JPH0598112A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a low-viscosity curable resin composition suitable for etching resist, readily curable by irradiation with active energy rays or by heating to form a cured material having alkali solubility and releasability. CONSTITUTION:100 pts.wt total amounts of (A) 20-70 pts.wt., preferably 30-60 compound containing one carboxyl group and one (meth) acryloyl group in the molecule and (B) 30-80 pts.wt., preferably 40-70 pts.wt. compound containing two or more (meth) acryloyl groups in the molecule are blended with (C) 0.01-5 pts.wt., preferably 0.05-1 pt.wt. leveling agent and (D) 130 pts.wt., preferably 3-10 pts.wt. granular filler which is soluble in a mixture of the components A and B and has >=50 deg.C glass transition point and 1,000-500,000 number-average molecular weight or is insoluble in the mixture of the components A and B and has >=50 deg.C glass transition point.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The resin composition according to the present invention is applied to the surface of a material having fine irregularities without generating bubbles and can be cured by irradiating with ultraviolet rays, and a resin film after curing can be obtained. However, it has the property of exhibiting corrosion resistance against acid treatment and having solubility or peelability (hereinafter referred to as “dissolution / peelability”) against alkali treatment,
In various industries, it can be used as a casting material, a coating material or a molding material, and is particularly useful as a resin composition for an etching resist, especially as a resin composition for a backing material in a secondary etching step during the production of a shadow mask. ..

[0002]

2. Description of the Related Art A shadow mask has a function of causing electrons emitted from an electron gun in a cathode ray tube for a color television to collide with an illuminant of a predetermined color, and the ratio of the long side to the short side is 10 ² to 1 1. 0 ³ is of rectangular elongated hole (hereinafter simply elongated as rectangular holes) or minute holes such as circular holes, a thin metal plate provided numerous in a predetermined pattern by etching. The formation of the minute holes is performed by providing recesses at corresponding positions on the front and back surfaces of the metal plate, and communicating the bottoms of the corresponding recesses.

The outline of the manufacturing process of the shadow mask is as follows. First, a photosensitive resin film is applied to both front and back surfaces of a thin metal plate made of iron or the like, and then a negative film having a pattern is adhered to the metal plate to make it photosensitive. Photographic printing is performed to cure the exposed portion of the resin film, and the non-exposed portion of the photosensitive resin film is removed by a development process. Next, primary etching is performed with a corrosive solution such as iron perchloride to form fine recesses that do not penetrate each other from the front and back surfaces. A resin composition for a backing material is applied to only one surface to form a film that fills minute recesses on one surface of a metal plate, and the resin composition is cured by irradiation with light such as ultraviolet rays. After protecting one side in this way, again perform a secondary etching targeting the concave portion on the other surface with a corrosive solution, and connect the concave portion on one surface and the concave portion on the other surface by the primary etching to communicate at the bottom portion. Then, each cured resin film of the photosensitive resin for pattern formation and the resin composition for backing material is removed by alkali treatment to obtain a shadow mask.

In the above shadow mask manufacturing method, the resin composition for the backing material applied after the primary etching must satisfy the following characteristics (1) to (3). Hole filling property: A property of uniformly wetting the surface of a material having a narrow rectangular recess having a width of 100 to 200 μm and a length of 10 to 20 cm, and filling the recess without generating bubbles in the recess. Surface smoothness: The property that the surface of the cured resin film is smooth because bubbles caused by minute gas generated when the resin composition for backing material fills the elongated rectangular recesses does not remain in the cured resin surface layer. Curability: The property that the bottom of the recess is uniformly cured. Etching resistance: The cured resin film has etching resistance against secondary etching by a corrosive liquid such as iron perchloride,
The property of protecting the surface of the coated material. Alkali solubility: The property that the cured resin film is easily dissolved and peeled by alkali treatment. Pattern formability: The property of forming fine holes in a thin metal plate faithfully to the pattern drawn on a negative film (negative pattern). For example, long and narrow rectangular fine holes are formed with their long sides parallel to each other. In the case of a negative pattern in which a large number are provided at regular intervals, the long sides are linear, the long sides of adjacent holes are parallel to each other, and the long sides of adjacent holes have a constant long side interval. The property that the regular shape peculiar to the negative pattern is retained to form holes in the metal plate and the metal parts sandwiched between the long sides of the elongated holes are not twisted.

