JPH022897B2 - - 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 properties. 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. By the way, such active energy ray-curable resins, especially ultraviolet-curable resist inks and dry films that have become widely used in recent years for manufacturing printed wiring boards, cannot be obtained from conventional epoxy resin-based resins. The main products are those that utilize photopolymerization of acrylic resins, which have properties that could not be achieved previously, such as high sensitivity to active energy rays, short curing times, and the ability to form precise patterns. ing. and,
Regarding these acrylic resin-based resist inks and dry films, the suitability for manufacturing printed wiring boards, such as the adhesion between printed wiring boards and these materials, the etching ability for metals such as copper that are circuit forming materials, and the suitability for these metals. Active development is currently underway to improve properties such as resistivity during plating and heat resistance and electrical insulation when used as a permanent protective film for wiring areas. However, the drawbacks of the resist inks and dry films mentioned above, which are noticeable when they are used as permanent protective films, are compared to the epoxy resin resist inks and overlay coating materials that have been widely used for a long time. Poor adhesion, heat resistance, chemical resistance, insulation, etc. In addition, since the dry film described above is capable of forming precise patterns, it is used as a structural material for precision equipment such as inkjet recording heads, but it is still insufficient to obtain patterns with high precision and high resolution. It was hot. Furthermore, (i) adhesion to the surface of an inorganic support such as glass, ceramics, silicon wafer, etc. or to the surface of an organic polymer support such as polyester, polyimide, polysulfon, etc., (ii) water resistance, and (iii) resistance. It did not necessarily have sufficient performance in terms of chemical resistance, (iv) dimensional stability, (v) mechanical strength as a structure, etc. 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 object of the present invention is to provide excellent adhesion to a support, which could not be achieved with such conventional active energy ray-curable resins, and to provide resistance to active energy rays. An object of the present invention is to provide an active energy ray-curable resin composition that has high sensitivity and can form precise and high-resolution patterns. 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 that is hardened and formed by irradiation with active energy rays and heat treatment as required has chemical resistance. Another object of the present invention is to provide an active energy ray-curable resin composition that has excellent mechanical strength and high durability as a structural material. [Means for Solving the Problems] The active energy ray-curable resin composition of the present invention comprises (i) one selected from the group consisting of alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, acrylonitrile, and styrene; Obtained with the above monomers as main components, and has a glass transition temperature of 50℃
and (ii) an acrylic ester or methacrylic ester of a polyfunctional epoxy resin having two or ^more epoxy groups in one molecule. , acrylic ester or methacrylic ester of alkylene oxide adduct of polyhydric alcohol, molecular weight 500-3000 consisting of dibasic acid and dihydric alcohol
A monomer having one or more ethylenically unsaturated bonds selected from the group consisting of polyester acrylate having an acrylic acid ester group at the molecular chain end of polyester and a reaction product of a polyvalent isocyanate and an alkyl acid monomer having a hydroxyl group. and (iii) a resin obtained 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. It is contained as an essential component. [Preferred embodiments for carrying out the invention] The active energy ray-curable resin composition of the present invention can be used to maintain the composition in a solid film form, for example, when the composition is put into practical use as a dry film. (i) The monomer is obtained as the main component, has a glass transition temperature of 50°C or higher, and has a weight average molecular weight of about 3.0×. 10 ⁴
It contains the above linear polymer as an essential component. When the glass transition temperature and weight average molecular weight of the linear polymer are less than the above values, for example, when producing a dry film, it is formed as a film-like solid resin layer on a support such as a plastic film. The composition gradually flows during storage, causing wrinkles or uneven layer thickness, making it impossible to obtain a good dry film. Specifically, such linear polymers include monomers (A) (i.e., methyl methacrylate, ethyl methacrylate,
The main component is one or more monomers (A) selected from the group consisting of alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms such as isobutyl methacrylate and t-butyl methacrylate, acrylonitrile, and styrene, and as necessary. As a second component, for example, (B) a hydroxyl group-containing acrylic monomer, (C) an amino- or alkylamino group-containing acrylic monomer, (D ) monomers such as carboxyl group-containing acrylic or vinyl monomers, (E) N-vinylpyrrolidone or its derivatives, (F) vinylpyridine or its derivatives, and (G) monomers that impart high cohesive strength to the compositions of the present invention; The following general formula can improve the mechanical strength of objects (However, R ¹ is hydrogen or has 1 to 3 carbon atoms.
an alkyl group, R ² is a divalent hydrocarbon group which may have an ether bond therein and may be substituted with a halogen atom, and R ³ is an alkyl group having 3 to 3 carbon atoms.
