JP2005300764A - Curable resin composition, resist pattern forming method, and resin cured object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for a photoresist which improves photosensitivity and heat resistance. <P>SOLUTION: The curable resin composition contains (A) a resin containing radical polymerizable unsaturated groups, carboxyl groups, and hydroxyl groups obtained as follows; a resin (a) containing radical polymerizable unsaturated groups and secondary hydroxyl groups prepared by reacting a polyepoxy resin with a carboxyl-containing radical polymerizable unsaturated monomer is reacted with a polyisocyanate compound (b) to prepare a resin (c) containing radical polymerizable unsaturated groups and isocyanato groups, and then the resin (c) is reacted with a carboxyl-containing polyol (d), (B) a curing agent having a functional group which reacts with a hydroxyl group and/or a carboxyl group, and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a curable resin composition, a method for forming a resist pattern, and a cured resin, and more specifically, excellent adhesion to a substrate, heat resistance, flexibility, chemical resistance, plating resistance, and the like, particularly a solder resist. The present invention relates to a curable resin composition suitable for forming a pattern.

Conventionally, solder resist is used for the purpose of preventing solder adhesion to parts other than necessary and protecting circuits when soldering parts to a printed wiring board. Therefore, adhesion, electrical insulation, solder heat resistance Various properties such as solvent resistance, alkali resistance, acid resistance and plating resistance are required.
The initial solder resist used was an epoxy melamine thermosetting type, but there were problems such as solder heat resistance, chemical resistance, and plating resistance. The thermosetting type is disclosed (Patent Document 1).
In addition, since the above-described thermosetting type is inferior in productivity, an ultraviolet curable solder resist that has been improved is disclosed (see Patent Document 2).
Furthermore, a thermosensitive thermosetting resin composition suitable for a solder resist that combines the thermosetting type and the photocurable type described above is disclosed (see Patent Document 3).

Japanese Patent Publication No. 51-14044

JP-A-57-55914 JP-A-1-141904

Although the thing of patent document 2 is excellent in productivity, there existed a problem in internal hardenability in a thick film, and the problem that solder heat resistance was also inferior.
The one described in Patent Document 3 is a resin composition that has been considered in order to compensate for the problems described in Patent Documents 1 and 2, and this is a printed wiring that accompanies the recent trend toward lighter and thinner electronic devices. When applied to high-density boards, thin-film boards, flexible boards, and boards with high heat-generating components, cracking of the resist film occurs when the board is processed, the resist film peels off the board, and soldering or high heat generation occurs. When heat application by parts is applied to the resist film, there is a problem in that the resist film is cracked or peeled off from the substrate.

The curable resin composition according to the present invention comprises (A) a radical polymerizable unsaturated group obtained by reacting a polyepoxy resin and a carboxyl group-containing radical polymerizable unsaturated monomer and a secondary hydroxyl group-containing resin (a). Radical polymerization produced by reacting with a polyisocyanate compound (b) to produce a radically polymerizable unsaturated group- and isocyanate group-containing resin (c), and then reacting the resin (c) with a carboxyl group-containing polyol (d). A resin containing a functional unsaturated group, a carboxyl group and a hydroxyl group-containing resin, (B) a curing agent having a functional group that reacts with a hydroxyl group and / or a carboxyl group, and (C) a photopolymerization initiator (hereinafter, “ It may be abbreviated as “curable resin composition (I)”.)

  The curable resin composition according to the present invention comprises (D) a radically polymerizable unsaturated group and a secondary hydroxyl group-containing resin (a) obtained by reacting a polyepoxy resin with a carboxyl group-containing radically polymerizable unsaturated monomer. Reaction with polyisocyanate compound (b) to produce a radically polymerizable unsaturated group and isocyanate group-containing resin (c), and then reacting the resin (c) with a carboxyl group-containing polyol (d) to cause radical polymerization A radical produced by producing an unsaturated group, carboxyl group and hydroxyl group-containing resin (A), and then introducing a radically polymerizable unsaturated group into a part or all of the hydroxyl group in the resin (A) via a urethane bond It contains a polymerizable unsaturated group and carboxyl group-containing resin, and (C) a photopolymerization initiator and a curing agent having a functional group that reacts with the carboxyl group. To have (hereinafter, may be abbreviated to "curable resin composition (II)".).

  A resist pattern forming method according to the present invention includes (1) a step of coating a curable resin composition (curable resin composition (I)) according to claim 1 on a substrate to form a curable resin film. (2) A step of exposing and curing the surface of the curable resin film formed on the substrate so as to obtain a desired resist film (image), and (3) developing the unexposed part on the substrate. A step of forming a resist pattern, and (4) a step of heating and thermosetting the resist pattern.

A resist pattern forming method according to the present invention includes (i) a step of coating a curable resin composition (curable resin composition (II)) according to claim 2 on a substrate to form a curable resin film. , (Ii) a step of exposing and curing the surface of the curable resin film formed on the substrate so as to obtain a desired resist film (image), and (iii) developing the unexposed portion on the substrate. It includes a step of forming a resist pattern.
The cured resin according to the present invention is obtained by curing a film formed of the curable resin composition according to claim 1 (curable resin composition (I)) on a base material by light and heat. It is a feature.

  The cured resin product according to the present invention is obtained by curing a film formed of the curable resin composition according to claim 2 (curable resin composition (II)) on a substrate with light. Yes.

