JP4705426B2 - Alkali development type photosensitive resist ink composition for printed wiring board production, cured product thereof and printed wiring board - Google Patents

Description

  The present invention relates to an alkali development type photosensitive resist ink composition for producing a printed wiring board, which can be suitably used as a solder resist ink, an etching resist ink, and the like, a cured product thereof, and a printed wiring board.

  Conventionally, the formation of a resist such as a solder resist or an etching resist on a printed wiring board or the like has been performed by a printing method, but it is not sufficient to cope with the recent refinement of a printed wiring board and the like, so photo development Type resist ink has been used (see Patent Documents 1 and 2).

  Evaluation items for the photo-developing resist ink include finger touch, photo-curing property, developability and the like. If the finger touch is poor, there are problems in terms of work such as resist transfer failure due to sticking of the mask film and contamination of the mask film. In addition, if the photocurability is low, the workability deteriorates because a long time is required for exposure. Also, if the developability is poor, the development time becomes long and the workability is lowered, and the resist component remains in the portion that should be developed originally, so that in the case of an etching resist or the like, an etching failure occurs, and the solder resist In some cases, problems such as poor solder adhesion occur.

  For this reason, it is desirable that the performance such as finger touch, photo-curing property, developability, etc. is all good, but with conventional photo-developing resist ink, there is a trade-off relationship between finger tack, photo-curing property and developability. It is in. That is, if the molecular weight of the base resin in the resist ink is increased, the tactile tack after drying can be improved, but the base resin contains more high molecular weight components than the desired molecular weight, leading to unexposed areas. As a result, the penetrability of the developer decreases and the developability deteriorates. Conversely, if the molecular weight is decreased for the purpose of improving developability, more components having a lower molecular weight than the desired molecular weight are mixed, and the photocurability of the dried coating film is improved, but the finger tack is deteriorated. End up.

  In addition, due to the demand for finer printed wiring boards, further improvement in the resolution of photographic development resist ink is desired, but it is formed by the current exposure and development processing of photographic development resist ink. The edge portion of the resist film is uneven and tends to be rough, and it is difficult to form a sharp shape that can cope with further refinement of photographic resist ink. This is because, due to the molecular weight distribution of the base resin in the photo-developing resist ink, the solubility of the resist ink in the exposed portion and the unexposed portion becomes non-uniform in the developing solution such as an alkaline developer. Conceivable.

These problems occur because the molecular weight distribution in the base resin is wide, but it is difficult to narrow the molecular weight distribution. That is, an acrylic polymer often used as a base resin for a photo-developing resist is usually produced by radical polymerization, and the molecular weight distribution tends to be wide due to the nature of the polymerization method. In addition, it is difficult to control the monomer arrangement within the molecule, and when the monomers are charged all at once, the monomer composition between the polymers changes as the reaction proceeds. The polymer becomes a mixture of polymers having various monomer compositions. In addition, in order to solve this problem, there is a method in which the polymerization reaction proceeds while dropping the monomer in order to make the monomer composition in the polymer as uniform as possible between the polymers by the conventional radical polymerization method. Although it can be considered, it takes a long time to synthesize the polymer, and the uniformity of the molecular weight of the obtained polymer becomes insufficient.
JP 2003-252938 A JP 2004-264773 A

  The present invention has been made in view of the above points, and is an alkali development type photosensitive resist ink composition for producing a printed wiring board, which is excellent in low tackiness, photocurability and developability, and excellent in resolution, It is another object of the present invention to provide a cured product and a printed wiring board produced using the alkali development type photosensitive resist ink composition for producing the printed wiring board.

The alkali development type photosensitive resist ink composition for producing a printed wiring board according to the present invention comprises the following components (A) to (C).
(A) Alkali-soluble polymer having a dispersity of 1.8 or less obtained by living radical polymerization method (B) Photopolymerizable monomer (C) Photopolymerization initiator This composition is an etching resist for producing printed wiring boards. It can be suitably used as ink, solder resist ink, etc., and at this time, it contains an alkali-soluble polymer with a narrow molecular weight distribution produced by the living radical polymerization method. It is possible to prevent the deterioration of developability due to a decrease in the permeability of the developer to the unexposed area and the deterioration of the touch of the dry paint film due to the mixing of low molecular weight components. Unevenness is hardly generated in the alkali-soluble distribution in the unexposed portion, and a dry coating film having uniform alkali-solubility can be formed.

  The alkali development type photosensitive resist ink composition for producing a printed wiring board according to the present invention contains the component (A) and the component (C), and the component (A) has photosensitivity. good. Even in such a composition, it can be suitably used as an etching resist ink for manufacturing a printed wiring board, a solder resist ink, etc., and at this time contains an alkali-soluble polymer having a narrow molecular weight distribution generated by a living radical polymerization method. Therefore, the deterioration of the developability due to the decrease in the permeability of the developer to the unexposed part of the dry coating due to the mixing of high molecular weight components and the touch of the dry coating due to the mixing of low molecular weight components Deterioration of tack can be prevented, and unevenness in the alkali-soluble distribution in the unexposed portion of the dried coating film is less likely to occur, so that a dried coating film having uniform alkali solubility can be formed. At this time, it is possible to maintain good cured product characteristics only by adding the component (C) without adding a photosensitive component in addition to the component (A).

  In this case, when the component (B) is further contained, further photosensitivity can be imparted to the composition, and the physical properties of the cured product can be adjusted.

  In the composition as described above, the component (A) is preferably synthesized by an atom transfer radical polymerization method, and the component (A) is a reversible addition-fragmentation chain transfer polymerization method. It is also preferred that it is synthesized. Such a living radical polymerization method has a wide range of application of monomers and is suitable for the production of component (A).