As a material satisfying the above-mentioned performance required for a resin composition for a backing material, a composition in which a resin forming a film soluble in an alkaline liquid is dissolved in an organic solvent is used at present. After being applied by spraying or another method, the organic solvent is evaporated in a warm air drying oven or the like to form a resin coating film.

[0006]

However, the resin composition for a backing material in which a resin forming a film is dissolved in an organic solvent has the following two problems. 1) Since a large amount of organic solvent is contained, a drying furnace for evaporating the organic solvent after applying the resin composition for backing material and a device for collecting the evaporated solvent are required. 2) Since a large amount of organic solvent evaporates during drying, there is a risk of toxicity, ignition and explosion. In order to reduce the risk of ignition, explosion and fire in the drying process, the use of flame retardant chlorine-based solvents such as trichlorethylene has been considered, but it has recently been pointed out that these cause problems such as air pollution. And their use is regulated. In order to solve these problems, a method of using a water-based UV-curable resin (Japanese Patent Laid-Open Nos. 1-261410 and 2-1334).
04), a method using an essentially solvent-free UV curable resin (Japanese Patent Laid-Open No. 2-110166) has been proposed.

However, these resins have been developed for a metal plate having a large number of fine hemispherical holes, and when used for a metal plate having a large number of elongated rectangular recesses, the metal after secondary etching is used. In the plate, there is a problem that the intervals between the elongated rectangular holes are not constant, or a metal portion sandwiched between the long sides of the elongated rectangular recesses is twisted. Such defects may occur during the secondary etching or during the alkali treatment after the secondary etching, but the detailed mechanism has not been clarified. In addition, all of the conventional ultraviolet curable resins used for producing shadow masks have a flash point, and there is a problem in that the handling thereof needs to be careful.

The present invention solves the above problems of conventional UV-curable resins, and is particularly excellent as a resin composition for a backing material of a shadow mask, has no flash point, and is substantially solvent-free. It is an object of the present invention to provide a resin composition that is cured by irradiation with heat or active energy rays.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and as a result, as a component of a curable resin composition, a glass transition point is 50 ° C. or higher and a number average molecular weight is By mixing 1,000 to 500,000 polymer or granular filler having a glass transition point of 50 ° C or higher, generation of strain in the cured resin film due to heating and cooling in secondary etching or alkali dissolution is prevented, and long rectangular holes are formed. It has been found that defects such as non-uniform spacing and twisting of the metal plate can be prevented, and further that this resin composition causes rapid gelation by heating and does not have a flash point. Has been completed. That is, the present invention is a curable composition comprising the following (a), (b), (c) and (d) and having a viscosity at 25 ° C. of 5000 cps or less. (A) Compound having one carboxyl group and one acryloyl or methacryloyl group in the molecule (b) Compound having two or more acryloyl or methacryloyl groups in the molecule (c) Leveling agent (d) Above It is soluble in the mixture of (a) and (b), has a glass transition point of 50 ° C or higher, and has a number average molecular weight of 1,000 to 500,0.
Granular filler which is insoluble in the polymer of 00 or the mixture of the above (a) and (b) and has a glass transition point of 50 ° C. or higher.