In the present invention, a secondary hydroxyl group generated by a reaction between an epoxy resin and a carboxyl group-containing radical polymerizable unsaturated monomer is reacted with a polyisocyanate compound and a carboxyl group-containing polyol to form a urethane bond, a carboxyl group, a hydroxyl group, and an unsaturated group. It is characterized by using resin which has.
The urethane bond introduced into this resin can form a resist film with excellent flexibility and chemical resistance, and the carboxyl group is easy to develop with a developer such as alkaline water and is safer than organic solvents. It is hygienic, the hydroxyl group has a functional group that reacts with the hydroxyl group, for example, it can be reacted with a melamine resin curing agent to form a thermosetting resist film having further excellent thermal stability, heat resistance, etc. The resin can be instantly cured by active energy rays such as irradiation, and the productivity is excellent, and the hydroxyl group in the resin can be further reacted with, for example, a polyisocyanate compound and a hydroxyl group-containing radical polymerizable unsaturated monomer. Can introduce a radically polymerizable unsaturated group into the resin to form a photocured resist film having a higher crosslinking density. There is an effect.
Further, in the resin (A) used in the present invention, when all the raw materials used in the resin (A) are mixed and the target resin is synthesized, the resin is polymerized or the amount of functional groups to be introduced is The present invention can introduce the desired resin molecular weight and functional group amount, and exhibits the performance required for a solder resist film.

  The curable resin composition (I) according to the present invention comprises (A) a radical polymerizable unsaturated group and a secondary hydroxyl group-containing resin (A) obtained by reacting a polyepoxy resin with a carboxyl group-containing radical polymerizable unsaturated monomer ( a) (hereinafter, this may simply be abbreviated as “unsaturated resin (a)”) and the polyisocyanate compound (b) to react with the radical polymerizable unsaturated group and isocyanate group-containing resin (c) ( Hereinafter, this may be simply abbreviated as “unsaturated resin (c)”), and then this is reacted with a carboxyl group-containing polyol (d). Group- and hydroxyl group-containing resin (hereinafter, this may be simply abbreviated as “unsaturated resin (A)”), (B) a curing agent having a functional group that reacts with a hydroxyl group (hereinafter, this product is simply May be abbreviated as the curing agent (B) ".) And (C) a photopolymerization initiator (hereinafter, this one" photopolymerization initiator (C) are those which contain may be abbreviated to ".).

Unsaturated resin (A):
The unsaturated resin (A) is obtained by reacting an unsaturated resin (a) obtained by reacting a polyepoxy resin and a carboxyl group-containing radical polymerizable unsaturated monomer with a polyisocyanate compound (b). Next, this is a radical polymerizable unsaturated group, carboxyl group and hydroxyl group-containing resin obtained by reacting this with a carboxyl group-containing polyol (d).

  Hereinafter, the unsaturated resins (a) and (b) used in the unsaturated resin (A) will be described.

Unsaturated resin (a):
The unsaturated resin (a) is a radical polymerizable unsaturated group- and secondary hydroxyl group-containing resin obtained by reacting a polyepoxy resin with a carboxyl group-containing radical polymerizable unsaturated monomer.

  The unsaturated resin (a) has a number average molecular weight of 300 to 100,000, preferably 400 to 10,000. When the number average molecular weight is less than 300, chemical resistance, heat resistance, hardness and the like are inferior. On the other hand, when the number average molecular weight exceeds 100,000, the viscosity becomes high and gelation and thickening occur during resin synthesis.

The unsaturated resin (a) has 0.1 to 10 moles, preferably 0.5 to 10 moles of radically polymerizable unsaturated groups in 1 kg of the unsaturated resin, and has 0.1 to 10 secondary hydroxyl groups. Mol to 10 mol, preferably 0.5 mol to 5 mol.
If the radically polymerizable unsaturated group is less than 0.1 mol in 1 kg of the unsaturated resin, the photocurability is lowered. On the other hand, if it exceeds 10 mol, improvement in performance by photocuring cannot be expected.
When the secondary hydroxyl group is less than 0.1 mol, the number of urethane bonds, carboxyl groups, and hydroxyl groups introduced next is reduced, so the performance and the like are lowered. On the other hand, when the mol exceeds 10 mol, chemical resistance, water resistance, Inferior in heat resistance and hardness.

  Suitable examples of the polyepoxy resin include those obtained by reacting phenols such as phenol, cresol, halogenated phenol and alkylphenol with formaldehyde in the presence of an acidic catalyst. For example, YDCN-701, YDCN-704, YDPN-638, YDPN-602 as manufactured by Toto Kasei Co., Ltd .; DEN-431, DEN-439 as manufactured by Dow Chemical Company; manufactured by Ciba-Geigy Corporation EPN-1138, EPN-1235, EPN-1299; manufactured by Dainippon Ink & Chemicals, Inc. N-730, N-770, N-865, N-665, N-673, N-695, VH- 4150, VH-4240, VH-4440; Nippon Kayaku Co., Ltd. EOCN-120, EOCN-104, BRRN-1020; Asahi Kasei Kogyo Co., Ltd. ECN-265, ECN-293, ECN-285, ECN -299.

