JPH0326682B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to resin compositions that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and particularly to adhesiveness and chemical resistance to supports such as glass, ceramics, and plastic films, and mechanical resistance. The present invention relates to an active energy ray-curable resin composition that has excellent physical strength and is capable of pattern formation. This active energy ray-curable resin composition is a resin composition that can be shaped into a solid photoreceptor sheet (dry film). [Prior art] In recent years, active energy ray-curable resins have been used in paints,
It is widely used as ink, sealing material, resist material, and pattern forming material. In addition, active energy ray-curable resins as pattern-forming materials were initially used to create printing plates, but more recently they have been used in electronic industry fields such as printed wiring and integrated circuits, as well as in the As disclosed in Japanese Patent No. 57-43876, it is also being used as a structural material for precision equipment such as inkjet recording heads. However, active energy ray-curable resins used for pattern formation, especially dry film types, have excellent adhesion to supports such as glass, ceramics, or plastic films. There was nothing. On the other hand, although the known photocurable paints and adhesives used for glass, metals, ceramics, etc. have excellent adhesion of the cured product, they require exposure to strong active energy rays or long-term irradiation. Moreover, they generally do not have properties suitable for pattern formation. That is, using these to irradiate active energy rays in a pattern,
Even if an attempt was made to obtain a pattern by removing the unexposed areas through development, it was not possible to obtain a precise, high-resolution pattern. In this way, with conventional technology, precise patterns with excellent adhesion can be formed on various supports,
Moreover, there was no material whose pattern had high durability as a structural material. [Problems to be Solved by the Invention] The purpose of the present invention is to create a precise, high-resolution pattern with excellent adhesion to a support, which could not be achieved with such conventional active energy ray-curable resins. An object of the present invention is to provide an active energy ray-curable resin composition capable of forming. Another object of the present invention is that it can be shaped into a dry film that is convenient for pattern formation, and that the pattern formed by hardening by irradiation with active energy rays has excellent chemical resistance and mechanical strength, and can be used as a structural material. An object of the present invention is to provide an active energy ray-curable resin composition that has high durability. [Means for Solving the Problems] The active energy ray-curable resin composition of the present invention mainly contains structural units derived from (i) one or more monomers selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene. In the backbone chain, (A) hydroxyl group-containing acrylic monomer, (B)
Amino or alkylamino group-containing acrylic monomer, (C) carboxyl group-containing acrylic or vinyl monomer, (D) N-vinylpyrrolidone or its derivative, (E) vinylpyridine or its derivative, and (F) represented by the following general formula A graft copolymer polymer having branched chains mainly composed of structural units derived from one or more monomers selected from the group consisting of acrylamide derivatives; (However, R ¹ is hydrogen or has 1 carbon atom
~3 alkyl or hydroxyalkyl group, ^R2 represents hydrogen or an alkyl or acyl group optionally having a hydroxy group having 1 to 4 carbon atoms. ) (ii) a resin formed by esterifying a part of the epoxy groups present in an epoxy resin containing at least one compound having two or more epoxy groups in the molecule with an unsaturated carboxylic acid; An active energy ray-curable resin composition. [Preferred embodiments for carrying out the invention] The graft copolymer polymer (i), which is an essential component of the active energy ray-curable resin composition of the present invention, has relatively rigid properties that are suitable as a structural material. It is made by adding branch chains, which are mainly composed of the above-mentioned hydrophilic monomers (A) to (F), to the main chain and exhibits excellent adhesion to the support. When constituting the graft copolymer polymer, the monomers (A) to (F) above used to constitute the branch chain are specifically shown as (A), the 2-hydroxy Ethyl (meth)acrylate (hereinafter, when referred to as (meth)acrylate, it is meant to include both acrylate and methacrylate), 2
-Hydroxypropyl (meth)acrylate, 3
-chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, or 1 , 4-cyclohexanedimethanol and monoesters of acrylic acid or methacrylic acid.
M5700 (manufactured by Toagosei Kagaku Co., Ltd.), TONE M100 (caprolactone acrylate, Union Carbide Co., Ltd.)