12 alkyl or phenyl alkyl group or phenyl group. Examples include thermoplastic copolymer polymers obtained by using monomers represented by the following as components of copolymerization in a range of 40 mol% or less. The monomer (A) used as component (A) is preferably contained in an amount of 60% mole or more in order for the linear copolymer polymer to sufficiently achieve the glass transition reaction. Specifically, the monomers (B) to (G) above used as the second component include 2-hydroxyethyl (meth)acrylate (hereinafter referred to as (meth)acrylate) as the hydroxyl group-containing acrylic monomer (B). When written as , 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 Examples include monoesters of 1,4-cyclohexanedimethanol and acrylic acid or methacrylic acid, and the product name is Aronix.
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 (C) includes (meth)acrylamino,
N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamino, N,N-dimethylaminopropyl (meth)acrylamino, N,N-di-t-butylaminoethyl (meth)acrylamide Examples include. The carboxyl group-containing acrylic or vinyl monomer (A) is (meth)acrylic acid, fumaric acid, itaconic acid, or the product names Aronix M-5400 and Aronix M- manufactured by Toagosei Kagaku Co., Ltd.
Examples include those known as 5500. (F) 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 above monomers (B) to (F) have hydrophilic properties, and when the composition of the present invention adheres to a support such as glass, ceramics, or plastic, it provides strong adhesion. It is intended to give. Specifically, the monomer represented by the general formula (G) contains one hydroxyl group in one molecule (α-
Examples include (α-alkyl)acrylic esters having one or more urethane bonds in one molecule, which are obtained by reacting a monoisocyanate compound with an alkyl) acrylic ester. Note that R ² in the monomer represented by the general formula can be any divalent hydrocarbon group that may have an ether bond therein and may be substituted with a halogen atom, but is preferably R ² is an alkylene group having 2 to 12 carbon atoms which may be substituted with a halogen atom, an alicyclic hydrocarbon group such as 1,4-bismethylenecyclohexane, and an aromatic group such as bisphenyldimethylmethane. Examples include hydrocarbon groups containing rings. Examples of (meth)acrylic esters containing at least one hydroxyl group in one molecule used in producing the monomer represented by the above general formula include 2-hydroxyethyl (meth)acrylate and 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 Light ester HO−
Examples include mpp (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). In addition to the above, as (α-alkyl)acrylic acid ester containing one hydroxyl group in one molecule,
(a) Esters of aliphatic or aromatic dihydric alcohols and (meth)acrylic acid and (b) (meth)acrylic esters of monoepoxy compounds can be used similarly. The dihydric alcohol used in (a) above is:
1,4-cyclohexanedimethanol, 1,10-
Examples include decanediol, neopentyl glycol, bis(2-hydroxyethyl) terephthalate, and an addition reaction product of 2 to 10 moles of ethylene oxide or propylene oxide to bisphenol A. In addition, as the monoepoxy compound used in the above (b), Epolite M-1230 (trade name manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, octylene oxide, n-
Examples include butylphenol glycidyl ether. In addition, as monoisocyanate compounds used in producing the monomer represented by the general formula, alkyl monoisocyanates formed by adding one isocyanate group to an alkyl group having 3 to 12 carbon atoms, and Examples include enyl isocyanate and cresyl monoisocyanate. The monomer represented by the general formula is 50 mol%
It is preferable that the linear copolymer polymer contains the above amount. If the content exceeds 50 mol%, the softening point of the resulting composition will decrease significantly, and the surface hardness of the pattern obtained by curing the composition will decrease.
This causes problems such as deterioration of chemical resistance due to swelling. 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 it is easier to use it in the form of a dry film, and it is easier to control the film thickness. It is also easy and particularly advantageous. Of course, there is no problem in using it in the form of a solution. Although the case where a thermoplastic linear polymer is mainly used has been described above, in the present invention, a linear polymer having thermal crosslinkability or photocrosslinkability can be used. A thermally crosslinkable linear polymer is, for example, a thermoplastic linear polymer with the following general formula: (However, R ⁴ is hydrogen or has 1 to 3 carbon atoms.