  Moreover, a part or all of a polyepoxy compound is made into a brand name, for example as a product made by Japan Epoxy Resin Co., Ltd., Epicoat 828, Epicoat 1007, Epicoat 807; Dainippon Ink and Chemicals Ltd. make Epicron 840, Epicron 860, Epicron 3050, Epicron 830; DER-330, DER-337, DER-361 manufactured by Dow Chemical Company; Celoxide 2021, Celoxide 3000 manufactured by Daicel Chemical Industries, Ltd .; TETRAD-X, TETRAD-C manufactured by Mitsubishi Gas Chemical Company, Inc. EPB-13, EPB-27 manufactured by Nippon Soda Co., Ltd .; YD-116, YD-128, YD-013, YD-020, YDG-414, ST-3000, ST-110, YDF manufactured by Toto Kasei Co., Ltd. -190, YDF-2004, YDF-2007; GY-260, GY-255, XB-2615 manufactured by Ciba-Geigy; bisphenol A such as DER-332, DER-662, DER-542 manufactured by Dow Chemical Mold, bisphe As a solder resist for printed wiring boards, it can be replaced with glycidyl ether type epoxy compounds such as Nord F type, hydrogenated bisphenol A type, brominated bisphenol A type, amino group-containing, alicyclic, or polybutadiene modified. It is particularly preferable to use a cresol polyepoxy compound.

  Examples of the carboxyl group-containing radically polymerizable unsaturated monomer include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, and saturated or unsaturated. Half esters of dibasic acid anhydrides and (meth) acrylates having one mole of hydroxyl group in one molecule, or half esters of saturated or unsaturated dibasic acids and unsaturated monoglycidyl compounds, such as phthalic acid , Saturated or unsaturated dibasic anhydrides such as tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, itaconic acid, chlorendic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid and methyltetrahydrophthalic acid And hydroxyethyl acrylate, hydroxypropyl acrylate , Hydroxybutyl acrylate, polyethylene glycol monoacrylate, glycerin acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and diglycerides of triglycidyl isocyanurate, or methacrylates corresponding to the above acrylates or saturated or A half ester obtained by reacting an unsaturated dibasic acid and glycidyl (meth) acrylate at an equimolar ratio by a conventional method is used alone or in combination, and acrylic acid is particularly preferred.

  Unsaturated resin (a) can manufacture the said polyepoxy resin and a carboxyl group-containing radically polymerizable unsaturated monomer by a conventionally well-known manufacturing method. As the production method, for example, if necessary, a reaction catalyst of a carboxyl group and an epoxy group is blended in an organic solvent solution obtained by dissolving or dispersing the mixture in an inert organic solvent as necessary. The reaction can be carried out under known reaction conditions such as a reaction temperature of 50 to 300 ° C., preferably 60 to 200 ° C. for about 10 minutes to 24 hours, preferably 20 minutes to 12 hours. The reaction is preferably performed, for example, in an oxygen atmosphere so that the radical polymerizable unsaturated group does not cause a radical polymerization reaction.

As the reaction catalyst, a conventionally known reaction catalyst of a carboxyl group and an epoxy group, for example, a catalyst such as tetrabutylammonium bromide can be used.
Further, as the organic solvent, it is preferable to use an inert solvent that does not substantially react with a functional group such as a carboxyl group, an epoxy group, a hydroxyl group, a radical polymerizable unsaturated group, or an isocyanate group. Specifically, for example, benzene, toluene, xylene, etc. as hydrocarbons, acetone, methyl ethyl ketone, hexanone, methyl isobutyl ketone as ketones, ethyl acetate, propyl acetate, butyl acetate, cellosolve as esters And carbitol acetate.
The blending ratio of the polyepoxy resin and the carboxyl group-containing radical polymerizable unsaturated monomer is such that the carboxyl group is in the range of 0.5 to 2 mol, preferably 0.8 to 1.2 mol, per mol of epoxy group. It is desirable to blend in.

Unsaturated resin (c):
The unsaturated resin (c) is a resin containing a radical polymerizable unsaturated group and an isocyanate group by reacting the unsaturated resin (a) with the polyisocyanate compound (b).

  The unsaturated resin (c) has a number average molecular weight of 400 to 100,000, preferably 500 to 10,000. When the number average molecular weight is less than 400, chemical resistance and flexibility are inferior. On the other hand, when it exceeds 100,000, the viscosity may increase and gelation may occur, and the coating workability may be inferior.

The unsaturated resin (c) has 0.1 to 10 mol, preferably 0.5 to 10 mol of a radical polymerizable unsaturated group in 1 kg of the unsaturated resin, and 0.1 to 10 mol of an isocyanate group, Preferably it has 0.5-10 mol.
If the radically polymerizable unsaturated group in 1 kg of the unsaturated resin is less than 0.1 mol, the photocurability is inferior. On the other hand, if it exceeds 10 mol, improvement in performance by photocuring cannot be expected.

When the number of isocyanate groups in 1 kg of unsaturated resin is less than 0.1 mol, the number of hydroxyl groups and carboxyl groups to be introduced next decreases, and the number of urethane bonds in the resin also decreases. I cannot expect much improvement in performance.
Examples of the polyisocyanate compound (b) include tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluidine diisocyanate, and lysine diisocyanate. In particular, aromatic polyisocyanates such as tolylene diisocyanate and xylylene diisocyanate are preferable from the viewpoint of heat resistance.