Each component constituting the composition of the present invention will be described in detail below. The component (a) is a compound having one carboxyl group and one acryloyl or methacryloyl group (hereinafter referred to as (meth) acryloyl group) in the molecule, and is dissolved in a cured product of the resin composition of the present invention by alkali treatment. -A component that imparts releasability. Examples of preferable component (a) include the following. Dibasic acid or / and its acid anhydride, and acrylate or methacrylate having a hydroxyl group at the terminal (hereinafter,
Reaction product with (meth) acrylate). As the dibasic acid and / or its acid anhydride, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic anhydride, succinic acid and the like are used, and as the (meth) acrylate having a hydroxyl group at the terminal, hydroxyethyl ( Meta)
Acrylate and hydroxypropyl (meth) acrylate can be used, and among the above reaction products, those having a carboxyl group at the molecular end are used. Specific compounds include (meth) acryloyloxyethyl monophthalate (trade name "Aronix M-5400" manufactured by Toagosei Chemical Industry Co., Ltd.), (meth) acryloyloxypropyl monophthalate, (meth) acryloyloxyethyl monophthalate. Tetrahydrophthalate, (meth) acryloyloxypropyl monotetrahydrophthalate,
(Meth) acryloyloxyethyl monohexahydrophthalate, (meth) acryloyloxypropyl monohexahydrophthalate, (meth) acryloyloxyethyl monosuccinate (trade name "Aronix M-5500" manufactured by Toagosei Chemical Industry Co., Ltd.), Examples thereof include (meth) acryloyloxypropyl monosuccinate and monohydroxyethyl maleic anhydride (meth) acrylate.

A reaction product of a lactone and a (meth) acrylate having a carboxylic acid group at the terminal. Ε-caprolactone or the like can be used as the lactone, and (meth) acrylic acid or the like can be used as the (meth) acrylate having a carboxylic acid group at the terminal, and a specific compound is a molecule obtained by reacting these. Examples thereof include compounds having a carboxyl group at the terminal (for example, "Aronix M-5300" manufactured by Toagosei Chemical Industry Co., Ltd.).

Other compounds. Specific compounds include compounds such as (meth) acrylic acid and its dimer (trade name “Aronix M-5600” manufactured by Toagosei Chemical Industry Co., Ltd.). By blending one or more of the compounds exemplified in the above to as the component (a) in the composition of the present invention,
It is possible to obtain a composition having a good dissolution and peeling property of a cured product by an alkali treatment, and in particular, acrylic acid dimer (trade name “Aronix M-560 manufactured by Toagosei Kagaku Kogyo Co., Ltd.
0 "), monohydroxyethyl maleic anhydride (meth)
Acrylate itself has a relatively low viscosity (viscosity at 25 ° C. is 200 to 400 cps), and is preferable because it makes the resin composition of the present invention a low viscosity composition.

The preferable blending amount of the above-mentioned component (a) is
The total amount of the components (a) and (b) is 100 parts by weight (hereinafter, "parts" means "parts by weight"), and is 20 to 70 parts, more preferably 30 to 60 parts. Compounding amount is 20
If the amount is less than 70 parts, the alkali dissolution / peeling property is not sufficient, and if the amount is more than 70 parts, the corrosion resistance during secondary etching may be deteriorated.

The component (b) is a compound having two or more (meth) acryloyl groups in the molecule, which enhances the curability of the resin composition of the present invention and enhances the etching resistance of the cured product. Yes. Examples of preferable component (b) include the following. Polyol poly (meth) acrylate. It is a reaction product of a polyhydric alcohol and (meth) acrylic acid. As the polyhydric alcohol, polyglycols such as polyethylene glycol and polypropylene glycol, trimethylolpropane and pentaerythritol can be used. Specific compounds include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like. Also,
Obtained by reacting a reaction product of (meth) acrylic acid with a compound obtained by adding alkylene oxide such as ethylene oxide or propylene oxide to polyhydric alcohol, and (meth) acrylate having a terminal hydroxyl group with an acid such as phosphoric acid. A bifunctional or trifunctional compound such as phosphoric acid acrylate can also be used.

Polyester poly (meth) acrylate. A reaction product of a polyester type polyhydric alcohol and (meth) acrylic acid, for example, a dibasic acid such as adipic acid or phthalic acid and an anhydride thereof and a polyhydric alcohol such as diethylene glycol, trimethylolpropane, or pentaerythritol (meth) ) A polyfunctional compound obtained by the reaction with acrylic acid can be used.

Epoxy (meth) acrylate. A compound obtained by reacting an epoxy group of an epoxy compound having two or more epoxy groups in a molecule with (meth) acrylic acid, for example, polyglycidyl of polyhydric alcohol such as diglycidyl ether of bisphenol A. The polyfunctional compound obtained by reaction of ether and (meth) acrylic acid is mentioned. Among the above compounds, the polyol poly (meth) acrylate is preferable in that it can lower the viscosity of the resin composition of the present invention and can obtain a cured product having excellent etching resistance, and trimethylolpropane. Tri (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferred compounds. One or more of the above compounds can be incorporated into the composition of the present invention. Among the above compounds, those having a boiling point of 100 ° C. or higher under normal pressure have an advantage of low irritation to the skin when handling the compound.

