compound which is a solid at 20 ° C. obtained by reacting the components b), (c) and (d) in the above proportion (B) component: Non-reactive organic solvent that dissolves component (A) 90 to 10% by weight (C) component: Photosensitizer 0.05 to 5% by weight of the above component (A) Components (A), (B) and (C) The present invention provides a photocurable resin composition containing:

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, (c) acrylic amide,
(D) A polymerizable compound having an -OH group and an acryloyloxy group or a methacryloyloxy group is used as a raw material in the above proportions, and a catalyst is mixed in the raw material at 50 to 150 ° C, preferably 2 to 20 at 80 to 130 ° C. It is obtained by reacting for a time.

Specific examples and some of the methylolated melamine compounds and alkyl etherified melamine compounds of the component (a) are as follows. Hexamethylol melamine,
Pentamethylolmelamine, tetramethylolmelamine, trimethylolmelamine, dimethylolmelamine,
Hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, trimethoxymethylmelamine, tributoxymethylmelamine, hexaethoxymethylmelamine, pentaethoxymethylmelamine, tetraethoxymethylmelamine, trimethoxymethyl-diethoxymelamine, triethoxy Methyl-dibutoxymethylmelamine, hexapropoxymethylmelamine, tripropoxymethylmelamine, dibutoxymethylmelamine, trimethoxymethylmelamine, dipropoxymelamine, hexabutoxymethylmelamine, monomethoxymethylmelamine, tetrabutoxymethylmelamine, tetramethoxymethylmelamine , Methyl guanamine, dimethoxymethyl guanamine, dibutoxymethyl guanamine, monomethoxyme Ruguanamin, 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.

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. The α-lower alkyl group generally has 1 to 4 carbon atoms.
The ones are suitable. Mixtures of these can also be used.

Furthermore, as the acrylic acid alkyl ester or the methacrylic acid alkyl ester having at least one hydroxyl group and at least two acryloyloxy groups or methacryloyloxy groups in the molecule of the component (d), pentaerythritol triacrylate, pentaerythritol triester is used. Methacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, tripentaerythritol tetraacrylate, tripentaerythritol tetramethacrylate, Tripentaerythritol pentaacrylate, tripe Data dipentaerythritol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, ditrimethylolpropane triacrylate, include ditrimethylolpropane trimethacrylate and the like, also 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) to 1.5 moles of the methylolated melamine compound or the alkyl etherified melamine compound or the alkyl etherified melamine compound of the component (a) is 1.5 to 4 equivalents (equivalent to 1 mole of —OH group is 1 mole).
Equivalent)), 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. The proportion of the compound having a hydroxyl group of the component (d) and an acryloyloxy group or a methacryloyloxy group is 0.01 to 2 equivalents (-OH group 1
The molar equivalent is 1 equivalent), preferably 0.1 to 1 equivalent.

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 of 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. Further, if the amount of the component (d) charged is less than 0.01 equivalent, the hardness, scratch resistance, water resistance, and alcohol resistance of the cured film of the resin obtained will not be fully exhibited. On the other hand, when the amount is 2 equivalents or more, the polymer is excessively polymerized during the reaction, and the viscosity of the reaction solution becomes too high, which makes stirring difficult.

The reaction of components (a), (b), (c) and (d) is carried out in the presence of a suitable solvent. The solvent must be inert with respect to the reaction. Examples of such a solvent include hydrocarbons such as benzene, toluene, xylene, and tetralin, cyclohexanone, dioxane,
Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Also, a mixture of these may be used.

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 and a compound having a hydroxyl group (-OH) and an acryloyloxy group or a methacryloyloxy group are used as reactants, and an ethylenically unsaturated bond is present in the product. Therefore, it is generally necessary to prevent its 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, (a), (b), in a reactor equipped with a stirrer, a cooler, and an air blower,
The components (c) and (d), the catalyst and the solvent are charged, and the temperature is gradually raised while blowing a small amount of air into the reaction system (liquid phase part).

When the reaction system temperature is around 80 ° C, water or alkanol (R '
(OH) starts to distill, the temperature is raised to about 100 to 120 ° C., and heating is continued until the alkanol stops distilling to complete the reaction.

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 (X).

[Wherein Z is ^{_{-CH 2 NHCOCR 1 = CH 2,}} -CH 2 OR 2, -RX)
_n , R ¹ and R ² are H or an alkyl group having 1 to 4 carbon atoms, R is an alcohol residue of a compound containing a hydroxyl group and an acryloyloxy or methacryloyloxy group, X is an acryloyloxy group or a methacryloyloxy group, and n is 2 ~ Indicates an integer obtained by subtracting the hydroxyl value from the alcohol value. When the resin of the component (A) is combined with the composition of the present invention, it may be used as it is without removing the solvent used in the reaction, or with 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) Organic solvent: As the organic solvent of the component (B), 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.