  Unsaturated resin (c) can manufacture the said unsaturated resin (a) and a polyisocyanate compound (b) by a conventionally well-known manufacturing method. The reaction between the isocyanate group and the hydroxyl group is usually performed at a reaction temperature of about 20 to 250 ° C., particularly 30 to 100 ° C. for about 10 minutes to about 24 hours, particularly about 20 minutes to about 12 hours. Is preferred. In the reaction, known reaction catalysts of isocyanate groups and hydroxyl groups, for example, tetrabutyltin, triphenylaluminum, tetra-n-butyl-1,3-diacetyloxydistanoxane, N-ethylmorpholine, etc. may be mentioned as necessary. Can do.

The blending ratio of the unsaturated resin (a) to the polyisocyanate compound (b) is such that the average number of isocyanate groups per hydroxyl group of the unsaturated resin (a) is 1.1 or more, preferably 1.5 to 2 It is desirable to blend so that
The unsaturated resin (A) is a radically polymerizable unsaturated group, carboxyl group and hydroxyl group-containing resin obtained by reacting the unsaturated resin (c) and the carboxyl group-containing polyol (d).

  The unsaturated resin (A) has a number average molecular weight of 530 to 100,000, preferably 630 to 10,000. When the number average molecular weight is less than 530, heat resistance and chemical resistance are inferior. On the other hand, when it exceeds 100,000, thickening or gelation occurs during resin synthesis, and the workability of coating the resist resin composition is also inferior. It is not preferable.

The unsaturated resin (A) has 0.1 to 10 moles, preferably 0.5 to 10 moles of radically polymerizable unsaturated groups in the unsaturated resin, and preferably 0.1 to 10 moles of carboxyl groups. Has from 0.5 to 10 moles and from 0.1 to 10 moles of hydroxyl groups, preferably from 0.5 to 10 moles.
When the radical polymerizable unsaturated group is less than 0.1 mol, the photocurability and the like are inferior.

When the carboxyl group is less than 0.1 mol, adhesion to the substrate and developability are poor, while when it exceeds 10 mol, developability and chemical resistance are poor.
When the hydroxyl group is less than 0.1 mol, the functional groups necessary for thermosetting are reduced and the heat resistance, plating resistance, solder resistance and the like are inferior, while when it exceeds 10 mol, the chemical resistance is inferior.

  The carboxyl group-containing polyol (d) is a compound containing an average of about 1 or more carboxyl groups in one molecule and an average of 2 or more hydroxyl groups in one molecule, such as dimethylolpropionic acid and dimethylolbutane. Examples of the acid include dimethylol valeric acid and the like, but are not particularly limited thereto. These can be used alone or in combination of two or more. In particular, dimethylolpropionic acid and dimethylolbutanoic acid are preferably used because they are easily dissolved in an organic solvent.

Unsaturated resin (A) can manufacture the above-mentioned unsaturated resin (c) and carboxyl group-containing polyol (d) by a conventionally well-known manufacturing method. The reaction between the isocyanate group and the hydroxyl group is carried out under the conditions described above, for example, the reaction temperature is usually about 20 to 250 ° C., particularly 30 to 100 ° C. It is preferable to make it react in the range. Moreover, the above-mentioned known reaction catalyst can be blended as necessary in the reaction.
The blending ratio of the unsaturated resin (c) and the carboxyl group-containing polyol (d) is such that the average number of hydroxyl groups of the carboxyl group-containing polyol (d) per isocyanate group of the unsaturated resin (c) is 0.8 or more, preferably It is desirable to blend so that the average is in the range of 0.9 to 1.2.

Curing agent (B):
As long as the curing agent (B) is a curing agent having a functional group that reacts with the hydroxyl group and / or the carboxyl group of the unsaturated resin (A), a conventionally known curing agent can be used without particular limitation. .

    Specifically, examples of the curing agent having a functional group that reacts with a hydroxyl group include amino resins, acid anhydrides, blocked polyisocyanate compounds, and curing agents having a functional group that reacts with a carboxyl group include, for example, poly An epoxy compound (for example, the polyepoxy resin described in the unsaturated resin (a)) and the like can be mentioned.

Examples of the amino resin include methylolated amino resins obtained by reacting an amino component such as melamine, urea, benzoguanamine, acetogranamamine, sterogtanamine, spiroguanamine, and dicyandiamide with an aldehyde. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. In addition, those obtained by etherifying this methylolated amino resin with an appropriate alcohol can be used. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, and n-butyl alcohol. I-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
Examples of the acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, dodecinyl succinic anhydride, pyromellitic dianhydride, chlorendic anhydride, and the like.

Examples of the blocked polyisocyanate compound include those obtained by blocking the polyisocyanate compound (b) with a blocking agent.
As the blocking agent, for example, phenol, lactam, active methylene, alcohol, mercaptan, acid amide, imide, amine, imidazole, urea, carbamate ester, imine, oxime, Alternatively, any blocking agent such as a sulfite salt may be used, but a phenol-based, lactam-based, alcohol-based or oxime-based blocking agent is particularly preferably used.

    The mixing ratio of the curing agent (B) is in the range of 10 to 100 parts by weight, preferably 20 to 80 parts by weight per 100 parts by weight of the unsaturated resin (A).

  When the blending ratio of the curing agent (B) is less than 10 parts by weight, the heat resistance and solder resistance are inferior. On the other hand, when it exceeds 100 parts by weight, the chemical resistance, adhesion and adhesion are inferior.