The preferable amount of the component (b) is 30 to 80 parts, more preferably 40 to 70 parts, with the total amount of the components (a) and (b) being 100 parts. If the blending amount is less than 30 parts, the curability of the composition is lowered, and further the etching resistance of the cured product is lowered. On the other hand, if it is more than 80 parts, the alkali dissolution / peeling property of the cured product may be insufficient.

The component (c) is a leveling agent. This component makes it possible to enhance the hole filling property of the resin composition of the present invention and the surface smoothness of the cured product, and the purpose can be sufficiently achieved by using a general surfactant.
Specific compounds include, for example, nonionic fluorinated alkyl ester, Florard FC-430 (manufactured by Sumitomo 3M Limited), Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc.), Megafac F-179. (Manufactured by Dainippon Ink and Chemicals, Inc.) and NUC Silicone L7002 (manufactured by Nippon Unicar Co., Ltd.) as a silicone compound
Etc. Among the above compounds, Megafac F-17
9 and NUC Silicone L7002 having low foaming property are preferable because a resin coating film having excellent surface smoothness can be easily obtained.

The blending amount of the component (c) is preferably 0.01 to 5 parts, more preferably 0.05 to 1 part, based on 100 parts of the total amount of the components (a) and (b). 0.01
If it is less than 5 parts, it may be difficult to impart properties such as hole filling and surface smoothness to the resin composition of the present invention, and if it exceeds 5 parts, conversely cracking of the cured product (abbreviated as cissing) is performed. ) Or swelling may occur, and defects in the resin coating film may easily occur.

The component (d) is the above component (a) and (b).
It is insoluble in a polymer having a glass transition point of 50 ° C. or higher and a number average molecular weight of 1,000 to 500,000 or a mixture of the components (a) and (b) and having a glass transition point of 50 ° C. It is the above-mentioned granular filler. These ingredients are
By relaxing or reducing the strain generated when the composition of the present invention is cured, a metal plate provided with a large number of elongated rectangular holes, during the secondary etching, or a defect that is twisted during alkali dissolution after the secondary etching It has the effect of preventing. The preferred polymer in the present invention is a linear polymer, specifically, a polymer of a monomer having a vinyl group such as polystyrene, polyethylene and a styrene-maleic acid copolymer. As polystyrene, α- or β-position in the vinyl group of styrene, poly α- or β-alkyl styrene or poly α- or β-alkoxy obtained by polymerizing a monomer substituted with an alkyl group or an alkoxy group, etc. Styrene is preferred, and specific examples of poly α- or β-alkyl styrene include poly α-methyl styrene and poly β-ethyl styrene, and specific examples of poly α- or β-alkoxy styrene include poly α-methoxy styrene. And poly β-ethoxystyrene. The number average molecular weight of the polymer is 1,
It is 000 to 500,000. The polymer having a low number average molecular weight acts as a plasticizer, and the cured product of the composition of the present invention has tack, and there is a problem of contaminating the roll of a coating machine, and when the number average molecular weight is too high, the composition of the present invention There is a problem that the viscosity of the product becomes high and coating becomes difficult. The particulate filler in the present invention is insoluble in the mixture of the above-mentioned components (a) and (b) and is not affected by heat change during secondary etching or alkali dissolution, and therefore has a glass transition point of 50 ° C or higher. It is necessary to be. The average particle size of the granular filler is
It is preferably 10 μm or less, more preferably 5 μm or less. Specific preferred examples of the granular filler include calcium carbonate,
Inorganic granular filler such as clay or bentonite, Tospearl 103, Tospearl 105 (all are trade names of Toshiba Silicone Co., Ltd.), Bell Pearl R-800, Bell Pearl S-830
There are organic granular fillers such as (all are trade names manufactured by Kanebo Co., Ltd.). The compounding amount of the component (d) is preferably 1 to 30 parts, with the total amount of the components (a) and (b) being 100 parts. If it is less than 1 part, the effect of relaxing or reducing the strain due to curing shrinkage becomes insufficient, the intervals between the elongated rectangular holes formed in the metal plate may become uneven, and the metal part may be twisted. If so, the mechanical strength of the resin becomes small, and the cured resin film may be cracked during the secondary etching, making it unsuitable for use. A more preferable compounding amount of the component (d) is 3 to 10 parts.