an alkyl or hydroxyalkyl group, R ⁵
represents hydrogen or an alkyl or acyl group which may have a hydroxyl group having 1 to 4 carbon atoms. It can be obtained by introducing a thermally crosslinkable monomer as shown in ) as the second component of copolymerization. The monomer represented by the above general formula has not only thermal crosslinkability but also hydrophilicity, and due to the thermal crosslinkability, the composition of the present invention has excellent properties as a structural material, such as heat resistance, It exhibits chemical resistance, mechanical strength, etc., and excellent adhesion to the support due to its hydrophilicity. Specifically, the monomer represented by the above general formula is N-methylol (meth)acrylamide (hereinafter, when referred to as (meth)acrylamide, it is meant to include both acrylamide and methacrylamide); N-propoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, β-hydroxyethoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N- Acetoxymethyl (meth)acrylamide, α-hydroxymethyl-N-methylolacrylamide, α-hydroxyethyl-N-butoxymethylacrylamide, α-hydroxypropyl-N-propoxymethylacrylamide, α-ethyl-N-methylolacrylamide, α- Examples include acrylamide derivatives such as propyl-N-methylolacrylamide. Monomers represented by these general formulas are not only hydrophilic as described above, but also have condensation crosslinking properties when heated, and generally, water molecules or alcohol are released at temperatures of 100°C or higher to form crosslinked bonds, and after curing, The linear copolymer itself also forms a network structure, giving the pattern obtained by curing excellent chemical resistance and mechanical strength. When a thermosetting linear polymer is used, it is preferred that the linear polymer contains 5 to 30 mol% of the monomers represented by these general formulas. If the content is within the above range,
Provides sufficient chemical resistance due to heat curing. On the other hand, if the content exceeds 30 mol%, problems such as the pattern obtained by curing will become brittle. In addition to the monomer represented by the above general formula, by appropriately using a thermally ring-opened and crosslinking monomer such as glycidyl (meth)acrylate as a component of the copolymerization, the same as in the case of the above general formula can be obtained. effect can be obtained. The photocrosslinkable linear polymer can be obtained, for example, by a method such as the one illustrated below, in which a photopolymerizable monomer is introduced into the linear polymer. An example of such a method is to copolymerize a monomer containing a carboxyl group, such as (meth)acrylic acid, or a monomer containing an amino group or a tertiary amine group, and then react it with glycidyl (meth)acrylate, etc. A method, a polyisocyanate partial urethane compound 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, a branched chain. Examples of methods include a method of condensing the hydroxyl group of and the condensation crosslinking monomer exemplified in (F) to leave an acrylamine group on the side chain, a method of reacting the hydroxyl group of the branch chain with glycidyl (meth)acrylate, and the like. When the linear polymer in the present invention is thermally crosslinkable, it is preferable to perform heating after forming a pattern by irradiation with active energy rays. On the other hand, even in the case of photopolymerizable linear polymers, 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. The linear polymers used in the present invention are broadly classified into those without curability, those with photocrosslinkability, and those with thermal crosslinkability, as described above, but in any case, the linear polymers used in the composition of the present invention are In the curing process (i.e., pattern formation by active energy ray irradiation and thermal curing as necessary), shape retention is imparted to the composition to enable precise patterning, and the pattern obtained by curing is It provides excellent adhesion, chemical resistance, and high mechanical strength. The monomer (ii) having an ethylenically unsaturated bond used in the composition of the present invention is the resin component (iii) described later.
In addition, it is a component for causing the composition of the present invention to exhibit curability with active energy rays, and particularly for imparting excellent sensitivity to active energy rays to the composition of the present invention, preferably at 100% under atmospheric pressure.