), Light Ester HO-mpp (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Light Ester M-600A (trade name of 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) Known and dihydric alcohols, e.g. 1,10
-Decanediol, neopentyl glycol, bis(2-hydroxyethyl) terephthalate, an addition reaction product of bisphenol A and ethylene oxide or propylene oxide, etc., and a monoester of (meth)acrylic acid, etc. can be used. The amino or alkylamino group-containing acrylic monomer (B) includes (meth)acrylamide,
N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-di-t-butylaminoethyl (meth)acrylamide, etc. Can be mentioned. Examples of the carboxyl group-containing acrylic or vinyl monomer (C) include (meth)acrylic acid, fumaric acid, itaconic acid, and Toagosei Kagaku Co., Ltd. product names Aronix M-5400 and Aronix M-.
Examples include those known as 5500. (E) vinylpyridine or its derivatives include 2-vinylpyridine, 4-vinylpyridine,
2-vinyl-6-methylpyridine, 4-vinyl-
Examples include 1-methylpyridine, 2-vinyl-5-ethylpyridine, and 4-(4-pipenylinoethyl)pyridine. All of the monomers (A) to (E) above have hydrophilicity, and the composition of the present invention can be used for glass,
It provides strong adhesion when bonded to supports such as ceramics and plastics. Examples of acrylamide derivatives represented by the general formula (F) include N-methylol (meth)acrylamide, N-propoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, and β-hydroxyethoxymethyl (meth)acrylamide.
Acrylamide, N-ethoxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, α-hydroxymethyl-N-methylolacrylamide, α-hydroxyethyl-N
-Butoxymethylacrylamide, α-hydroxypropyl-N-propoxymethylacrylamide, α-ethyl-N-methylolacrylamide, α-propyl-N-methylolacrylamide, and other hydrophilic and thermally crosslinkable monomers are mentioned. These monomers (F) have not only hydrophilic properties but also condensation crosslinking properties when heated, and generally, water molecules or alcohol are released at temperatures of 100°C or higher, forming crosslinking bonds and forming graft copolymer polymers themselves. This also forms a network structure after curing, further improving the chemical resistance, mechanical strength, etc. of the pattern obtained by curing, thereby making the present invention more effective. In addition, by adding a portion of monomers that ring-open and crosslink by heat, such as glycidyl (meth)acrylate, to the monomers (A) to (F) above to form a branch chain, the monomers (F The same effect as in ) can be obtained. In addition to the above thermal crosslinking, it is also effective to introduce a photopolymerizable monomer into a part of the branch chain of the graft copolymer of the present invention and crosslink the graft copolymer with active energy rays for the same purpose. be. Such methods for imparting photopolymerizability to branch chains include, for example, copolymerizing monomers containing carboxyl groups such as (meth)acrylic acid, or monomers containing amino groups or tertiary amine groups. A partial urethane compound of polyisocyanate having one isocyanate group and one or more acrylic ester groups in one molecule, and a branched hydroxyl group,
A method of reacting with an amino group or a carboxyl group, a method of reacting a branched hydroxyl group with acrylic acid chloride, a method of reacting a branched hydroxyl group with an acid anhydride, and then reacting with glycidyl (meth)acrylate, Methods such as a method of condensing the hydroxyl group of and the condensation crosslinking monomer exemplified in (F) to leave an acrylamide group on the side chain, a method of reacting the hydroxyl group of the branch chain with glycidyl (meth)acrylate, etc. can be used. . When the branch chains of the graft copolymer polymer in the present invention are thermally crosslinkable, it is preferable to perform heating after forming a pattern by irradiation with active energy rays. On the other hand, even when the branch chain is photopolymerizable, there is no problem in heating within an allowable range in terms of the heat resistance of the support, and in fact, more favorable results can be obtained. In addition to those derived only from hydrophilic monomers as exemplified in (A) to (F) above, the branch chains may be derived from various hydrophobic monomers that exhibit various other functions.