The resin composition of the present invention can be easily cured by irradiation with active energy rays such as ultraviolet rays, visible rays or electron rays, or by heating, and depending on the curing means, the following component (e) is used. When blended with, the resin composition can be cured in a shorter time. When the resin composition is cured by irradiation with ultraviolet rays or visible light, a sensitizer that is generally used, for example, benzophenone and its derivatives, in order to sufficiently exhibit photocurability in the resin composition, Benzoin, benzoin alkyl ether, 2-methyl- [4- (methyl-4-phenyl]-
2-morpholino-1-propanone, benzyl dimethyl ketal and 1-hydroxycyclohexyl phenyl ketone (commercially available, Ciba Geigy Irgacure 18
There are four. ) Etc. are preferably blended.

When the resin composition is cured mainly by a heat energy source such as a heating furnace, infrared rays and microwaves,
It is preferable to add a thermal polymerization initiator, and the thermal polymerization initiator preferably used includes, for example, azo compounds such as azoisobutyronitrile, ketone peroxides, hydroperoxides, alkyl peroxides. , Various organic peroxides such as acyl peroxides and peroxyesters, and inorganic peroxides such as ammonium persulfate. Leave at room temperature or 100
When heated at a relatively low temperature of ℃ or less, it is preferable to blend a polymerization accelerator together with the above-mentioned thermal polymerization initiator. As preferable polymerization accelerators, for example, metals such as cobalt, iron and manganese and naphthenic acid, linoleic acid and acetylacetone. And the like, reducing amines such as dimethylparatoluidine, ascorbic acid, and other reducing substances. These polymerization accelerators are used in combination, for example, in the combination of hydroperoxides, ketone peroxides, peroxyesters and organic metal salts, or acylperoxides and reducing amines.

The amount of the component (e) is preferably 1 to 10 parts, with the total amount of the components (a) and (b) being 100 parts. If it is less than 1 part, the effect of accelerating the initiation of photopolymerization becomes insufficient, and if it exceeds 10 parts, the components that are truly necessary for the cured product may be reduced, and the target properties of the cured product may deteriorate. The more preferable amount of the component (e) used is 2 to 8 parts.

In addition, in order to reduce the viscosity of the resin composition of the present invention, an organic solvent as the component (f) or a low-viscosity compound having one (meth) acryloyl group in the molecule other than the component (a) is appropriately blended. You can also do it. Preferred specific examples of the organic solvent include alcohols such as methanol, ethanol, butanol and IPA, butyl cellosolve, methyl cellosolve, cellosolve such as ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cellosolve acetate such as butyl cellosolve acetate, propylene. Examples include glycol monomethyl ether, toluene and xylene. The preferable mixing ratio of the organic solvent is 0 to 10 parts per 100 parts of the total of the components (a) and (b).

Further, as a preferred specific example of the low-viscosity compound having one acryloyl or methacryloyl group in the molecule, those having a viscosity at 25 ° C. of 20 cps or less are preferred, and specific examples of suitable compounds include, for example, Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylamide, diacetone acrylamide, dimethyl acrylamide, benzyl (meth) acrylate, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, poly Alkylene (C2-3) Glycol monoalkyl (C1-9)
There are ether mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and phenoxyethoxyethyl acrylate (trade name "Aronix M-101" manufactured by Toagosei Chemical Industry Co., Ltd.).
One kind or two or more kinds can be used. The preferable blending ratio of the low-viscosity compound is the sum of the components (a) and (b).
It is 0 to 20 copies per 100 copies. Among the above-mentioned low-viscosity compounds, those having a boiling point of 100 ° C. or higher at normal pressure have an advantage of low irritation to the skin when handling the compounds.