Photopolymerization initiator (C):
The photopolymerization initiator (C) is used for causing an unsaturated group of the unsaturated resin (A) to cause a radical reaction by light irradiation, and a conventionally known photopolymerization initiator is used. be able to.

  Specific examples of the photopolymerization initiator (C) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and benzyldimethyl ketal. 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, benzophenone, methyl benzoylbenzoate, hydroxybenzophenone, 2-isopropyl Pyrthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloro) -S-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, an iron-allene complex, a titanocene compound and the like are exemplified, but the invention is not particularly limited thereto.

  These photopolymerization initiators can be used alone or in admixture of two or more. The blending amount is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to about 8 parts by weight, based on 100 parts by weight (solid content) of the unsaturated resin (A).

  The curable resin composition (II) of the present invention includes a radical-polymerizable unsaturated group, a carboxyl group, and a hydroxyl group-containing resin (A) (unsaturated resin (A)) and a part or all of the hydroxyl groups in the resin. Radical polymerizable unsaturated group and carboxyl group-containing resin (D) in which a radical polymerizable unsaturated group is introduced via a urethane bond (hereinafter, this is simply abbreviated as “unsaturated resin (D)”). )Sometimes. ), The photopolymerization initiator (C).

  Since the unsaturated resin (A) and the photopolymerization initiator (C) are the same as described above, the details are omitted.

  The unsaturated resin (D) is preferably produced by reacting the unsaturated resin (A), the polyisocyanate compound (b), and a hydroxyl group-containing radical polymerizable unsaturated monomer.

  Examples of the hydroxyl group-containing radical polymerizable unsaturated monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, allyl alcohol, butanediol monoacrylate, butanediol monomethacrylate, N-methylolacrylamide. , Crotyl alcohol, propylene glycol monoacrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate DOO, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, hydroxypropyl isocyanurate mono (meth) acrylate, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, and the like.

In addition to the above, addition products of glycidyl acrylate or glycidyl methacrylate and monocarboxylic acid compounds (for example, acetic acid, propionic acid, crotonic acid, methacrylic acid, acrylic acid, etc.), (meth) acrylic acid and epoxy compounds (for example, epichlorohydrin) Etc.) can also be used. These can be used alone or in admixture of two or more.
Among the above, unsaturated monomers having 2 mol or more of radically polymerizable unsaturated groups and 1 mol or more of hydroxyl groups in one molecule (for example, pentaerythritol tri (meth) acrylate) are preferable.

    Unsaturated resin (D) can manufacture the above-mentioned polyisocyanate compound (b) and a hydroxyl-containing radically polymerizable unsaturated monomer by a conventionally well-known manufacturing method. For example, it can be produced by a reaction between the above-described hydroxyl group and isocyanate group.

The blending ratio of the unsaturated resin (A), the polyisocyanate compound (b), and the hydroxyl group-containing radical polymerizable unsaturated monomer is such that an average of about two isocyanate groups per hydroxyl group of the unsaturated resin (A), and hydroxyl group-containing radical polymerization. It can mix | blend so that the hydroxyl group of an unsaturated monomer may be about 1 on average.
The unsaturated resin (D) is a resin that can contain a radical polymerizable unsaturated group, a carboxyl group, and, if necessary, a hydroxyl group.

  The unsaturated resin (D) has a number average molecular weight of 630 to 100,000, preferably 730 to 10,000. When the number average molecular weight is less than 630, the heat resistance and chemical resistance are poor. On the other hand, when the number average molecular weight exceeds 100,000, the coating workability is poor.

The unsaturated resin (D) has 0.2 to 20 mol, preferably 0.6 to 15 mol of a radical polymerizable unsaturated group in 1 kg of the unsaturated resin, 0.1 to 10 mol of a carboxyl group, Preferably it has 0.5-10 mol.
When the radical polymerizable unsaturated group is less than 0.2 mol, the curability, solder resistance, heat resistance, plating resistance, etc. are inferior. On the other hand, when it exceeds 20 mol, the internal stress of the coating film due to rapid curing is large. That is, the adhesion to the substrate is poor.

  When the carboxyl group is less than 0.1 mol, developability is inferior, while when it exceeds 10 mol, chemical resistance is inferior.

    In addition to the above, the curable resin compositions (I) and (II) of the present invention include dyes, pigments, various additives (leveling agents, antifoaming agents, anti-sagging agents, adhesion improvers, coating surfaces as necessary. Modifiers, plasticizers, etc.), other radical polymerizable unsaturated compounds, other radical polymerizable unsaturated resins, photosensitizers, organic solvents, and the like.

  The curable resin compositions (I) and (II) of the present invention are generally known photosensitive materials such as paints, inks, adhesives, etching resist materials, solder resist materials, plating resist materials, photo resists, and the like. It can be used for a wide range of applications such as via buildup insulating materials, printing plate materials (plates and plate making plates for relief printing, PS plates for offset printing) information recording materials, relief image forming materials, and optical fiber coating materials. Among these, it is particularly preferable to use as a solder resist.

    The curable resin composition (I) of the present invention is applied to the substrate surface by means such as spray coating, electrostatic coating, spin coating, dip coating, roller coating, curtain flow coating, silk printing, and the like after exposure. It can be cured by heating.