  In addition, the component (A) preferably has a carboxyl group in the molecule, thereby imparting alkali solubility to the component (A), and polymerization of a monomer having a carboxyl group, or a hydroxyl group in the polymer. It is possible to introduce an alkali-soluble group by adding an acid anhydride to the base, and compared to the case of introducing another alkali-soluble group, it is easy to obtain a raw material having a carboxyl group and has an advantage that the introduction reaction is easy. There is. Moreover, when using the (G) component mentioned later as a component of resist ink especially, there exists an advantage that coating-film performance can be improved easily because reaction of a carboxyl group and an epoxy group occurs.

  Further, the component (A) is preferably one having an ethylenic double bond in the molecule, whereby the photosensitivity can be imparted to the component (A), and the curability of the composition can be adjusted. In addition, the physical properties of the cured product can be adjusted.

  In addition, the component (A) can react with at least one ethylenic double bond and at least one carboxyl group in the molecule of a part of the carboxyl group in the polymer (A1) having a carboxyl group in the side chain. It is also preferable that the compound is obtained by reacting a compound (d) having a reactive group. Since such a component has a carboxyl group and an ethylenic double bond introduced by a two-step synthesis and can impart sufficient coating performance as a temporary coating to the composition, it is particularly useful as an etching resist ink. It can be used suitably.

  Further, the component (A) is a hydroxyl group formed by reacting a saturated or unsaturated monocarboxylic acid (e) with a part or all of the epoxy group in the polymer having an epoxy group in the side chain, and further by the reaction. It is also preferable that it is obtained by reacting a part of the polybasic acid anhydride (f). Since such components can introduce more carboxyl groups and ethylenically unsaturated double bonds and can easily improve the performance as a permanent coating, the composition is particularly suitable as a solder resist ink. Can be used.

Moreover, it is also preferable to contain the following (G) component in the above compositions.
(G) Polyfunctional epoxy compound In this case, the composition can be given thermosetting properties, and further cured by photo-curing to further improve the cured product properties such as strength, hardness and chemical resistance. Is something that can be done.

Moreover, it is also preferable to contain the following (H) component in a composition.
(H) Diluent In this case, the resin component of the composition can be dissolved and diluted so that the composition can be applied as a liquid, and after application of the composition, it is volatilized by drying to form a dry coating film. A film can be formed.

  The cured product according to the present invention is obtained by curing and molding the above-mentioned alkali development type photosensitive resist ink composition for producing a printed wiring board on a substrate. This cured product has excellent properties as a resist for manufacturing printed wiring boards.

  The printed wiring board according to the present invention is characterized by having a layer made of the cured product. For this reason, the resist which has a favorable film | membrane characteristic can be formed in the layer which consists of the said hardened | cured material with respect to a printed wiring board.

  According to the present invention, there is no deterioration in developability or deterioration in touch and tack due to the wide molecular weight distribution of the alkali-soluble polymer, and performance such as touch and tackiness, photocurability and developability is achieved. It is possible to obtain a good composition for all, and since it is excellent in resolution, it can form a fine and sharp pattern, and can cope with further finer printed wiring boards in recent years. It can be.

  Hereinafter, the best mode for carrying out the present invention will be described.

[Constituent Components of Alkali Development Type Photosensitive Resist Ink Composition for Printed Wiring Board Production]
First, components for preparing an alkali developing type photosensitive resist ink composition (hereinafter referred to as a composition) for producing a printed wiring board will be described.

(A) Alkali-soluble polymer having a dispersity of 1.8 or less obtained by the living radical polymerization method The component (A) is a polymer having an alkali-soluble group in the molecule, and is obtained by the living radical polymerization method. The degree of dispersion (Mw / Mn) defined by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 1.8 or less. The degree of dispersion can be derived based on the measurement result of molecular weight by GPC (gel permeation chromatography).

  About the monomer used for the synthesis | combination of (A) component, what is necessary is just a copolymerizable ethylenically unsaturated monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (Meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl Linear, branched or alicyclic alkyl (meth) such as (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. Acryle 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate; polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 23) mono (meth) acrylates; methoxyethyl (meth) Acrylate, ethoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, methoxydiethylene glycol (meth) acrylate Ethylene glycol ester-based (meth) acrylates such as rate, and similar propylene glycol-based (meth) acrylates, butylene glycol-based mono (meth) acrylates; dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, Amino group-containing (meth) acrylates such as 2-dimethylaminoethyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide Acrylamides such as N-propyl (meth) acrylamide, N-tertiary butyl (meth) acrylamide, N-tertiary octyl (meth) acrylamide and diacetone (meth) acrylamide; styrene, o-vinyltoluene Ene, m-vinyltoluene, p-vinyltoluene, α-methylstyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, vinyl aromatic compounds such as p-hydroxy-α-methylstyrene and p-vinylbenzyl alcohol; maleimides such as maleimide, N-benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; 2- (meth) acrylamide ethane Sulfonic acid group-containing (meth) acrylates such as sulfonic acid, 2- (meth) acrylamidepropanesulfonic acid, and 3- (meth) acrylamidepropanesulfonic acid; in addition, glycerol mono (meth) acrylate, vinyl acetate, vinyl ethers, ( Meta) Lil alcohol, vinylidene cyanide, vinyl chloride, vinylidene chloride, vinyl pyrrolidone, and (meth) acrylonitrile.