The branched chain may be used as a component of the copolymerization in the range of up to about 25% by weight. The monomers constituting the backbone chain of the graft copolymer polymer in the present invention are methyl methacrylate,
These include alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, such as ethyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate, acrylonitrile, and styrene. In addition to those derived only from the above monomers,
For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, vinyl acetate, etc.
The backbone may be used as a copolymerization component in an amount up to 50% by weight. In the composition of the present invention, the backbone chain imparts high cohesive strength to the composition. The composition of the present invention can be provided in various forms depending on the purpose of use, such as a solution or a solid film, but if it is to be put to practical use as a dry film, the composition may be maintained in a film form. In order to achieve this, it is preferable to use a relatively rigid backbone having a glass transition temperature of about 50° C. or higher. In this case, the backbone chain used may be composed of two or more types having different glass transition temperatures. Furthermore, if the composition of the present invention is used in the form of a solution, it is also possible to use a backbone chain with a low glass transition temperature that gives flexibility to the composition. However, even in this case,
In order to obtain a pattern with excellent chemical resistance and high mechanical strength, it is preferable that the backbone chain has a high glass transition temperature. The graft copolymer polymer used in the present invention is
They are roughly classified into non-curable, photo-crosslinkable, and thermally crosslinkable, but in any case, the curing process of the composition of the present invention (i.e., active energy ray irradiation and, if necessary, In addition to imparting shape retention to the composition and enabling precise patterning, the resulting curing pattern also has excellent adhesion, chemical resistance, and high mechanical strength. It is something to give. The above-mentioned graft copolymer polymer used in the composition of the present invention can be produced by a known method, and specifically, for example, "Basics and Applications of Polymer Alloys", pp. 10-35 (edited by the Society of Polymer Engineers). , published by Tokyo Kagaku Dojin Co., Ltd., 1981). Examples of these methods include a chain transfer method, a method using radiation, an oxidative polymerization method, an ion graft polymerization method, and a macromonomer method. The graft copolymer used in the present invention has a more pronounced surfactant effect when the branch chain lengths are uniform.
It is preferable to use the following methods, and among them, the macromonomer method is particularly preferable because it is advantageous in terms of material design. The weight average molecular weight of the graft copolymer is approximately
The range is preferably from 5,000 to 300,000, and when used as a dry film, the range is preferably from about 30,000 to 300,000. One of the compounds containing two or more epoxy groups in one molecule, which is another component used in the composition of the present invention.
Resin (ii) (hereinafter abbreviated as half-esterified epoxy resin) obtained by esterifying a portion of the epoxy groups present in an epoxy resin consisting of at least one species with an unsaturated carboxylic acid is the composition of the present invention. The resin composition of the present invention is applied in liquid form onto various supports made of glass, plastics, ceramics, etc. and then cured to form a cured film. The cured film made of the resin composition of the present invention has better adhesion to the support, water resistance, and chemical resistance when used in dry film form or by adhering to various supports. , is a component for imparting dimensional stability and the like. The half-esterified epoxy resin (ii) contained in the resin composition of the present invention is produced by adding a predetermined amount of unsaturated carboxylic acid to an epoxy resin in the presence or absence of a solvent in the coexistence of an addition catalyst and a polymerization inhibitor. Under the following conditions, the reaction is carried out at a temperature of 80 to 120°C.