As a light beam used for exposure, a conventionally known light beam can be used without any particular limitation. Examples of the light beam include ultraviolet light, visible light, and laser light (near infrared light, visible light laser, ultraviolet laser, etc.). The irradiation dose is usually in the range of 0.5 to 2000 mJ / cm ² , preferably 1 to 1000 mJ / cm ² .

    In addition, as an irradiation source of light, those conventionally used, for example, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, A light source obtained by each light source such as sunlight, a light beam in a visible region cut by an ultraviolet cut filter, or various lasers having an oscillation line in the visible region can be used.

  When an amino resin is used as the curing agent, for example, the temperature is about 100 to 300 ° C., preferably 120 to 250 ° C., and the time is 10 minutes to 30 hours, preferably 20 minutes to 24 hours. is there.

  The curable resin composition (II) of the present invention is applied to the surface of the substrate by means of spray coating, electrostatic coating, spin coating, dip coating, roller coating, curtain flow coating, silk printing, etc., and exposed. Can be cured. The exposure can be performed under the same irradiation conditions as described above.

The resist pattern forming method of the present invention includes (1) a step of coating a curable resin composition (I) on a substrate to form a curable resin film,
(2) a step of exposing and curing so that a desired resist film (image) is obtained on the surface of the curable resin film formed on the substrate;
(3) a step of developing the unexposed portion to form a resist pattern on the substrate;
(4) Next, the method includes a step of heating and thermosetting.

      As the above-mentioned base material, an electrically insulating glass epoxy plate, a polyethylene terephthalate film, a polyimide film or other plastic film or plastic plate; a metal foil such as copper or aluminum is adhered to the surface of these plastic plate or plastic film Or a conductive film formed by a method such as vacuum deposition, chemical vapor deposition, or plating of a metal such as copper, nickel, silver, or a conductive oxide typified by indium-tin oxide (ITO): Through Examples include a plastic plate provided with a hole portion, a surface of a plastic film and a through-hole portion formed with a conductive coating: a metal plate such as a copper plate: a patterned copper through-hole printed wiring board, and the like.

    The coating and exposure can be performed by the above-described methods.

    The film thickness of the above-described photosensitive resin film is preferably about 0.5 to 100 μm, particularly preferably about 1 to 50 μm.

       In the development process (3), a weak alkaline aqueous solution in which caustic soda, sodium carbonate, caustic potash, ammonia, amine or the like is diluted in water is usually used for washing out the uncured film.

    When the amino resin is used as the curing agent, the heating is, for example, in the range of about 100 to 300 ° C, preferably 120 to 250 ° C.

The resist pattern forming method of the present invention includes (i) a step of coating a curable resin composition (II) on a substrate to form a curable resin film,
(Ii) a step of exposing and curing so as to obtain a desired resist film (image) on the surface of the curable resin film formed on the substrate;
(Iii) a step of developing the unexposed portion to form a resist pattern on the substrate;
It is a method including.

In the resist pattern forming method, the above-described step (1) is the same step as (i), (2) is the same step (ii), (3) is the same step as (iii), and the forming method of the present invention is a curable resin. The steps are the same as those already described except that the curable resin composition (II) is used in place of the composition (I).
The resin cured product of the present invention is obtained by curing a film formed of the curable resin composition (I) on the above-described substrate with light and heat.
The resin cured product of the present invention is obtained by curing a film formed of the curable resin composition (II) on the above-described base material with light and heat.
Curing can be performed by the above-described method and conditions using light and heat.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples described below. In the synthesis examples and examples, “parts” and “%” are based on weight.

Example of production of unsaturated resin A 1090 parts of cresol polyepoxy resin (YDCN-702, manufactured by Toto Kasei Co., Ltd.) having an epoxy equivalent of 218 was placed in a three-necked flask equipped with a stirrer and a condenser, and heated at 90 to 100 ° C. Melt and stir. Next, 360 parts (5 mol) of acrylic acid, 0.6 part of hydroquinone and 7 parts of tetraethylammonium bromide were added. Next, the mixture was heated to 110 to 115 ° C., stirred and reacted for 12 hours, taken out from the reactor and cooled to room temperature, and an unsaturated resin acrylic acid of a polyepoxy compound having an acid value of 0.5 mgKOH / g (Unsaturated group about 3.4 mol / kg) was obtained.
Next, while blowing air into this product, 870 parts (5 mol) of tolylene diisocyanate and 2990 parts of cellosolve acetate solvent were mixed with 1450 parts of the above unsaturated resin a and reacted at 80 ° C. for 8 hours to obtain an isocyanate group-containing unsaturated resin. b (unsaturated group about 2.2 mol / kg, isocyanate group about 2.2 mol / kg) was obtained.
The resulting isocyanate group-containing unsaturated resin b2320 parts and dimethylolpropionic acid 670 parts (5 moles) were mixed and reacted at 80 ° C. for 8 hours to confirm that almost no isocyanate groups remained, carboxyl groups And a hydroxyl group-containing unsaturated resin A (unsaturated group 1.6 mol / kg, hydroxyl group 1.6 mol / kg, carboxyl group 1.6 mol / kg). The resin solid content was 50% by weight.

Production Example of Unsaturated Resin B 2990 parts (as resin solids) of the above unsaturated resin A were reacted with 174 parts (1 mole) of tolylene diisocyanate and 298 parts (1 mole) of pentaerythritol triacrylate at 80 ° C. for 8 hours. After confirming that almost no residual groups were observed, carboxyl group- and hydroxyl group-containing unsaturated resin B (unsaturated group 2.3 mol / kg, hydroxyl group 1.1 mol / kg, carboxyl group 1.4 mol / kg ) The resin solid content was 53% by weight.