In addition, a chain transfer agent such as a monothiol compound may be added to the composition of the present invention in order to improve the alkali solubility of the cured resin film.

The composition of the present invention has a viscosity at 25 ° C. of 50.
00cps or less, more preferable viscosity is 2000cps
It is below. The viscosity of the composition can be easily adjusted by appropriately selecting and using the kinds and blending amounts of the above-mentioned various components. Viscosity of composition at 25 ℃ is 5000cp
When it exceeds s, it becomes difficult to uniformly wet the surface of the material having the concave portions to fill the holes.

In order to obtain the resin composition of the present invention, it is sufficient to uniformly mix the above-mentioned components by a usual mixing method, and there is no particular limitation on the order of mixing the components or the mixing device. However, when a solid component is mixed at room temperature, it is possible to heat the mixture to a temperature at which the component melts or disperses to perform the mixing.

As the method for applying the resin composition of the present invention, any ordinary application method such as spraying, flow coating and dip coating can be used.

In order to cure the resin composition of the present invention, any curing means such as irradiation with active energy rays or heating may be adopted, but it is capable of curing with high energy efficiency and equipment of energy source. Curing by irradiation with an active energy ray is preferable from the viewpoint of saving space. The curing operation such as irradiation with active energy rays or heating and the alkali treatment of the cured product may be carried out according to a conventional method.

[0031]

EXAMPLES AND COMPARATIVE EXAMPLES Next, examples and comparative examples will be given.
The present invention will be described in more detail. The evaluation of various properties of the resin composition and the cured resin film thereof was performed by the following methods. <Viscosity> The viscosity of the composition at 25 ° C. was measured using an E-type viscometer. <Hole filling property> A resin composition of the present invention is formed on one surface of an iron plate (hereinafter simply referred to as a test iron plate) having a negative pattern formed from a casein-based photosensitive resin film and having a large number of elongated rectangular recesses on both sides by primary etching. The state of filling the hole when was applied was visually determined. The dimensions of the test iron plate are shown in FIG. 1, and the dimensions of the elongated rectangular recesses formed in the test iron plate are shown in FIG. ◯: There are no bubbles at all. Δ: Air bubbles are present in some holes. ×:
There are bubbles on the entire surface. <Surface smoothness> 80w /
cm Concentration type high pressure mercury lamp, conveyor speed 3m / min
The resin composition of the present invention was cured by irradiating it with ultraviolet rays, and the surface condition of the cured resin film was visually determined. ○: No repelling. Δ: Some cissing is present. X: Many repelling occurred. <Etching resistance> The iron plate after the surface smoothness was evaluated was immersed in an aqueous 43% FeCl ₃ solution at 60 ° C for 30 minutes, and the surface state of the cured resin film was visually determined. ○: No change. Δ: There is coloring. X: Swelling or peeling occurred. <Alkali dissolution / peelability> After the etching resistance is evaluated, the iron plate is immersed in a 20% aqueous NaOH solution at 80 ° C for 1 minute,
The solubility or releasability of the cured resin film was visually evaluated. A: Completely melted and peeled. ◯: It did not completely dissolve, but peeled off. X: It did not peel. <Pattern formability> After the iron plate after evaluating the alkali dissolution / peeling property is washed with water and dried, the iron plate obtained by illuminating it from the back side penetrates the shape of the elongated rectangular hole formed in the iron plate. The size of the holes, the distance between the holes, and the linearity of the long side portion of the rectangle were judged by the uniformity of the brightness of the transmitted light so that they could be visually observed. ⊚: The hole size and hole interval are completely constant, and the long side of the rectangle is a straight line ○: One out of ten products has a defect. △: 3 out of 10 products had defects at 1 or 2 places. X: Many defects <Stability of resin> 250c containing 150g of the resin composition of the present invention
The glass bottle of c was stored in a constant temperature bath set at 60 ° C, and the number of days required for the viscosity to change by 10% or more from the initial value was measured. <Flash point> The flash point was measured according to the Cleveland open type flash point test method described in JIS K2265 (Crude oil and petroleum product flash point test method). All the resin compositions of the present invention gelled when heated and had no flash point. <Surface tack> Using a high pressure mercury lamp of 80 w / cm condensing type, a sample irradiated with ultraviolet rays at a conveyor speed of 3 m / min was touched with a finger and judged. ◎ No tack at all ○ It feels a little tight △ There is some tack × Feels like sticking to fingers