Various known monomers that have a boiling point of .degree. C. or higher, preferably have two or more ethylenically unsaturated bonds, and are cured by irradiation with active energy rays can be used. Such monomers having two or more ethylenically unsaturated bonds include acrylic esters or methacrylic esters of polyfunctional epoxy resins having two or more epoxy groups in one molecule, and alkylene polyhydric alcohols. Acrylic ester or methacrylic ester of oxide adduct, molecular weight 500 ~ consisting of dibasic acid and dihydric alcohol
It is one or more monomers selected from the group consisting of polyester acrylate having an acrylic acid ester group at the end of the molecular chain of polyester 3000, and a reaction product of a polyvalent isocyanate and an acrylic acid monomer having a hydroxyl group. The above monomers ~ may be urethane modified products having a urethane bond in the molecule. Examples of monomers belonging to this category include acrylic acid or methacrylic acid esters of polyfunctional epoxy resins used for producing component (iii) (half-esterified epoxy resin) of the resin composition of the present invention, which will be described later. Examples of monomers belonging to this group include ethylene glycol di(meth)acrylate, diethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6 hexanediol (meth)acrylate, polyethylene glycol (meth)acrylate, and pentaerystol. Examples include tri(meth)acrylate, and the product names are KAYARAD HX-220, HX-620, D-310,
D-320, D-330, DPHA, R-604, DPCA-
20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), trade name NK ester BPE-
200, BPE-500, BPE-1300, A-BPE-4 (manufactured by Shin-Nakamura Kagaku Co., Ltd.) and the like can be used. Monomers belonging to this category include the product names Aronix M-6100, M-6200, M-6250, M-6300, M
-6400, M-7100, M-8030, M-8060, M-
8100 (manufactured by Toagosei Kagaku Co., Ltd.), etc. Aronix M-
1100, Aronix M-1200 (manufactured by Toagosei Kagaku Co., Ltd.), and the like. Monomers belonging to this group include polyisocyanates and hydroxyl group-containing monomers such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and diphenylmethane diisocyanate. Reactants with acrylic monomers are listed, and the product name is Sumidyur N.
(Biuret derivative of hexamethylene diisocyanate), Sumidyur L (trimethylolpropane modified product of tolylene diisocyanate) (the above,
A reaction product obtained by adding a hydroxyl group-containing (meth)acrylic acid ester to a polyisocyanate compound known as Sumitomo Bayer Urethane Co., Ltd.) can be used. The hydroxyl group-containing acrylic monomer mentioned here is typically a (meth)acrylic acid ester, with hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate being preferred. Further, other hydroxyl group-containing acrylic monomers mentioned above for producing monomers represented by the linear polymer formula can also be used. In addition to the monomers having two or more ethylenically unsaturated bonds as described above, monomers having only one ethylenically unsaturated bond, such as those listed below, can also be used. Examples of such monomers having one ethylenically unsaturated bond include carboxyl group-containing unsaturated monomers such as acrylic acid and methacrylic acid; glycidyl group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate. Monomer; _C2 - _C8 hydroxyalkyl ester of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol mono Monoesters of acrylic acid or methacrylic acid and polyethylene glycol or polypropylene glycol such as acrylate, polypropylene glycol monomethacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, acrylic Acrylic acids such as octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc. or _C1 - _C12 acrylic or cycloalkyl esters of methacrylic acid; other monomers such as styrene, vinyltoluene, methylstyrene, vinyl acetate, vinyl chloride, vinyl isobutyl ether,
Acrylonitrile, acrylamide, methacrylamide, acrylic or methacrylic acid adducts of alkyl glycidyl ethers, vinylpyrrolidone, dicyclopentenyloxyethyl (meth)acrylate, ε-caprolactone modified hydroxyalkyl (meth)acrylate, tetrahydrofurfuryl acrylate, phenolic acid Examples include ethyl acrylate and the like. In any case, by using the above monomer having an ethylenically unsaturated bond, the composition of the present invention is provided with sufficient curability and high sensitivity to active energy rays. Obtained by esterifying with an unsaturated carboxylic acid a part of the epoxy groups present in an epoxy resin made of one or more compounds containing two or more epoxy groups in one molecule used in the resin composition of the present invention. The resin (iii) (hereinafter abbreviated as half-esterified epoxy resin) is made to exhibit curability by active energy rays together with the monomer (ii) having an ethylenically unsaturated bond in the composition of the present invention, In addition, when the resin composition of the present invention is applied in liquid form onto various supports made of glass, plastic, ceramic, etc. and then cured to form a cured film, or as a dry film. In order to impart better adhesion to the support, chemical resistance, dimensional stability, etc. to the cured film made of the resin composition of the present invention when used by adhering it to various supports in the form of It is an ingredient. The half-esterified epoxy resin (iii) contained in the resin composition of the present invention is prepared 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. , by reacting under temperature conditions 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 (iii) 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, pentaerythol 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 as a pattern forming material, which is imparted mainly by a monomer having an ethylenically unsaturated bond as an essential component and a half-esterified epoxy resin. It has high resolution and can be used to form patterns with high density and high resolution. Moreover, in the active energy ray-curable resin composition of the present invention, the characteristics of the linear polymer and 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 linear polymer, the main advantages include excellent chemical resistance and dimensional stability provided 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 a structural member that requires long-term durability. Furthermore, when a linear 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 Methyl methacrylate, t-butyl methacrylate, and dimethylaminoethyl methacrylate (=70/20/10 molar ratio) were solution polymerized in toluene to give a polymerization average molecular weight of 7.8×10 ⁴ and a glass transition temperature.