Production Example of Unsaturated Resin C 1450 parts of the above unsaturated resin a (unsaturated group: about 3.4 mol / kg) was mixed with 940 parts (5 mol) of xylylene diisocyanate and 2990 parts of cellosolve acetate solvent at 80 ° C. By reacting for an hour, an isocyanate group-containing unsaturated resin b (about 2.2 mol / kg of unsaturated groups, about 2.2 mol / kg of isocyanate groups) was obtained.
The resulting isocyanate group-containing unsaturated resin b2390 parts and dimethylolpropionic acid 670 parts (5 moles) were mixed and reacted at 80 ° C. for 8 hours to confirm that almost no isocyanate groups remained, and carboxyl groups And hydroxyl group-containing unsaturated resin C (unsaturated group 1.6 mol / kg, hydroxyl group 1.6 mol / kg, carboxyl group 1.6 mol / kg). The resin solid content was about 50% by weight.

Example 1
100 parts of unsaturated resin A (as resin solids), 5 parts of Irgacure 907 (trade name, manufactured by Ciba Geigy), 10 parts of Cymel 350 (trade name, manufactured by Mitsui Cytec Co., Ltd.), 100 parts of barium sulfate, 5 parts of finely divided silica And dispersed with a shaker to obtain a solder resist composition of Example 1.

This solder resist composition was coated on a 0.27mm thick (copper epoxy thickness 0.20mm, copper thickness 0.035mm x 2) copper-clad laminate with a bar coater to a dry film thickness of 15μm, and at 80 ° C for 10 minutes Dried. Next, the pattern-formed photomask was irradiated with 150 mJ / cm ² from the coating surface using a 3 kW ultrahigh pressure mercury lamp. Next, the unexposed area was washed with a 1 wt% sodium carbonate solution at 30 ° C. for 30 seconds and developed. Next, post-curing was performed at 150 ° C. for 60 minutes to form a solder resist pattern. The performance of the obtained solder resist pattern was as follows.

Developability test A, adhesion test A, pencil hardness 5H, acid resistance A, alkali resistance A, solvent resistance A, plating resistance A, solder resistance A, pot life was better than 1 month.
Example 2
100 parts of unsaturated resin B (as resin solids), 10 parts of Cymel 350 (trade name, manufactured by Mitsui Cytec Co., Ltd.), 5 parts of Irgacure 907 (trade name, manufactured by Ciba Geigy), 100 parts of barium sulfate, 5 parts of fine silica And dispersed with a shaker to obtain a solder resist composition of Example 2.

This solder resist composition was coated on a 0.27mm thick (copper epoxy thickness 0.20mm, copper thickness 0.035mm x 2) copper-clad laminate with a bar coater to a dry film thickness of 15μm, and at 80 ° C for 10 minutes Dried. Next, the pattern-formed photomask was irradiated with 150 mJ / cm ² from the coating surface using a 3 kW ultrahigh pressure mercury lamp. Next, the unexposed portion was washed with a 1 wt% sodium carbonate solution at 30 ° C. for 30 seconds and developed to form a solder resist pattern. The performance of the obtained solder resist pattern was as follows.

  Developability test A, adhesion test A, pencil hardness 5H, acid resistance A, alkali resistance A, solvent resistance A, plating resistance A, solder resistance A, pot life was better than 1 month.

Example 3
100 parts of unsaturated resin C (as resin solids), 10 parts of cresol polyepoxy resin (YDCN-702 manufactured by Tohto Kasei Co., Ltd.), 5 parts of Irgacure 907 (trade name, manufactured by Ciba Geigy), 100 parts of barium sulfate, fine silica 5 parts was mixed and dispersed with a shaker to obtain a solder resist composition of Example 3.

This solder resist composition was coated on a 0.27mm thick (copper epoxy thickness 0.20mm, copper thickness 0.035mm x 2) copper-clad laminate with a bar coater to a dry film thickness of 15μm, and at 80 ° C for 10 minutes Dried. Next, the pattern-formed photomask was irradiated with 150 mJ / cm ² from the coating surface using a 3 kW ultrahigh pressure mercury lamp. Next, the unexposed area was washed with a 1 wt% sodium carbonate solution at 30 ° C. for 30 seconds and developed. Next, post-curing was performed at 200 ° C. for 50 minutes to form a solder resist pattern. The performance of the obtained solder resist pattern was as follows.

  Developability test A, adhesion test A, pencil hardness 5H, acid resistance A, alkali resistance A, solvent resistance A, plating resistance A, solder resistance A, pot life was better than 1 month.