Example 1 An active energy ray-curable resin composition was obtained by dissolving the following 5 components while mixing. Component (a): Acryloyloxyethyl monophthalate (trade name “Aronix M- manufactured by Toagosei Chemical Industry Co., Ltd.
5400 ") 60 parts (b) Component: trimethylolpropane triacrylate (trade name" Aronix M- manufactured by Toagosei Chemical Industry Co., Ltd. "
309 ") (c) Component: Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.1 part (d) Component: Styrene-maleic acid copolymer having a number average molecular weight of 1900 (Arco Chemical Co., Ltd.) Product name "SMA300
0 ") 20 parts (e) component: 1-hydroxycyclohexyl phenyl ketone (trade name" Irgacure 18 "manufactured by Ciba Geigy)
4 ") 5 parts

Examples 2 to 5 Example 1 was repeated, except that 20 parts of SMA3000 was replaced by the following polymers as component (d) in the proportions shown in Table 1.
An active energy ray-curable resin composition was obtained in the same manner as in. -SMA resin 1000 (styrene-maleic anhydride copolymer having a number average molecular weight of 1600, a trade name of Arco Chemical Co., Ltd.)-Polystyrene A (a number average molecular weight of 10,000 and a glass transition temperature of 90 ° C) The curable resin composition obtained in each of Examples 1 to 5 was applied to a test iron plate so as to have a film thickness of 30 μm. The resin coating film was irradiated with ultraviolet rays for about 1 second using an 80w / cm condensing type high pressure mercury lamp. When the properties of the resin composition and the cured resin film were evaluated, the results were as follows, and the results shown in Table 1 were obtained for properties other than the following properties. Hole filling: ○ Surface smoothness: ○ Resin stability: 6 days or more

[0034]

[Table 1]

Comparative Examples 1 to 3 Active energy ray-curable resin compositions were obtained in the same manner as in Example 1 except that the following polymers were blended in the proportions shown in Table 2 in place of the component (d). High wax 100P (number average molecular weight is 900, glass transition temperature is 40 ° C) Polystyrene B (number average molecular weight is 60,000, glass transition temperature is 100 ° C) In Comparative Examples 1 to 3 above The active energy ray-curable resin composition obtained was applied to a test iron plate so as to have a film thickness of 30 μm. The resin coating film was irradiated with ultraviolet rays for about 1 second using an 80w / cm condensing type high pressure mercury lamp. When the properties of the resin composition and the cured resin film were evaluated, the results were as follows, and the results shown in Table 2 were obtained for properties other than the following properties. Etching resistance: ○ Resin stability: 6 days or more

[0036]

[Table 2]

Examples 6 to 11 An active energy ray-curable resin was prepared in the same manner as in Example 1 except that 20 parts of SMA3000 was replaced by the following granular filler as component (d), as shown in Table 3. A composition was obtained.・ Super SS (trade name of calcium carbonate, Maruo Calcium Co., Ltd.) ・ Ultra White-90 (trade name of clay, Engelhard Co., Ltd.) ・ Kunigel V-1 (trade name of bentonite, Kunimine Industry Co., Ltd.) The active energy ray-curable resin composition obtained in 6 to 11 was applied to a test iron plate so as to have a film thickness of 30 μm. The resin coating film was irradiated with ultraviolet rays for about 1 second using an 80w / cm condensing type high pressure mercury lamp. When the resin stability of the resin composition was evaluated, it was 6 days or longer, and the results shown in Table 3 were obtained for the other properties of the resin composition and the cured resin film.

[0038]

[Table 3]

Example 12 Of the active energy ray-curable resin composition obtained in Example 6 above, a resin composition containing no component (e) was used to obtain a film thickness of 30 μm.
It was applied to a test iron plate so as to be m. Using an electron beam irradiation device, an acceleration voltage of 175 KV and an irradiation dose of 3 for resin coatings
It was confirmed that the resin was cured by irradiating it with an electron beam with Mrad and there was no tack on the surface of the resin coating film. When the characteristics of the resin composition and the cured resin film were evaluated, the results shown in Table 3 were obtained.