Linear polymer compound at 89℃ (this is called LP-1)
I got it. Also, Epiclon 855, a bisphenol A type with an epoxy equivalent of 183 to 193 (Dainippon Ink & Chemicals Co., Ltd.)
), 4 g of triethylbenzylammonium chloride as a catalyst, and 0.5 g of hydroquinone as a thermal polymerization inhibitor was heated to 80°C,
The reaction was carried out while dropping 0.5 equivalent of acrylic acid per equivalent of epoxy group present. After dropping the acrylic acid, stirring was continued for another 4 hours.
The reaction was terminated. In this way, an epoxy half ester (referred to as HE-1) in which the epoxy group was partially acrylic esterified was obtained. Linear polymer compound obtained as above
An active energy ray-curable resin composition having the following composition was prepared using LP-1 and epoxy half ester HE-1. LP-1 100 parts by weight HE-1 80 〃 Aronik M8060*1 120 〃 Irgakiure 65 10 〃 Crystal Violet 0.5 〃 t-Butylhydroquinone 0.5 〃 1:1 mixture of MIBK/toluene 300 〃 *1: Polyester acrylate (Toagosei Co., Ltd.) (manufactured by Kagaku Co., Ltd.) This composition was treated with ultrasonic cleaning in a cleaning liquid Daiflon (manufactured by Daikin Industries, Ltd.) and dried.
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, using a resolution test mask, we used the semiconductor exposure light source "Mask Alignment Equipment MA-10" (which uses an ultra-high pressure mercury lamp with a central wavelength of 365 nm and a light energy of 12 mW/cm ² at the irradiated surface). By Mikasa Co., Ltd.)
Exposure was made for 60 seconds. After exposure, development was carried out for 45 seconds in an ultrasonic cleaner using a developer of 1,1,1-trichloroethane. 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. A cross-cut tape peeling test using industrial cellophane tape was conducted on this board, and it showed adhesion of 100/100, with complete adhesion except for clear scratches on the cross-cuts. Furthermore, this substrate was immersed in an NaOH aqueous solution with pH=9.0, and a 4-hour boiling test was conducted. After the boiling test, cross-cut tape peeling test and 50μm
A peel test was conducted on the patterned portion, but no deterioration in adhesion such as peeling or lifting was observed in any of the cases. Moreover, no deterioration such as whitening of the coating film was observed. Example 2 Methyl methacrylate, butyl carbamylethyl methacrylate, and butoxymethyl acrylamide (=80/10/10 molar ratio) were solution-polymerized in toluene to give a weight average molecular weight of 1.4×10 ⁵ and a glass transition temperature of 75°C. A linear polymer compound having crosslinking properties (this will be referred to as LP-2) was obtained. In addition, Example 1 except that the epoxy resin Epiclon 1050 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) of bisphenol A type with an epoxy equivalent of 450 to 500 was used.
In exactly the same manner as above, an epoxy half ester (referred to as HE-2) was obtained by adjusting the amount of acrylic acid to 1 equivalent of epoxy group to 0.5 equivalent. In addition, the same procedure as in Example 1 was used, except that an alicyclic epoxy resin Celoxide 2021 (manufactured by Daicel Chemical Co., Ltd.) with an epoxy equivalent of 128 to 145 was used, and the amount of acrylic acid to be used as an epoxy group was 0.5 equivalent. In this way, epoxy half ester (this is HE-3
) was obtained. Using the thermally crosslinkable linear polymer compound LP-2 obtained as described above and the epoxy half esters HE-2 and HE-3, an active energy ray-curable resin composition having the following composition was prepared. did. LP-2 100 parts by weight Aronix M-8060 50 〃 HE-2 50 〃 HE-3 20 〃 Irgakiure 651 10 〃 Para-toluenesulfonic acid 3 〃 Crystal Violet 0.5 〃 t-Butylhydroquinone 0.5 〃 MIBK/Toluene 1:1 Mixture 300 A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition. The resulting pattern image is clear and has a resolution of 50μ
It was m. Next, post-exposure and heating were carried out in the same manner as in Example 1, and a cross-cut tape peeling test was performed, which showed adhesion of 100/100, with complete adhesion except for clear scratches on the cross-cuts. Further, this substrate was immersed in a NaOH aqueous solution having a pH of 9.0, and a boiling test was conducted for 8 hours. After the boiling test, cross-cut tape peel test and 50μm
A peel test was conducted on the patterned portion, but no deterioration in adhesion such as peeling or lifting was observed in any of the tests. Furthermore, no deterioration such as whitening of the paint film was observed. Example 3 Methyl methacrylate, acrylic acid, and 2-hydroxyethyl methacrylate (=70/10/20 molar ratio) were solution polymerized in toluene to obtain a copolymer. Next, an equivalent amount of glycidyl methacrylate was added to the carboxyl groups in this copolymer, and the reaction was carried out at 80°C using triethylbenzylammonium chloride as a catalyst, resulting in a weight average molecular weight of 1.1.