  Also, a small amount of a compound having a plurality of copolymerizable ethylenically unsaturated groups can be used as long as gelation does not occur. Such polyfunctional ones include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, etc. . These can be used alone or in combination, in order to adjust the hardness of the coating film after pre-curing and the final resist hardness in the case of resist ink, or dispersibility, solubility, printability, etc. It is used for adjustment of workability in the process of using resist ink.

  In the present invention, the component (A) is synthesized by a living radical polymerization method using the monomers exemplified above.

  The living radical polymerization method is a polymerization method characterized in that a growth radical is reversibly led to a stable dormant species. Compared with a normal radical polymerization method, the bimolecular termination reaction is less likely to occur, and the dispersity (Mw / A polymer having a small Mn) is obtained. Moreover, since the molecular weight of the polymer obtained is determined by the charge ratio of the initiating group and the monomer, the molecular weight can be easily set.

  Living radical polymerization methods are based on dissociation-bonding mechanisms using stable radicals such as nitroxide compounds, and on atom transfer radical polymerization methods in which reversible radicalization occurs by extracting halogen atoms of organic halogen compounds with transition metal complexes. And radical transfer to a chain transfer agent (RAFT agent) such as a dithioester compound, and can be broadly divided into those by reversible addition-fragmentation chain transfer polymerization method in which exchange reaction occurs reversibly. Since the range is wide, it is preferable to employ an atom transfer radical polymerization method or a reversible addition-fragmentation chain transfer polymerization method.

  In the atom transfer radical polymerization method, a reaction in which a growth radical is generated by reversibly extracting a halogen atom from a carbon-halogen bond of an organic halogen compound to a transition metal by oxidation of a transition metal of a transition metal complex, Like normal radical polymerization, a reaction that causes a growth reaction with the monomer and a reaction that reversibly reduces the transition metal of the transition metal complex in a highly oxidized state to regenerate the carbon-halogen bond occur. Due to the fast equilibrium of this reaction, the bimolecular termination reaction seen in conventional radical polymerization is suppressed, and a polymer with a narrow molecular weight distribution and a controlled molecular weight can be obtained.

  As the transition metal complex used in this atom transfer radical polymerization method, a transition metal complex belonging to Groups 7 to 11 of the periodic table is effective, and as such a metal, copper, ruthenium, iron, nickel, rhodium, Examples include palladium and rhenium.

  Among these, in the atom transfer radical polymerization system using a copper complex, as a transition metal complex, for example, a monovalent copper compound such as cuprous chloride and cuprous bromide and a complex of a nitrogen-based multidentate ligand are used alone. Can be used in combination, or multiple types can be used in combination. At this time, the complex of the nitrogen-based multidentate ligand is added in an amount equal to or more than the coordination number with respect to the copper compound, but usually 1 to 10 mol is added to 1 mol of the copper compound. As the nitrogen-based multidentate ligand, for example, those shown in the following structural formulas (1) to (10) can be used.

R ₁ : H, t-C ₄ H ₉ , n-C ₇ H ₁₅ or n-C ₉ H _{19
R 2: n-C 3 H} 7, 5-C 9 H 19 or n-C ₅ H ₁₁
R ₃ : H or Ph (phenyl group)
R ₄ : H or CH ₃
In addition, in an atom transfer radical polymerization system using a ruthenium complex, a divalent ruthenium complex can be used as a transition metal complex in the presence of aluminum alkoxides. As such a transition metal complex, the following structural formula ( 11) to (13). In the formula, Ph represents a phenyl group.
[RuCl ₂ (PPh ₃ ) ₃ ] (11)
[RuH ₂ (PPh ₃ ) ₄ ] (12)

In addition, in an atom transfer radical polymerization system using a nickel complex, a divalent or zero-valent nickel phosphine complex can be used as a transition metal complex. Examples of such a transition metal complex include the following structural formulas (14) to (14) to (18) can be mentioned. In the formula, Ph represents a phenyl group.
[NiBr ₂ (PPh ₃ ) ₂ ] (14)
[NiBr ₂ (PnBu ₃ ) ₂ ] (15)
[Ni (PPh ₃ ) ₄ ] (16)
[NiCO ₂ (PPh ₃ ) ₂ ] (17)

In an atom transfer radical polymerization system using an iron complex, a divalent iron phosphine complex can be used as a transition metal complex. Examples of such a transition metal complex include those represented by the following structural formula (19). In the formula, Ph represents a phenyl group. X represents halogen, for example, Cl, Br or the like.
[FeX ₂ (PPh ₃ ) ₂ ] (19)
As the initiator used in such an atom transfer radical polymerization method, one that contains a halogen atom and generates a radical when the halogen atom is extracted can be used, and the reaction is initiated by the generation of the radical. Therefore, the addition amount of the initiator is determined by the number average molecular weight Mn of the desired polymer and the number of halogen atoms contained in the initiator.

As such an initiator, for example, as shown in the following structural formula (20), sulfochlorides and the like can be used. In the formula, X represents chlorine or bromine. A _{1 to} A ₃ are substituents that easily generate a carbon radical when the halogen atom X is extracted, and examples include a halogen atom (X), a carbonyl group, a nitrile group, and a phenyl group (Ph).