It can be obtained by a method such as esterifying a part of the epoxy groups present in the epoxy resin with a carboxylic acid (half esterification). Epoxy resins containing one or more compounds containing two or more epoxy groups in one molecule that can be used to form the half-esterified epoxy resin (ii) include bisphenol A type, novolak type,
Epoxy resins represented by alicyclic type, bisphenol S, bisphenol F, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol triglycidyl ether, isocyanuric acid triglycidyl ether, Glycidyl ether and the following general formula (However, R is an alkyl group or an oxyalkyl group, R ₀ is

【formula】

〔Effect of the invention〕

The active energy ray-curable resin composition of the present invention has excellent sensitivity and resolution as a pattern forming material, and can form a pattern with high density and high resolution. Moreover, in the active energy ray-curable resin composition of the present invention, the characteristics of the graft copolymer polymer and the half-esterified epoxy resin as essential components are effectively utilized. In addition to the excellent adhesion to the support and mechanical strength provided by the graft copolymer polymer, the excellent chemical resistance and dimensions provided mainly by the half-esterified epoxy resin. The pattern formed by the composition has these excellent properties when viewed as a coating material, and is suitable as a protective coating or structural member that requires long-term durability. . Furthermore, when a graft copolymer polymer having curability is used, it is possible to obtain an active energy ray-curable resin composition that has even better adhesion, mechanical strength, or chemical resistance. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 A living polymer (2-hydroxyethyl methacrylate/butyl acrylate (=80/20 weight ratio) obtained by anionic polymerization method) was reacted with p-vinylbenzyl chloride to form a vinyl group at one end of the molecular chain. A macromonomer (p-vinylbenzyl poly-2-hydroxyethyl methacrylate/butyl acrylate) with a weight average molecular weight of about 1800 was obtained. 30 parts by weight of this macromonomer and 70 parts by weight of methyl methacrylate were solution polymerized in methyl cellosolve. and a thermoplastic graft copolymer polymer with a weight average molecular weight of 7.0×10 ⁴ (this was GP-1
) was obtained. Note that the glass transition temperature of the polymethyl methacrylate chain constituting the main chain of GP-1 is 100°C. In addition, Epicote 828 (manufactured by Ciel Chemical Co., Ltd.) having an epoxy equivalent of 190 was dissolved in a mixed solution of 50% toluene and 50% butyl acetate to make a 30% solution. Add 0.5 equivalents of methacrylic acid to the epoxy groups present,
After adding 0.2% of N-nitrosodiphenylamine to the solid content as a polymerization inhibitor, it was added as a catalyst.
LiCl was added at 0.5% based on the solid content. reaction is 70
It was carried out for 5 hours at ~80°C. In this way, an epoxy resin in which 0.5 equivalent of 1.0 equivalent of epoxy was esterified with methacrylic acid, that is, a half-esterified epoxy resin was obtained. The half-esterified epoxy resin obtained here was designated as HE-1. Using this HE-1 and the above GP-1, an active energy ray-curable resin composition having the following composition was prepared. GP-1 100 parts by weight HE-1 100 boron trifluoride monoethylamine 10 benzophenone 10 Michler's ketone 5 crystal violet 0.3 methyl cellosolve 350 ) Ultrasonic cleaning treatment and drying 10cm×
On a 10cm Pyrex substrate, the thickness after drying is approx.
It was coated with a bar coater to a thickness of 50 μm. A polyethylene terephthalate film (Lumirror T type) with a thickness of 16 μm is placed on the surface of this composition.
was laminated. Next, a mask for resolution testing was used, and the semiconductor exposure light source ``Mask Alignment System MA-10'' (Mikasa) uses an ultra-high pressure mercury lamp with a center wavelength of around 365 nm and a light energy of 12 mW/cm ² at the irradiated surface. Co., Ltd.) for 60 seconds. After exposure, development was carried out for 45 seconds in an ultrasonic cleaner using a developer of 1,1,1-trichloroethane/ethanol (=80/20). The resolution of the resin composition after development accurately reproduced a pattern of lines/intervals with a width of 50 μm. The substrate was then heat dried, post-exposed at 10 J/cm ² and heated at 150° C. for 30 minutes. When a cross-cut tape peeling test using industrial cellophane tape was carried out on this board, it showed adhesion of 100/100, with complete adhesion except for clear scratches on the cross-cuts. In addition, this substrate was immersed in a NaOH aqueous solution with a pH of 9.0, and a pressurization test was conducted at 121°C.