(C) Photosensitizer: As the photosensitizer of the component (C), 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 methylbenzoin and α-phenylbenzoin; anthraquinone compounds such as anthraquinone and methylanthraquinone; benzyl; diacetyl; phenylketone compounds such as acetophenone and benzophenone; diphenyldisulfide, tetramethylthiuramsulfide and the like [Alpha] -chloromethylnaphthalene; 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) As for the mixing ratio of the component (A) and the component (B), the resin of the component (A) is 10 to 90% by weight, preferably 35 to 70% by weight, the component (B) is 90 to 10% by weight, It is preferably 65 to 30% by weight.

The photosensitizer of the component (C) is used in a proportion of 0.01 to 5% by weight, preferably 0.05 to 1% by weight of the component (A). The accelerator is 0.05 to 5% by weight of the component (A).

The composition of the present invention is generally prepared to have a viscosity of 30 to 5,000 centipoise at 25 ° C. 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 the base material by drying in a heating furnace set at 65 ° C for 0.1 to 1 minute, and the photocurable resin layer is patterned by a stamper, 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.

Furthermore, a photocurable resin composition is applied onto a release film made of polyethylene terephthalate, dried, a pattern is printed on the photocurable resin, and then a hot stamping agent is applied onto 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 a high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as Kotsk Croft accelerator, Van De Graaf accelerator, linear accelerator, betatron, cyclotron is the most convenient and economical in industry. 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 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 Toatsu Chemical Cymel 30
3) 390 parts (1 mol), acrylamide 248.5 parts (3.5 mol), ethylene glycol 45 parts (1.5 equivalents), pentaerythritol triacrylate 216.7 parts (0.7 equivalents) cyclohexanone 708 parts, paratoluene sulfonic acid 2 parts and hydroquinone 0.7 parts. Then, while blowing air at a rate of 200 ml / min, gradually raise the temperature to 100 ° C and bring it to the same temperature.
The reaction was terminated by keeping the time.

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 was 540 cps (25 ° C), and the melting point of the resin obtained by evaporating the solvent was 108 ° C.

Production Examples 2 to 20 In Production Example 1, the melamine compound as the component (a),
(B) Component polyhydric alcohol, (c) component acrylamide, (d) component OH alkyl group and acryloyloxy group or methacryloyloxy group-containing alkyl acrylate or methacrylic acid alkyl ester, and blending ratio of each component Was changed as shown in Table 1 to obtain a resin solution having the viscosity shown in Table 1 in the same manner.

Reference Example 1 Diglycidyl ether of Bisphenol A manufactured by Yuka Shell Epoxy Co., Ltd. "Epicoat 1004" (trade name, epoxy equivalent 913) 464 parts, acrylic acid 37 parts, hydroquinone monomethyl ether 1 part, tetramethylbenzyl ammonium bromide 5 Parts and 500 parts of methyl isobutyl ketone are charged into a 4-neck flask of 1, and a stirrer, a reflux condenser,
Attach an air blowing tube and a thermometer, and heat while stirring and blowing air at a rate of 200 ml / min.
The temperature was raised to 0 ° C.

The reaction was carried out at the same temperature for 5 hours to obtain an epoxy acrylate resin solution having a viscosity (25 ° C.) of 280 cps. The melting point of the resin from which the solvent was removed was 75 ° C.

Application Examples 1 to 13, Comparative Examples 1 to 7, Reference Example 2 100 parts of the resin solutions obtained in the above Production Examples 1 to 20 and Reference Example were mixed with 2,2-dimethoxy-2-phenylacetophene as a photosensitizer. A non-1.5 part was compounded to obtain a photocurable resin composition.

(I) Application Example of Relief Layer Formation These compositions are applied to the surface of offset printed coated paper with a Meyer bar at a coating amount of 5 g / m ³ and 1
Dry at 50 ℃ (Epoxy acrylate of the reference example is 30 g /
The coating amount of m ^3, after being stripped 120 ° C. Drying) solvent, embossed, and then an ultraviolet ray generated from the mercury lamp to form a transparent relief layer by photocuring the coated paper surface. 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 ³ and dried at 80 ° C. to volatilize the solvent, and then laser light was applied. A fine stamp layer was formed by hot pressing at 150 ° C. with a press stamper that was subsequently created from the master hologram that was made using the above. 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. Thermal transfer was performed on the plywood 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.

The physical properties of these processed products are shown in Table 2. 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 brought into contact with methanol, ethanol and water at room temperature for 24 hours, those with no abnormalities on the surface are considered good, and there are 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 regarded as poor.

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 mol (d) component: molecule 0.01 to 2 equivalents of acrylic acid alkyl ester or methacrylic acid alkyl ester having at least one hydroxyl group and at least two acryloyloxy groups or methacryloyloxy groups therein (one hydroxyl group is 1 equivalent), (a) above. Melamine acryl compound solid at 20 ° C. obtained by reacting components (b), (c) and (d) in the above proportions 10 to 90% by weight Component (B) Non-reactive organic solvent that dissolves the above component (A) 90 to 10% by weight (C) component: Photosensitizer 0.05 to 5% by weight of the above component (A) The above (A), (B) and (C) A photocurable resin composition containing components.