Specific examples of such initiators include, for example, haloalkanes such as CX ₄ , CHX ₃ and CH ₂ X ₂ ; haloketones such as CX ₃ COCH ₃ and CHX ₂ COPh, corresponding to the structural formula (20). Halonitriles such as CH ₃ CH (CN) X; haloalkylbenzenes such as CH ₃ CH (Ph) X and CH ₂ (Ph) X; CX ₃ CO ₂ CH ₃ , CHX ₂ CO ₂ CH ₃ , and CH ₃ CH (CO ₂ CH ₃ ) X, CH ₃ CH (CO ₂ CH ₂ CH ₃ ) X, CH ₃ CH (CO ₂ C (CH ₃ ) ₃ ) X, CH ₃ C (CH ₃ ) (CO ₂ CH ₃ ) X _{, CH 3 C (CH 3)} (CO 2 CH 2 CH 3) X, CH 3 C (CO 2 Et) 2 X, CH 3 C (CH 3) (CO 2 CH 3) CH 2 CH (CO 2 CH 3 ) X, CH ₃ C (CH ₃ ) (CO ₂ CH ₃ ) CH ₂ C (CH ₂ ) (CO ₂ CH ₃ ) Haloesters such as X.

Examples of the sulfonyl chlorides include sulfonyl chlorides such as CH ₃ SO ₂ Cl, CCl ₃ SO ₂ Cl, PhSO ₂ Cl, CH ₃ OPhSO ₂ Cl, and ClPhSO ₂ Cl.

  Living radical polymerization by the valence transfer radical polymerization method can be performed by introducing a transition metal complex and an initiator as described above into a polymerization reaction system containing a monomer to be polymerized. It can be carried out in a solvent or solvent.

  In the case of using a solvent, for example, water, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol, ethylene glycol and other linear, branched, secondary or polyhydric alcohols; methyl ethyl ketone Ketones such as cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; Petroleum aromatic mixed solvents such as Swazil series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co., Ltd.); Cellosolve Cellosolves such as butyl cellosolve; Carbitols such as carbitol and butylcarbitol; Propylene glycol alkyl ethers such as propylene glycol methyl ether; Polypropylene glycol such as dipropylene glycol methyl ether Lumpur alkyl ethers; can be used dialkyl glycol ethers; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve sol blanking acetate, butyl carbitol acetate, acetic acid esters such as propylene glycol monomethyl ether acetate. Such organic solvents can be used alone or in combination of two or more.

  The reaction temperature at this time can be in the range of 0 ° C. to 200 ° C., and the reaction is usually performed in an inert gas atmosphere such as nitrogen or argon.

  In the reversible addition-fragmentation chain transfer polymerization method (RAFT polymerization method), living radical polymerization is caused by introducing a RAFT agent typified by a dithioester compound into a radical polymerization reaction system.

  As the RAFT agent, dithioesters having a C═S unsaturated group in the molecule as described above can be used, and specific examples include those represented by the following structural formula (21).

  Here, R in the structural formula (21) represents any of the following structural formulas (21a) to (21g), and Z represents any of the following structural formulas (21h) to (21o).

  The living radical polymerization by the reversible addition-fragmentation chain transfer polymerization method is a RAFT agent as described above in a normal radical polymerization reaction system in which an appropriate polymerization initiator is contained as necessary in the monomer to be subjected to the polymerization reaction. In this case, the reaction can be carried out without solvent or in a solvent.

  In the case of using a solvent, for example, water, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol, ethylene glycol and other linear, branched, secondary or polyhydric alcohols; methyl ethyl ketone Ketones such as cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; Petroleum aromatic mixed solvents such as Swazil series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co., Ltd.); Cellosolve Cellosolves such as butyl cellosolve; Carbitols such as carbitol and butylcarbitol; Propylene glycol alkyl ethers such as propylene glycol methyl ether; Polypropylene glycol such as dipropylene glycol methyl ether Lumpur alkyl ethers; can be used dialkyl glycol ethers; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve sol blanking acetate, butyl carbitol acetate, acetic acid esters such as propylene glycol monomethyl ether acetate. Such organic solvents can be used alone or in combination of two or more.

  Moreover, reaction temperature can be made into the range of 0 to 200 degreeC, and it is normally performed in inert gas atmosphere, such as nitrogen and argon.

  The component (A) is produced by the living radical polymerization method as described above. At this time, as a method of introducing an alkali-soluble group into the component (A) to make an alkali-soluble type, there is one in the molecule. A monomer having both two radical polymerizable double bonds and one or more alkali-soluble groups is copolymerized by the living radical polymerization method, and an appropriate reactive group is previously added to the polymer obtained by the living radical polymerization method. Introducing a compound having both a functional group that reacts with the reactive group and an alkali-soluble group, or a method of reacting and combining with the reactive group to react with a compound that generates a carboxyl group Can be mentioned. Here, examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group.

  As the component (A), those having photosensitivity can be used, but those having no photosensitivity can also be used. Here, the photosensitivity means a property that causes a polymerization reaction upon irradiation with energy rays such as ultraviolet rays, visible rays, infrared rays, and electron beams in the presence of an appropriate photopolymerization initiator.

  Specific examples of such component (A) include the following components (A1) to (A3).

  (A1) A polymer having a carboxyl group in the side chain.

  (A2) Obtained by reacting a part of the carboxyl group of component (A1) with a compound (d) having a reactive group capable of reacting with at least one ethylenic double bond and one carboxyl group in the molecule. Polymer.

  (A3) After producing a polymer having an epoxy group in the side chain, all or part of the epoxy group is reacted with a saturated or unsaturated monocarboxylic acid (e), and all or all of the hydroxyl groups in the product are reacted. A polymer obtained by partially reacting a polybasic acid anhydride (f).

  The component (A1) contains at least one monomeric component having at least one copolymerizable ethylenically unsaturated group, and at least one or all of the monomer components subjected to the polymerization, Using a compound having a heavy bond and at least one carboxyl group, this polymerization can be carried out by the living radical polymerization method as described above.