It was carried out under the conditions of 2 atoms and 10 hours. After the pressure puller test, a cross-cut tape peel test and a peel test on the 50 μm pattern were carried out again, but no deterioration in adhesion such as peeling or lifting was observed in either case. Moreover, no deterioration such as whitening of the coating film was observed. Example 2 Living polymer obtained by anionic polymerization method (N-methylol methacrylamide/2-hydroxyethyl methacrylate (=30/70 weight ratio))
and p-vinylbenzyl chloride are reacted,
A macromonomer (p-vinylbenzyl poly-N-methylolmethacrylamide/2-hydroxyethyl methacrylate) having a weight average molecular weight of about 1500 and having a vinyl group at one end of the molecular chain was obtained. 30 parts by weight of this macromonomer with a molecular weight of approximately 1,500 and 70 parts by weight of methyl methacrylate were solution polymerized in methyl cellosolve, ^and a graft copolymer polymer (this
GP-2) was obtained. The glass transition temperature of the polymethyl methacrylate chain constituting the main chain of GP-2 is 100°C. This GP-2 and Example 1
An active energy ray-curable resin composition having the following composition was prepared using HE-1 obtained in . GP-2 100 parts by weight HE-1 100〃 Triphenylsulfonium tetrafluoroborate 10〃 Paratoluenesulfonic acid 2〃 Crystal Violet 0.3〃 Methyl cellosolve 350〃 Using this composition, on a Pyrex substrate of 10 cm x 10 cm. Same as Example 1, the film thickness is 40μm and 50μm.
formed a pattern of lines and spaces. After the developer was evaporated to dryness, a 10 minute post-exposure was performed using the same light source. Then, heat treatment was performed at 150°C for 30 minutes. The substrate having the cured pattern thus formed is immersed in an NaOH aqueous solution with a pH of 9.0,
A pressurization test was conducted at 121°C, 2 atoms, and 20 hours. After the test was completed, the board was washed with water and dried, and a cross-cut tape peeling test and a pattern part peeling test were performed. As a result, the adhesion
There was no peeling of the 100/100 and pattern parts. Example 3 A living polymer (3-chloro-2-hydroxypropyl methacrylate/N-vinylpyrrolidone (=90/10 molar ratio)) obtained by anionic polymerization method is reacted with acrylic acid chloride to form one end of the molecular chain. Weight average molecular weight with vinyl groups in approx.
2500 macromonomers (acrylic acid poly-3-chloro-2-hydroxypropyl methacrylate/
N-vinylpyrrolidone) was obtained. 25 parts by weight of this macromonomer, 65 parts by weight of methyl methacrylate, and 10 parts by weight of dimethylaminoethyl methacrylate were copolymerized in methyl isobutyl ketone (weight average molecular weight: 6.5×10 ⁴ ). Then this copolymer
In a polymer solution in which 100 parts by weight of hexamethylene diisocyanate and 2-hydroxyethyl acrylate are dissolved, NCO group equivalent: OH group equivalent =
11 parts by weight of the partial urethane compound obtained by the reaction at a ratio of 2.0:1.1 was added and reacted, converting 30% of the 3-chloro-2-hydroxypropyl methacrylate component into acrylic urethane, and photopolymerizable in the branch chain. A graft copolymer polymer having an acrylic ester group (hereinafter referred to as GP-3) was obtained. The glass transition temperature of the copolymer chain of methyl methacrylate and dimethylaminoethyl methacrylate that constitutes the main chain of GP-3 is 90°C. Separately, use Epicote 828 as an epoxy equivalent.
The epoxy group was treated in the same manner as in Example 1, except that 450 Epikote 1001 (manufactured by Ciel Chemical) was used.
0.5 equivalent of methacrylic acid was added to obtain a half-esterified epoxy resin (HE-2). Using this HE-2 and the above-mentioned GP-3, an active energy ray-curable resin composition having the following composition was prepared. GP-3 100 parts by weight HE-2 150〃 Dicyandiamide 8〃 Irgakiure 651 11〃 Crystal Violet 0.2〃 Methyl isobutyl ketone 300〃 Thickness after drying this composition on a silicon wafer with an oxide film SiO ₂ formed on the surface It was coated with a bar coater so that the thickness was 50 μm. Next, a pattern for a resolution test was formed in the same manner as in Example 1.