Example 13 Instead of 20 parts of SMA3000 in the active energy ray-curable resin composition obtained in Example 1 above, as the component (d),
8 parts Super SS are mixed, 5 parts Irgacure 18
A thermosetting resin composition was obtained in the same manner as in Example 1 except that 1 part of benzoyl peroxide (manufactured by NOF CORPORATION) was added as the component (e) in place of 4. The resin composition thus obtained was applied in the same manner as in Example 1, allowed to stand at room temperature for 1 minute, and then heated at 100 ° C for 5 minutes to cure the resin, thereby tacking the surface of the resin coating film. It was confirmed that the resin was cured because there was no The characteristics of the resin composition and the cured resin film were as follows. Hole fillability: ○ Surface smoothness: ○ Etching resistance: ○ Alkali dissolution / peelability: ◎ Pattern formability: ◎ Resin stability: 6 days or more

[0041]

The composition of the present invention is a low-viscosity resin composition which can be easily and quickly cured by irradiation with active energy rays or heating to form a cured product having an alkali-dissolving / releasing property. It is particularly useful as a resin composition for a backing material after primary etching, which is one step of the mask manufacturing process. By producing a shadow mask using the curable resin composition of the present invention, various properties such as hole filling, surface smoothness, curability, etching resistance, alkali dissolution / removability and pattern formability are satisfied. It is possible to manufacture a shadow mask that does. Since the composition of the present invention has the above-mentioned features, it is used in many fields other than the resin composition for the backing material at the time of producing a shadow mask, for example, as a casting material, a paint or a molding material. .. Further, since the composition of the present invention does not require an organic solvent, there is no need for a drying furnace for evaporating the organic solvent and a solvent recovery device, and there is no need to worry about the toxicity of the organic solvent when handling raw materials, The risk of ignition and explosion during drying can be prevented. Moreover, it is possible to perform short-time curing that does not require a drying step involving evaporation of an organic solvent, achieves reduction of energy cost and prevention of fire occurrence, and is useful in that it can be improved by utilizing existing steps. The industrial value is extremely large.

[Brief description of drawings]

FIG. 1 is a size of a test iron plate used in Examples.

FIG. 2 is a dimension of an elongated rectangular recess formed in a test iron plate used in Examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09D 5/00 PNW 6904-4J 7/06 PSL 7211-4J G03F 7/004 501 7124-2H 7 / 027 501 9019-2H (72) Inventor Hiroshi Sasaki 1 at 1 Funami-cho, Minato-ku, Nagoya, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute (72) Inventor Tetsuji Minematsu Funami, Minato-ku, Nagoya, Aichi 1 at Toago Synthetic Chemical Industry Co., Ltd., Nagoya Research Institute (72) Inventor Hiroyuki Ota 1 at 1 Funamicho, Minato-ku, Aichi Prefecture Nagoya City Toagosei Synthetic Chemical Industry Co., Ltd. (72) ) Inventor Masanobu Sato 1 at 1 Tenjin Kitamachi, Tenjin Kitamachi 4-chome, Horikawa-dori Teranouchi, Kamigyo-ku, Kyoto Who Hiroshi Nishimuta 1 Dainippon Screen Manufacturing Co., Ltd. Hikone district office in Shiga Prefecture Hikone Takamiya-cho address 480

Claims (1)

[Claims] 1. A curable resin composition comprising the following (a), (b), (c) and (d) and having a viscosity at 25 ° C. of not more than 5000 cps. (A) Compound having one carboxyl group and one acryloyl or methacryloyl group in the molecule (b) Compound having two or more acryloyl or methacryloyl groups in the molecule (c) Leveling agent (d) Above It is dissolved in the mixture of (a) and (b), has a glass transition point of 50 ° C or higher, and has a number average molecular weight of 1,000 to 50.
A granular filler which is insoluble in 0,000 polymer or a mixture of the above (a) and (b) and has a glass transition point of 50 ° C or higher.