A linear polymer compound (hereinafter referred to as LP- ³ ) having photocrosslinkability and a glass transition temperature of 96° C. and a glass transition temperature of 96° C. was obtained. In addition, the same procedure as in Example 1 was carried out except that a cresol novolak type epoxy resin Epiclon N-665 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) with an epoxy equivalent of 200 to 230 was used. Acrylic acid was added in an amount of 0.5 equivalent to obtain an epoxy half ester (referred to as HE-4). An active energy ray-curable resin composition having the following composition was prepared using the photocrosslinkable linear polymer compound LP-3 obtained as described above and the epoxy half ester HE-4. LP-3 100 parts by weight HE-4 120 〃 Aronix M-7100*2 60 〃 Irgaquia 651 10 〃 2-Ethyl-4-methylimidazole 7.0 〃 Crystal Violet 0.5 〃 t-Butylhydroquinone 0.5 〃 MIBK/Toluene 1: 1 Mixture 300 〃 *: 2 Polyester acrylate (manufactured by Toagosei Kagaku Co., Ltd.) This composition was coated with a bar coater on a silicon wafer with an oxide film SiO ₂ formed on the surface so that the thickness after drying was 50 μm. did. Next, a pattern for a resolution test was formed in the same manner as in Example 1.
The formed pattern accurately reproduced a pattern of lines/intervals with a width of 50 μm. This silicon wafer was then heat dried and exposed using the same ultraviolet light source used for pattern exposure.
A post-exposure of 10 J/cm ² was performed. When this silicon wafer was subjected to a cross-cut tape peeling test, no peeling of the coating film was observed. Further, this substrate was immersed in a NaOH aqueous solution having a pH of 9.0, and a boiling test was conducted for 8 hours. After the boiling test, cross-cut tape peeling test and 50μm
A peel test was conducted on the patterned portion, but no deterioration in adhesion such as peeling or lifting was observed in any of the cases. Moreover, no deterioration such as whitening of the coating film was observed. Example 4 The epoxy group 1 was prepared in exactly the same manner as in Example 1, except that a cresol novolac type epoxy resin Epiclon N-680 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) with an epoxy equivalent of 205 to 250 was used. The acrylic acid was added in an amount of 0.5 equivalent to obtain an epoxy half ester (referred to as HE-5). Linear polymer compound LP-2 with thermal crosslinkability obtained in Examples 2 to 3, epoxy half ester
Using HE-1, HE-3, and HE-5 above, an active energy ray-curable resin composition having the following composition was prepared. LP-2 100 parts by weight HE-3 40 〃 HE-5 50 〃 Kayakiyua DPCA-60*3 90 〃 Irugakiyua 651 10 〃 Copper phthalocyanine 0.5 〃 t-Butylhydroquinone 0.5 〃 1:1 mixture of MIBK/toluene 300 〃 *3 : Aliphatic polyfunctional acrylate (Nippon Kayaku
A 1% ethanol solution of γ-mercaptopropyltrimethoxysilane, a silane coupling agent having a thiol group, was applied onto a 10 cm x 10 cm Virex glass plate (manufactured by Co., Ltd.) 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. The mill dispersion of the resin composition was applied to a 16 μm polyethylene terphthalate film using a wire bar and dried at 100°C for 20 minutes to reduce the film thickness.