The formed pattern accurately reproduced a line/interval pattern with a width of 50 μm. The silicon wafer was then heat dried and post-exposed using the same ultraviolet light source used for pattern exposure.
Heated at ℃ for 30 minutes. When this silicon wafer was subjected to a cross-cut tape peeling test, no peeling of the coating film was observed. Next, this silicon wafer was heated using NaOH with a pH of 9.0.
It was immersed in an aqueous solution and subjected to a pressurization test at 121°C, 2 atoms, and 20 hours. After the test was completed, a cross-cut tape peeling test and a peeling test of the pattern portion were carried out again, but no deterioration in adhesion such as peeling or lifting was observed in either case. Example 4 Living polymer (N
-Butoxymethylacrylamide/2-hydroxyethyl methacrylate (=70/30 weight ratio))
was reacted with acrylic acid chloride to obtain a macromonomer (acrylic acid polybutoxymethyl acrylamide/2-hydroxyethyl methacrylate) having a weight average molecular weight of about 3000 and having a vinyl group at one end of the molecular chain. 25 parts by weight of this macromonomer, 70 parts by weight of methyl methacrylate, and 5 parts by weight of acrylonitrile were polymerized in methyl cellosolve, and a graft copolymer polymer (GP-4) having a weight average molecular weight of 6.8×10 ⁴ and having thermal crosslinkability was )
I got it. The glass transition temperature of the copolymer chain of methyl methacrylate and acrylonitrile that constitutes the main chain of GP-4 is 105°C. Using this GP-4 and HE-2 obtained in Example 3, an active energy ray-curable resin composition having the following composition was prepared. GP-4 100 parts by weight HE-2 150〃 Copper phthalocyanine 1〃 Paratoluenesulfonic acid 3〃 Triphenylsulfonium tetrafluoroborate 10〃 Methyl cellosolve 300〃 Silane cup with thiol group on a 10cm x 10cm Pyrex glass plate A 1% ethanol solution of the ring agent γ-mercaptopropyltrimethoxysilane was applied onto a glass plate using a spinner. The application is
This was done by rotating at 2500 rpm for 25 seconds. Next, this glass plate was heat treated at 120°C for 10 minutes. Here, the mill dispersion of the resin composition is
A resin composition layer with a thickness of 10 μm was formed by applying it to a 16 μm polyethylene terephthalate film using a wire bar and drying it at 100° C. for 20 minutes. Next, use the laminator HRL-
24 (product name, manufactured by Dupont Co., Ltd.) at 120℃ circumferential speed
It was laminated onto the Pyrex glass plate at a speed of 1 m/min. Thereafter, in the same manner as in Example 1, a clear pattern colored blue with lines and intervals of 25 microns could be formed. Then 10J/
After exposure to ^cm2 and heat treatment at 150℃ for 30 minutes,
Completely hardened. The formed pattern was subjected to the same conditions as in Example 1,
The adhesiveness was examined using a pressurization test. No peeling of the coating film was observed in the cross-cut Scotch tape peeling test after the pressure maker test. Example 5 Dimethylaminoethyl methacrylate and 2-
Hydroxyethyl methacrylate (50:50, molar ratio) was reacted with thioglycolic acid as a chain transfer agent and azobisisobutylnitrile as a polymerization initiator to perform radical chain transfer polymerization. Next, the obtained reaction product is further reacted with glycidyl methacrylate to form a macromonomer (acrylic acid polydimethylaminoethyl methacrylate-2-hydroxyethyl methacrylate) was obtained. 30 parts by weight of this macromonomer and 70 parts by weight of methyl methacrylate were solution polymerized in ethylene glycol monomethyl ether to give a number average molecular weight of 55,000,
A graft polymer with a weight average molecular weight of 120,000 (this
GP-5) was obtained. Note that the glass transition temperature of GP-5 was 83°C. Next, a cresol novolak type epoxy resin (epoxy equivalent: 220) with an average degree of condensation of 6 was used in the same manner as in the case of HE-1, and an epoxy resin in which 0.7 equivalent of 1.0 equivalent of epoxy was esterified with acrylic acid, That is, a half-esterified epoxy resin was obtained. The epoxy resin obtained here is HE−