  Examples of the compound having one ethylenic double bond and at least one carboxyl group in the molecule include acrylic acid, methacrylic acid, acrylic acid dimer, cinnamic acid and the like; succinic anhydride, maleic anhydride, phthalic anhydride, and the like. Dibasic acid anhydrides such as acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride And hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate Reaction with compounds having an ethylenically unsaturated group containing one hydroxyl group in one molecule such as rate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate Half esters obtained by succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Dibasic acids such as itaconic acid and glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Examples include half esters obtained by reacting a compound having an ethylenically unsaturated group containing one epoxy group in one molecule such as tomonoglycidyl ether.

  Such compounds can be used alone or in combination of two or more. Among these, (meth) acrylic acid can be mentioned as a particularly preferred compound.

  Here, when the component (A1) is synthesized by an atom transfer radical polymerization method, if a carboxyl group is present in the system, the transition metal atom reacts with the carboxyl group, and the bimolecular termination reaction cannot be suppressed. It is preferable that a protective group such as a tertiary butyl group or a trimethylsilyl group is previously bonded to the carboxyl group in the monomer, and the protective group is eliminated after polymerization to generate the carboxyl group.

  Further, the component (A1) obtained as described above is further reacted with the component (d) (compound having a reactive group capable of reacting with at least one ethylenic double bond and one carboxyl group in the molecule). And when producing | generating said (A2) component, what has a glycidyl group, an isocyanate group, etc. as a reactive group which can react with a carboxyl group as (d) component can be mentioned. Specifically, as a compound having a glycidyl group, glycidyl (meth) acrylate, (3,4-epoxydicyclohexyl) methyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Glycidyl ether, allyl glycidyl ether, epoxidized stearyl acrylate (manufactured by Shin Nippon Rika Co., Ltd .; product number “Licar Resin ESA”) and the like are 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK; product number “ Karenz AOI ”, 2-methacryloyloxyethyl isocyanate (Showa Denko KK; product number“ Karenz MOI ”) and the like.

  This component (A2) has photosensitivity because it has an ethylenic double bond derived from the component (d).

  Although this (d) component can be used individually or in combination of multiple types, it is particularly preferable to use glycidyl (meth) acrylate.

  In reacting the component (d) with the component (A1), the acid value of the component (A2) produced by reacting the component (d) is in the range of 20 to 200 mgKOH / g (d). It is preferable to set the added amount of the components.

  Moreover, when making this reaction, it is preferable to use a catalyst in order to promote this reaction. Examples of the catalyst include tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine. The amount of the catalyst used is the total amount of the reaction raw material mixture (finally the total amount of raw materials contained in the reaction system), that is, the monomers used for the production of the component (A1), the solvent, the catalyst used in the living radical polymerization method, and The total amount of initiator, component (d), catalyst used for reaction of component (d), polymerization inhibitor used for reaction of component (d), etc. is preferably in the range of 0.1 to 10% by weight. .

  In addition, a polymerization inhibitor is preferably used for the purpose of preventing the polymerization reaction of the component (A1) during this reaction. Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether. The amount used is preferably 0.01 to 1% by weight based on the total amount of the reaction raw material mixture.

  The reaction conditions of this (A1) component and (d) component are made to react by the conventional method, Preferably it is 60-150 degreeC, Most preferably, it is made to react at the reaction temperature of 80-120 degreeC. The reaction time is preferably 5 to 60 hours.

  In addition, the polymer having an epoxy group in the side chain for obtaining the component (A3) is a monomer component that is subjected to polymerization in polymerizing a compound having at least one copolymerizable ethylenically unsaturated group. At least one or all of these compounds can be obtained by using a compound having one ethylenic double bond and at least one epoxy group in the molecule, and conducting the polymerization by the living radical polymerization method as described above.

  Examples of the compound having one ethylenic double bond and at least one epoxy group in the molecule include glycidyl (meth) acrylate, (3,4-epoxydicyclohexyl) methyl (meth) acrylate, β-methylglycidyl ( Examples thereof include (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, allyl glycidyl ether, epoxidized stearyl acrylate (manufactured by Shin Nippon Rika Co., Ltd .; product number “Rikaresin ESA”) and the like. These compounds can be used alone or in combination of a plurality of types, but it is particularly preferable to use glycidyl (meth) acrylate.

  Among the components (e) (saturated or unsaturated monocarboxylic acid), examples of the saturated monocarboxylic acid include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, isovaleric acid, and pivalin. Acid, palmitic acid, stearic acid, benzoic acid, glycolic acid, lactic acid, glyceric acid, dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolcaproic acid, and the like can be used.

  Moreover, when using unsaturated monocarboxylic acid as (e) component, photosensitivity can be provided to (A3) component produced | generated. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, acrylic acid dimer, cinnamic acid, etc .; succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydroanhydride Dibasic acid anhydrides such as phthalic acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipe Half esters obtained by reacting a compound having an ethylenically unsaturated group containing one hydroxyl group in one molecule such as taerythritol penta (meth) acrylate and tripentaerythritol hepta (meth) acrylate; succinic acid, Dibasic acids such as maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, itaconic acid and glycidyl (meta ) Acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate monoglycidyl ether, etc., containing one epoxy group in one molecule D Half esters obtained by reacting a compound having an alkylene unsaturated group.

  Although this (e) component can be used individually or in combination of multiple types, it is especially preferable to use (meth) acrylic acid.