A 50 μm resin composition layer was formed. Next, this film was laminated on the Pyrex glass plate at 120° C. and at a circumferential speed of 1 m/min using a laminator HRL-24 (trade name, manufactured by DuPont Co., Ltd.). Thereafter, in the same manner as in Example 1, a clear pattern colored blue with lines and intervals of 50 μm could be formed. Next, a post-exposure of 10 J/cm ² and heat treatment at 150°C for 15 minutes was performed to completely cure the tape, and a cross-cut tape peel test was performed, which showed adhesion of 100/100, with no defects other than the clear scratches on the cross-cuts. It was completely attached. Further, this substrate was immersed in a NaOH aqueous solution with a pH of 9.0, and a boiling test was conducted for 8 hours. After the boiling 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 5 The composition of Example 2 was applied to a 16 μm polyethylene terephthalate film (Lumirror T type) using a bar coater to obtain a resin laminated film with a dry thickness of about 50 μm. Drying was performed in a hot air oven at 100°C for 10 minutes. A copper-clad laminate for a printed wiring board was brush-polished and dried, and the active energy ray-curable resin layer of the resin laminate film was laminated on the surface of the copper foil. For laminate,
105℃ using Hottrol Laminator HRL-24 manufactured by I.A.I. Dupont. The circumferential speed was 1 m/min. After cooling the substrate, using a negative mask for resolution testing, the ultraviolet energy near 365 nm was measured at 12
Exposure was performed for 45 seconds using a highly collimated printing light source such as mW/cm ² . After exposure, the mask film was removed, the polyethylene terephthalate film was peeled off, and spray development was performed using 1,1,1-trichloroethane for 60 seconds. the result,
A pattern with lines and intervals of 40 μm was accurately formed on the substrate. This substrate was post-cured using a high-pressure mercury lamp with ultraviolet energy near 365 nm of 80 mJ/cm ² and heat cured at 120° C. for 30 minutes. After post-curing, the pattern on the substrate had become a hard film. When the obtained substrate was subjected to a cross-cut tape peeling test, the result was 100/100, indicating high adhesion. Further, the above substrate was placed in a copper sulfate plating solution with a pH of 1.2, and electrolytically plated at 45° C. for 30 minutes. When this board was subjected to a cross-cut tape peeling test, the results were 100/100, and no peeling was observed at all even in the patterned area that acted as a copper sulfate plating resist film, indicating high acid resistance. Further, the above substrate was immersed in a NaOH aqueous solution having a pH of 12.0, electrodes were attached, and electrolytic cleaning was performed for 2 minutes at a voltage of 10 V and a current of 1 A/dm ² . When a cross-cut tape peel test was performed on this board, the results were as follows.
At 100/100, no peeling was observed in the patterned portion that acted as a resist film for electrolytic cleaning, demonstrating high alkali resistance. In addition, the above substrate was made of 60% Pb. 260 consisting of 40% Sn
The exposed part of the copper foil was solder-plated by immersing it in solder solution at ℃ for 15 seconds. When this board was subjected to a cross-cut tape peeling test, the result was 100/100, and no peeling was observed at all even in the patterned part that acted as a resist film for solder plating, indicating that this board has sufficient heat resistance as a solder resist. I found out. Example 6 Methyl methacrylate, styrene, and acrylic acid (=60/25/15 molar ratio) were solution polymerized in toluene to give a weight average molecular weight of 15×10 ⁴ and a glass transition temperature.