It was set as 3. Using GP-5 and HE-3 obtained by the above operations, an active energy ray-curable resin composition having the following composition was prepared. GP-5...100 parts by weight HE-3...80 parts by weight Urethane obtained by reacting oligoester glycol (molecular weight 600) consisting of succinic acid and ethylene glycol, diphenylmethane diisocyanate and 2-hydroxyethyl methacrylate Acrylate (molecular weight 3000)...60 parts by weight neopentyl glycol diacrylate
…30 parts by weight Benzophenone …8 parts by weight Michler's ketone …3 parts by weight Triphenylsulfonium tetrafluoroborate …3 parts by weight Crystal violet …0.2 parts by weight Toluene …150 parts by weight Ethyl acetate 150 parts by weight This composition was used to conduct experiments. When the resolution and adhesion tests were conducted in the same manner as in Example 1, good results were obtained in both cases. Example 6 Oxazoline derivative (obtained by reacting methacrylic acid chloride and amino alcohol) and 2-hydroxyethyl methacrylate (70:
30, molar ratio) were reacted using thioglycolic acid as a chain transfer agent and azobisisobutylnitrile as a polymerization initiator to perform radical chain transfer polymerization. Next, the obtained reaction product was further reacted with glycidyl methacrylate to obtain a low polymer having a vinyl group at the end. The obtained low polymer was treated with hydrochloric acid and sodium hydroxide to hydrolyze the oxazoline ring. As a result, it is made of methacrylic acid and 2-hydroxyethyl methacrylate, has a vinyl group at the end, has a number average molecular weight of 7000, and has a weight average molecular weight of 7,000.
25000 macromonomers (polyacrylic acid-2-
Hydroxyethyl methacrylate) was obtained. 30 parts by weight of this macromonomer and 70 parts by weight of methyl methacrylate were solution polymerized in ethylene glycol monomethyl ether to obtain a number average molecular weight of 10,000,
A graft polymer with a weight average molecular weight of 58,000 (this
GP-6) was obtained. Note that the glass transition temperature of GP-6 was 75°C. Using this GP-6 and HE-2 obtained according to the procedure of Example 3, an active energy ray-curable resin composition having the following composition was prepared. GP-6...100 parts by weight HE-2...60 parts by weight Aronix M7100 (product of Toagosei Chemical Co., Ltd.)
...60 parts by weight triphenylsulfonium tetrafluoroborate ...3 parts by weight IRGAKIURE 651 (product of Ciba Geigy Co., Ltd.)
…8.5 parts by weight Crystal violet …0.2 parts by weight Toluene …150 parts by weight Methyl ethyl ketone …150 parts by weight Using this composition, the same evaluation as in Example 1 was conducted, and it was found that similarly good resolution and adhesion were performed. Indicated. Example 7 Vinylpyridine and 2-hydroxyethyl methacrylate (80:20, molar ratio) were reacted using thioglycolic acid as a chain transfer agent and azobisisobutylnitrile as a polymerization initiator to perform radical chain transfer polymerization. I went. Next, the obtained reaction product is further reacted with glycidyl methacrylate to form a macromonomer (poly-vinylpyridine-2-hydroxyethyl methacrylate acrylate) having a vinyl group at the end and having a number average molecular weight of 5,000 and a weight average molecular weight of 16,000. ) was obtained. 25 parts by weight of this macromonomer and 75 parts by weight of methyl methacrylate were solution polymerized in methyl cellosolve, resulting in a number average molecular weight of 16,000 and a weight average molecular weight of 40,000.
A graft polymer (referred to as GP-7) was obtained. Note that the glass transition temperature of GP-7 was 72°C. Using this GP-7 and HE-3 obtained according to the procedure of Example 5, an active energy ray-curable resin composition having the following composition was prepared. GP-7...100 parts by weight HE-3...70 parts by weight Polyester obtained from hydrogenated bisphenol A and adipic acid (molecular weight 1200), tolylene diisocyanate and 2-hydroxyethyl acrylate are reacted to form a terminal. Urethane acrylate with acrylic group (molecular weight 4500)
...50 parts by weight trimethylolpropane triacrylate
...20 parts by weight triphenylsulfonium tetrafluoroantimonate ...3 parts by weight IRGAKIURE 651 (product of Ciba Geigy Co., Ltd.)