Comparative Example 1
1090 parts of a cresol polyepoxy resin (YDCN-702 manufactured by Toto Kasei Co., Ltd.) having an epoxy equivalent of 218 is placed in a three-necked flask equipped with a stirrer and a cooler, heated and melted at 90 to 100 ° C., and stirred. Next, 360 parts (5 mol) of acrylic acid, 0.6 part of hydroquinone and 7 parts of tetraethylammonium bromide were added. Next, the temperature of the mixture was raised to 110 to 115 ° C., stirred and reacted for 12 hours, taken out from the reactor and cooled to room temperature. (Unsaturated group about 3.4 mol / kg) was obtained.
Next, while blowing air into this product, 870 parts (5 moles) of tolylene diisocyanate, 670 parts (5 moles) of dimethylolpropionic acid and 2990 parts of cellosolve acetate solvent were mixed with 1450 parts of the above unsaturated resin at 80 ° C. As a result of reaction for 8 hours, the resin gelled.
1) Developability test The development of a 1% by weight sodium carbonate aqueous solution at a spray pressure of ² kg / cm ² for 30 seconds was performed, and the state where the unexposed area was removed was visually determined. ◎: Completely developed ○: Some thinly undeveloped parts on the surface △: Overall developed residue ×: Little developed 2) Adhesion test 100 pieces in a grid pattern A cross cut was made, and then the peeled state after the peeling test with a cellophane tape was visually judged. Number of remaining grids / Number of created grids, ◎: 100/100 with no peeling ○: 100/100 with slightly cross-cut part △: 50/100 to 90/100 X: 0 / 100-50-100.

3) Pencil hardness test
The hardness was measured with a load of 1 kg according to the test method of JIS K 5400.
4) Acid resistance test
The film was immersed in a 10% by weight sulfuric acid aqueous solution at 20 ° C. for 30 minutes and then taken out, and the state and adhesion of the coating film were comprehensively evaluated. ◎: No change is observed at all ○: Slightly changed △: Significantly changed ×: The coating has blisters or swelling drops 5) Alkali resistance test
The film was taken out after being immersed in a 10% by weight aqueous sodium hydroxide solution at 20 ° C. for 30 minutes, and the state and adhesion of the coating film were comprehensively evaluated. ◎: No change is observed at all ○: Slightly changed △: Significantly changed ×: The coating has blisters or swelling detachment 6) Solvent resistance test Acetone solvent at 20 ° C The film was immersed for 30 minutes and then taken out, and the state and adhesion of the coating film were comprehensively evaluated. ◎: No change at all ○: Only slight change △: Significant change ×: The coating has blisters or swelling detachment 7) Plating resistance test “Autoronex CI” The state of the coating film after depositing gold with a thickness of 1.5 μm by plating for 9 minutes with a current density of 1 A / dm ² at a liquid temperature of 30 ° C. using a sock liquid manufactured by Celex, USA Evaluation was performed in the same manner as in the acid resistance test.
8) Solder resistance test
According to the test method of JIS C 6481, the state of the coating film after being immersed in a 260 ° C. solder bath for 10 seconds 5 times was evaluated in the same manner as in the acid resistance test.
9) Pot life measurement
The number of days until the viscosity value immediately after production doubles when stored at 20 ° C.

The curable resin composition of the present invention is composed of paint, ink, adhesive, etching resist material, solder resist material, plating resist material, photovia build-up insulating material, printing plate material (plate and letterpress plate making material, offset printing PS Plate) It can be used for a wide range of applications such as information recording materials, relief image forming materials, and optical fiber coating materials. Among these, it is particularly preferable to use as a solder resist.

Claims (6)

The following component (A) A radical polymerizable unsaturated group obtained by reacting a polyepoxy resin with a carboxyl group-containing radical polymerizable unsaturated monomer and a secondary hydroxyl group-containing resin (a) are reacted with a polyisocyanate compound (b). A radically polymerizable unsaturated group and an isocyanate group-containing resin (c), and then reacting the resin (c) with a carboxyl group-containing polyol (d) to form a radically polymerizable unsaturated group, a carboxyl group and a hydroxyl group Containing resin,
A curable resin composition comprising (B) a curing agent having a functional group that reacts with a hydroxyl group and / or a carboxyl group, and (C) a photopolymerization initiator. The following component (D) A radical polymerizable unsaturated group obtained by reacting a polyepoxy resin with a carboxyl group-containing radical polymerizable unsaturated monomer and a secondary hydroxyl group-containing resin (a) are reacted with a polyisocyanate compound (b). To produce a radically polymerizable unsaturated group and isocyanate group-containing resin (c), and then react the resin (c) with a carboxyl group-containing polyol (d) to contain a radically polymerizable unsaturated group, a carboxyl group and a hydroxyl group. Resin (A) is produced, and then a part or all of hydroxyl groups in the resin (A) are radically polymerizable unsaturated groups and carboxyl groups containing radically polymerizable unsaturated groups introduced through urethane bonds A curable resin comprising a resin (C) a photopolymerization initiator and, if necessary, a curing agent having a functional group that reacts with a carboxyl group Narubutsu. (1) A step of coating the curable resin composition according to claim 1 on a substrate to form a curable resin film;
(2) a step of exposing and curing so that a desired resist film (image) is obtained on the surface of the curable resin film formed on the substrate;
(3) a step of developing the unexposed portion to form a resist pattern on the substrate;
(4) Next, a resist pattern forming method comprising a step of heating and thermosetting. (I) a step of coating the curable resin composition according to claim 2 on a substrate to form a curable resin film;
(Ii) a step of exposing and curing so as to obtain a desired resist film (image) on the surface of the curable resin film formed on the substrate;
(Iii) a step of developing the unexposed portion to form a resist pattern on the substrate;
A resist pattern forming method comprising: A cured resin obtained by curing a film formed of the curable resin composition according to claim 1 on a substrate by light and heat. A cured resin obtained by curing a film formed of the curable resin composition according to claim 2 on a substrate with light.