  In addition, the component (f) (polybasic acid anhydride) introduces a carboxyl group by reacting with a hydroxyl group produced by the reaction between a polymer having an epoxy group in the side chain and the component (e), and a polymer. Alkali solubility can be imparted to. Examples of the component (f) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride. And dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride and itaconic anhydride, and trimellitic anhydride. A compound having one or more acid anhydride groups can also be used in a small amount within the range where gelation does not occur. For example, pyromellitic anhydride, biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, diphenylsulfonetetra Carboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenylmethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 5- (2,5-dioxo And tetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (“B-4400” manufactured by Dainippon Ink & Chemicals, Inc.).

  In the production of the component (A3), when the component (e) is reacted with the polymer having an epoxy group in the side chain, the component (e) is added in an amount of 0.7 to 1 epoxy equivalent of the polymer. It is preferable to use in the range of 1.2 chemical equivalents.

  Moreover, it is preferable to use a catalyst in order to promote this reaction. Examples of the catalyst include tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine. The amount of this catalyst used is the total amount of the reaction raw material mixture (finally the total amount of raw materials contained in the reaction system), that is, the monomers used for the production of the component (A3), the solvent, the catalyst used in the living radical polymerization method, and Preferably 0.1 to 10 weights with respect to the total amount of initiator, component (e), component (f), catalyst used for reaction of component (e), polymerization inhibitor used for reaction of component (e), etc. % Range.

  In addition, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization of a polymer having an epoxy group in the side chain during this reaction. Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether. The amount used is preferably 0.01 to 1% by weight based on the total amount of the reaction raw material mixture.

  The reaction conditions of the polymer having an epoxy group in the side chain and the component (e) are preferably reacted at a reaction temperature of 60 to 150 ° C., particularly preferably 80 to 120 ° C. according to a conventional method. The reaction time is preferably 5 to 60 hours.

  Next, in reacting the component (f), depending on the desired acid value to be imparted to the component (A3), the (f) component (f) is equivalent to 1 hydroxyl group equivalent of the intermediate product obtained by the reaction with the component (e). ) Component is preferably used in the range of 0.1 to 1.5 chemical equivalents.

  In order to promote this reaction, the same catalyst as in the reaction with the component (e) is used, and the reaction with the component (e) is performed for the purpose of preventing the polymerization of the intermediate product. It is preferable to use the polymerization inhibitor. As this catalyst and polymerization inhibitor, those added in the reaction with the component (e) can be used as they are.

  The reaction conditions of this intermediate product and (f) component are made to react at a reaction temperature of preferably 20 to 150 ° C., particularly preferably 50 to 100 ° C. by a conventional method. The reaction time is preferably 1 to 30 hours.

  The (A1) component and the (A2) component (A3) component as described above can be used to prepare the composition as an etching resist ink or a solder resist ink, but in particular, the (A1) component and the (A2) ) Component can obtain a polymer containing a carboxyl group and an ethylenic double bond by a one-step or two-step synthesis, thereby preparing a composition having sufficient coating performance as an etching resist ink. Therefore, it can be suitably used for preparing the composition as an etching resist ink. The component (A3) requires a three-step synthesis, but can introduce more carboxyl groups and ethylenically unsaturated double bonds, improving the performance as a permanent coating with a high level of coating performance requirements. In particular, it can be suitably used when the composition is prepared as a solder resist ink.

  Since the component (A) as described above is obtained by a living radical polymerization method, it can be produced so that the dispersity (Mw / Mn) is 1.8 or less. Here, when the degree of dispersion is greater than 1.8, a component having a higher molecular weight than a desired molecular weight and a component having a lower molecular weight enter the system. Although the photocurability of the dried coating film is improved by the molecular weight component, the finger tack is deteriorated. That is, it becomes difficult to achieve both finger touch, photo-curing property, and developability.

  Here, the theoretical lower limit of the dispersity is 1, but it is difficult to set the dispersity to 1, and the actual lower limit of the dispersity is 1.05.

  Here, the degree of dispersion can be adjusted by changing the living radical polymerization conditions during the synthesis of the component (A). By appropriately changing the living radical polymerization conditions (A) The degree of dispersion of the components can be made as desired. In other words, the parameters that determine the molecular weight distribution of the living radical polymerization system include the activation rate constant and growth radical concentration in the reversible activation of the dormant species, and the living radical polymerization system with a large activation rate constant of the dormant species should be selected. Thus, the molecular weight distribution of the obtained polymer can be narrowed and the degree of dispersion can be reduced.

  In addition, since the occurrence frequency of the bimolecular termination reaction can be suppressed by lowering the growth radical concentration, the molecular weight distribution can be narrowed and the degree of dispersion can be reduced. For example, the amount of polymerization initiator that is a radical source is reduced. In addition, in the case of the atom transfer radical polymerization method, adding a transition metal complex in a highly oxidized state corresponding to a transition metal complex as an initiator in advance to the system is also effective for lowering the growth radical concentration. In the case of using a complex of a monovalent copper compound such as cuprous bromide and a nitrogen-based multidentate ligand, a similar complex of a divalent copper compound such as cupric bromide is added. is there.

  The number average molecular weight of the component (A) is preferably in the range of 1000 to 200000, more preferably 2000 to 100000. Within such a range, developability and finger tackiness are ensured.

  Furthermore, in order to impart sufficient alkali solubility to the component (A), the acid value is preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 170 mgKOH / g.

  This component (A) is contained in an appropriate ratio in the composition, but the total amount of the composition (when the diluent (H) is contained in the composition, the diluent (H) is excluded). The total amount of the composition) is contained in the range of 10 to 90% by weight, whereby good photosensitivity and workability of the composition, and good physical properties of the finally formed cured film. Is ensured.