...8.5 parts by weight Crystal violet ...0.2 parts by weight Toluene ...150 parts by weight Methyl ethyl ketone 150 parts by weight This composition was evaluated in the same manner as in Example 1, and the same good results were obtained. Comparative example Methyl methacrylate, 2-hydroxyethyl methacrylate and butyl acrylate (=60/
30/10 molar ratio) in methyl mesobutyl ketone to obtain a thermoplastic linear polymer compound with a weight average molecular weight of 8.8×10 ⁴ . (Let this be LP-1) This
Using LP-1, an active energy ray-curable resin composition having the following composition was prepared and patterned in exactly the same manner as in Example 1. LP-1 100 parts by weight Triethylene glycol dimethacrylate 50 Benzophenone 10 Michler's ketone 5 Crystal violet 0.3 Methyl cellosolve 350 The obtained pattern had almost the same resolution as Example 1. However, in the pressure vacuum test, the pattern peeled off from the substrate before the start of the peel test, and the water resistance and adhesion were low. As is clear from the above Examples and Comparative Examples, the active energy ray-curable resin composition of the present invention is capable of forming a high-resolution pattern, and at the same time exhibits high adhesion to the support, especially It can be seen that when a thermally and photocurable graft copolymer polymer is used, it has considerably high adhesion, and also has excellent mechanical strength and chemical resistance.

Claims (1)

[Scope of Claims] 1 (i) A backbone chain mainly composed of structural units derived from one or more monomers selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene, (A) a hydroxyl group-containing acrylic monomer, ( B) Acrylic monomer containing amino or alkylamino group, (C) Acrylic or vinyl monomer containing carboxyl group, (D) N-vinylpyrrolidone or its derivative, (E) Vinylpyridine or its derivative, and (F) represented by the following general formula. a graft copolymer polymer having a branch chain mainly derived from one or more monomers selected from the group consisting of acrylamide derivatives; (However, R ¹ is hydrogen or has 1 carbon atom
~3 alkyl or hydroxyalkyl group, ^R2 represents hydrogen or an alkyl or acyl group optionally having a hydroxy group having 1 to 4 carbon atoms. ) (ii) a resin formed by esterifying a part of the epoxy groups present in an epoxy resin containing at least one compound having two or more epoxy groups in the molecule with an unsaturated carboxylic acid; An active energy ray-curable resin composition. 2. Claim 1, wherein the component (ii) is a resin obtained by esterifying 0.30 to 0.70 equivalents of 1.0 equivalents of epoxy groups present in the epoxy resin.
The active energy ray-curable resin composition described in 1. 3. Claim 1, wherein the component (ii) is a resin obtained by esterifying 0.45 to 0.55 equivalents of 1.0 equivalents of epoxy groups present in the epoxy resin.
The active energy ray-curable resin composition described in 1. 4. Any one of claims 1 to 3, characterized in that it contains 20 to 80 parts by weight of the graft copolymer polymer of (i) and 80 to 20 parts of resin of (ii). An active energy ray-curable resin composition according to claim 1. 5 0.1 to 20% by weight based on 100 parts by weight of the graft copolymer polymer described in (i) above and the resin described in (ii) above.
5. The active energy ray-curable resin composition according to any one of claims 1 to 4, which contains a radical polymerization initiator that can be activated by the action of active energy rays. 6 0.2 to 15% by weight based on 100 parts by weight of the total amount of the graft copolymer polymer of (i) and the resin of (ii)
Claims 1 to 5 are characterized in that the compound contains an aromatic onium salt compound having photosensitivity and containing an element belonging to Group A or Group A of the periodic table. The active energy ray-curable resin composition described in .