Linear polymer compound at 85℃ (this is called LP-4)
I got it. An active energy ray-curable resin composition having the following composition was prepared using LP-4. LP-4 100 parts by weight HE-1 80 〃 NK Ester EA-800*4 80 〃 Irgaquiure 651 10 〃 Triphenylsulfonium hexachloroantimonate ＊5 10 〃 Crystal Violet 0.5 〃 t-Butylhydroquinone 0.5 〃 *4: Epoxy acrylate Compound (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) *5: Compound (g) in the text This composition was subjected to pattern formation, oxide resistance, and adhesion tests in the same manner as in Example 1. Good results similar to those in Example 1 were obtained. Example 7 Methyl methacrylate, acrylonitrile, and butocyacrylamide (=70/20/10 molar ratio) were solution polymerized in toluene, resulting in a weight average molecular weight of 9.2×
10 ⁴ , a thermally crosslinkable linear polymer compound (referred to as LP-5) having a glass transition temperature of 110°C was obtained. LP-
An active energy ray-curable resin composition having the following composition was prepared using No. 5. LP-5 100 parts by weight HE-2 120 Photomer 6008*6 60 2-ethylanthraquinone 10 Ethyl-4-dimethylaminobenzoate
1 2-ethyl-4-methylimidazole 5 Crystal violet 0.5 t-butylhydroquinone 0.5 *6: Aliphatic urethane acrylate (manufactured by San Nopco) This composition was subjected to the same test as in Example 2. As a result, good results similar to those of Example 2 were obtained. Example 8 Methyl methacrylate, ethyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate (=60/30/10 molar ratio) were solution polymerized in toluene to give a weight average molecular weight of 8.5×10 ⁴ and a glass transition temperature of 70°C. linear polymer compound (this is called LP-6
) was obtained. An active energy ray-curable resin composition having the following composition was prepared using LP-6. LP-6 100 parts by weight HE-2 80 〃 A-BPE-4*7 80 〃 2-Ethylanthraquinone 10 〃 Ethyl-4-dimethylaminobenzoate
1 dicyanamide 5 crystal violet 0.5 t-butylanthraquinone 0.5 *7: Acrylic acid ester of 4 moles of ethylene oxide adduct to bisphenol A (manufactured by Shin-Nakamura Chemical Co., Ltd.) Examples of this composition When the same test as in Example 1 was conducted, good results similar to those in Example 1 were obtained. Comparative Example 1 Except for using 80 parts by weight of UE-8200 (product of Dainippon Ink & Chemicals Co., Ltd., estimated structure is acrylic ester of Epiclon 855) instead of 80 parts by weight of epoxy half ester HE-1. An active energy ray-curable resin composition was obtained in exactly the same manner as in Example 1. When a pattern was formed using this composition in exactly the same manner as in Example 1, a resolution of 50 μm was obtained, and the sensitivity was comparable to that in Example 1. However, when the substrate obtained here was subjected to the same cross-cut tape peel test as in Example 1, the result was 30/100, indicating poor adhesion. Further, when this substrate was immersed in a NaOH aqueous solution with a pH of 9.0 and subjected to a boiling test for 4 hours, peeling had occurred on the entire surface before the peeling test. Comparative Example 2 Active energy rays were produced in the same manner as in Example 1 except that 40 parts by weight of epoxy half ester HE-2 and 40 parts by weight of epoxy half ester HE-3 were used instead of 120 parts by weight of Aronix M8060. A curable resin composition was obtained. A pattern was formed using this composition in the same manner as in Example 1. The resulting pattern had good adhesion of 100/100, but an exposure time of 90 seconds was required to form a 100 μm pattern, and the accuracy of the pattern was poor.

Claims (1)

[Scope of Claims] 1 (i) A monomer which is obtained mainly from one or more monomers selected from the group consisting of alkyl methacrylates whose alkyl groups have 1 to 4 carbon atoms, acrylonitrile, and styrene, and whose glass transition temperature is
50℃ or higher, and the weight average molecular weight is approximately 3.0×10 ⁴
and (ii) an acrylic ester or methacrylic ester of a polyfunctional epoxy resin having two or more epoxy groups in one molecule, or an acrylic ester of an alkylene oxide adduct of a polyhydric alcohol. or methacrylic acid ester, molecular weight 500-3000 consisting of dibasic acid and dihydric alcohol
A monomer having one or more ethylenically unsaturated bonds selected from the group consisting of polyester acrylate having an acrylic acid ester group at the molecular chain end of polyester and a reaction product of a polyvalent isocyanate and an acrylic acid monomer having a hydroxyl group. and (iii) a resin obtained 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 comprising: 2 20 to 80 parts by weight of the linear polymer of (i) above, and (ii) above.
The active energy ray-curable resin composition according to claim 1, which contains a total of 80 to 20 parts by weight of the monomer (1) and the resin (iii). 3 The content ratio of the monomer (ii) above to the resin (iii) above is
The active energy ray-curable resin composition according to claim 1 or 2, wherein the ratio is 30:70 to 70:30. 4 0.1 to 20 parts by weight per 100 parts by weight of the linear polymer (i), the monomer (ii), and the resin (iii)
The active energy ray-curable resin composition according to any one of claims 1 to 3, which contains a radical polymerization initiator that can be activated by the action of active energy rays in an amount of % by weight. 5 0.2 to 15 parts by weight per 100 parts by weight of the linear polymer (i), the monomer (ii), and the resin (iii)
Any one of claims 1 to 4, which comprises a photosensitive aromatic onium salt compound containing % by weight of an element belonging to Group A or Group A of the Periodic Table. The active energy ray-curable resin composition described in .