(B) Photopolymerizable monomer As this (B) component, photopolymerizable monomers, such as a (meth) acrylate monomer, can be used, for example, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, (meth) acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethyl ( (Meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, melamine ( Meta) Acryle , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, cyclopentanyl mono (meth) acrylate Cyclopentenyl mono (meth) acrylate, cyclopentanyl di (meth) acrylate, cyclopentenyl di (meth) acrylate; mono-, di-, tri- or higher polyesters of polybasic acids and hydroxyalkyl (meth) acrylates Etc .: Examples thereof include polyester (meth) acrylate and urethane (meth) acrylate.

  Such a component (B) may have a function of adjusting the acid value of the composition to adjust the alkali solubility of the whole composition by diluting the composition to make it easy to apply.

  The component (B) is an essential component for imparting photosensitivity to the composition when the component (A) has no photosensitivity, and the component (A) Even if it has photosensitivity, further photosensitivity can be imparted to the composition by further containing the component (B).

  When (B) component is mix | blended in the said composition, it is 50 with respect to the composition whole quantity (when using an organic solvent as (H) component (diluent) mentioned later, this organic solvent remove | excludes this organic solvent)). It is preferable to make it contain in the range of the mass% or less. When the content exceeds 50% by mass, the surface adhesiveness of the dry coating film of the composition becomes too strong, and the negative mask is exposed when the negative mask on which the pattern is drawn is directly applied to the surface of the dry coating film. May cause problems such as fouling. Further, the lower limit of the content when the component (B) is contained is not particularly limited, but the lower limit is preferably 1% by weight in order to impart photosensitivity for obtaining good film properties.

(C) Photopolymerization initiator The component (C) is not particularly limited, and those for desired energy ray exposure such as ultraviolet rays, visible rays, infrared rays, near infrared rays, and electron beams are used. Specifically, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2- Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone; anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 -Thioxanthones such as chlorothioxanthone, 2,4-diisopropylthioxanthone, 1-chloro-4-propoxythioxanthone; acetophenone dimethyl ketal, benzyldi Ketals such as tilketal; benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxylcarbonyl) benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones or xanthones such as 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Those containing a nitrogen atom such as butanone-1,4,4'-bis-diethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

  These components (C) can be contained alone or in combination in the composition.

  Further, in addition to these (C) components, benzoic acid-based or tertiary amine-based compounds such as p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate, etc. These photopolymerization accelerators and sensitizers may be used in combination. Further, as a sensitizer for laser exposure method, coumarin derivatives such as 7-diethylamino-4-methylcoumarin, 4,6-diethyl-7-ethylaminocoumarin, other carbocyanine dyes, xanthene dyes, etc. are appropriately selected. You may mix.

  The blending amount of the component (C) in the composition is appropriately set, but in order to obtain a good balance between the photosensitivity of the composition and the physical properties of the resulting cured film, the total amount of the composition (When using an organic solvent as the component (H) (diluent) described later, the total amount excluding the organic solvent) is preferably in the range of 0.1 to 30% by mass.

(G) Polyfunctional epoxy compound The component (G) can be provided with thermosetting properties and a wide development width by being blended in the composition. The development width means a range of predrying conditions that can maintain developability, and is also referred to as a predrying management width or a predrying allowable range.

  As this (G) component, a solvent hardly soluble epoxy compound, a general purpose solvent soluble epoxy compound, etc. can be used, for example. Specifically, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolac type epoxy resin, bisphenol F type epoxy resin, triglycidyl isocyanurate, biphenyl type epoxy resin (for example, Product number “YX4000” manufactured by Japan Epoxy Resin Co., Ltd.), sorbitol polyglycidyl ether, N-glycidyl type epoxy resin, alicyclic epoxy resin (for example, product number “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.), polyol Polyglycidyl ether compound, glycidyl ester compound, N-glycidyl type epoxy resin, tris (hydroxydiphenyl) methane based polyfunctional epoxy resin (for example, product number “EPPN-50 manufactured by Nippon Kayaku Co., Ltd.) H ”, product numbers“ TACTIX-742 ”and“ XD-9053 ”manufactured by Dow Chemical Co., Ltd.), hydrogenated bisphenol A type epoxy resin, dicyclopentadiene-phenol type epoxy resin, naphthalene type epoxy resin, vinyl polymerization having an epoxy group Examples thereof include polymers and polyisocyanate-modified products of polyfunctional glycidyl compounds. These can be used individually by 1 type or in combination of multiple types.

  Among these, triglycidyl isocyanurate, biphenyl type epoxy resin (for example, product number “YX4000” manufactured by Japan Epoxy Resin Co., Ltd.), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol It is desirable to use A-novolak type epoxy resin or the like.

  When such (G) component is mix | blended in a composition, the compounding quantity is this amount when using an organic solvent as the whole quantity ((H) component (diluent) mentioned later) of ultraviolet curable resin composition. The total amount excluding the organic solvent) is preferably in the range of 0.1 to 50% by mass, and particularly in the range of 0.1 to 30% by mass, excellent thermosetting and wide development width are imparted. The

(H) Diluent As this (H) component, an organic solvent can be used, for example, water, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol, ethylene glycol, etc. Chain, branched, secondary or polyhydric alcohols; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; swazil series (manufactured by Maruzen Petrochemical Co., Ltd.), solvesso series (exxon chemical) Petroleum aromatic mixed solvent such as Cellosolve, cellosolves such as butylcellosolve; carbitols such as carbitol and butylcarbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; Examples include polypropylene glycol alkyl ethers such as coal methyl ether; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; dialkyl glycol ethers.

  Such (H) component can use only 1 type, or can use it in combination of 2 or more types as appropriate.

  This component (H) dissolves and dilutes the resin component of the composition so that the composition can be applied as a liquid, and after application of the composition, it volatilizes by drying to form a dry coating film. Make a film. The organic solvent blended as the component (H) is preferably contained in the composition, particularly when the composition is prepared as a resist ink that can be developed with a dilute alkaline solution. In addition, it is preferable to select and mix appropriately so as not to remain in the dry coating film.

  When the component (H) is contained in the composition, the blending amount is desirably 5% by weight or more based on the total amount of the composition. When the amount is less than this, application of the composition tends to be difficult. In addition, since this suitable compounding quantity changes with coating methods, it is preferable to adjust suitably according to the coating method selected.

(I) Other components In the composition, particularly when prepared as a photo solder resist ink, in addition to the above components, for example, tolylene diisocyanate, morpholine diisocyanate blocked with caprolactam, oxime, malonic acid ester, etc. , Isophorone diisocyanate, hexamethylene diisocyanate type blocked isocyanate, and amino resins such as n-butylated melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea cocondensation resin, benzoguatemine type cocondensation resin, etc. Thermosetting component and UV curable epoxy acrylate or UV curable epoxy methacrylate, such as bisphenol A type, phenol novolac type, cresol novolac type, alicyclic type epoxy resin, acrylic acid or meta High additions such as those with added crylic acid, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid resin, diallyl phthalate resin, phenoxy resin, melamine resin, urethane resin, fluorine resin, etc. Molecular compounds can be added.

  In addition, this composition may further contain an epoxy resin curing agent such as imidazole derivatives, polyamines, guanamines, tertiary amines, quaternary ammonium salts, polyphenols, polybasic acid anhydrides, melamine, dicyandiamide and the like as necessary. And curing accelerators; fillers and colorants such as barium sulfate, silicon oxide, talc, clay, calcium carbonate; leveling agents such as silicon, acrylate copolymers and fluorosurfactants; adhesion of silane coupling agents, etc. Property imparting agent; thixotropic agent such as aerosil; polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine; various additives such as antihalation agent, flame retardant, antifoaming agent, antioxidant; Surfactant and polymer dispersion to improve dispersion stability Or the like may be added.

[Preparation Method of Alkali Development Type Photosensitive Resist Ink Composition for Printed Wiring Board Production]
The composition of the present invention can be prepared by mixing each of the above components by an appropriate technique. For example, each compounding component and additive can be prepared by a known kneading method using a three-roll, ball mill, sand mill or the like.

[Preparation of cured product of alkali development type photosensitive resist ink composition for printed wiring board production and printed wiring board]
The composition of the present invention can be used for various applications such as photoresist inks, interlayer insulating materials for printed wiring boards, resists for color filters, etc., especially for printed wiring boards and laminated boards for producing printed wiring boards. It is preferably used for forming a resist pattern such as a solder resist or an etching resist by forming a layer on the substrate.

  An appropriate substrate can be used as the substrate. For example, a glass epoxy resin substrate, a flexible substrate made of a polyimide substrate or the like, or a printed wiring board formed from these substrates can be used.

  A method for forming a resist pattern on a substrate using the composition according to the present invention is not particularly limited, and the most general method is exemplified as follows.

  For example, the composition prepared as an alkali developing resist ink is applied to the substrate by dipping, spraying, spin coater, roll coater, curtain coater, screen printing or the like, and then (H) component (diluent). In order to volatilize the organic solvent, for example, preliminary drying is performed at 60 to 120 ° C. to form a preliminary drying film.

  Next, apply a negative mask with a pattern drawn directly or indirectly to the surface of the pre-dried film, using a chemical lamp, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, etc. After irradiation with ultraviolet rays, a pattern is formed by development. And when (G) component (polyfunctional epoxy compound) is mix | blended, the film strength, hardness, and chemical resistance of a resist are further hardened by heating for about 30 to 90 minutes at 120-180 degreeC, for example. It is possible to improve various properties such as property.

  Examples of the alkaline solution used in the development step include a sodium carbonate aqueous solution and a potassium carbonate aqueous solution. As the solvent of the alkaline solution, water or a mixture of water and an alcohol-based hydrophilic organic solvent can be used.

  The present invention will be described below based on examples, but the present invention is not limited thereto. The “parts” and “%” used below are all based on weight unless otherwise indicated.

  The “number average molecular weight”, “weight average molecular weight”, and “dispersion degree” are measured by GPC based on the following measurement conditions.

A THF solution was prepared so that the sample obtained in each of the following synthesis examples had a solid content of 10 mg / mL, and each sample was measured at an injection amount of 100 μL.
Measurement conditions GPC measuring device: SHODEX SYSTEM 11 manufactured by Showa Denko KK
Column: 4 series of SHODEX KF-800P, KF-805, KF-803 and KF-801 Moving layer: THF
Flow rate: 1 mL / min Column temperature: 45 ° C
Detector: RI
Conversion: Polystyrene Polymers corresponding to the component (A) were synthesized as in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 4 below. Synthetic Examples 1 and 2 and Comparative Synthetic Examples 1 and 2 are polymers synthesized aiming at structures suitable for etching resist applications, and Synthetic Examples 3 and 4 and Comparative Synthetic Examples 3 and 4 are suitable for solder resist applications. It is a polymer synthesized with the aim of the structure.

[Synthesis of alkali-soluble polymer]
[Synthesis Example 1]
In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer, 25 parts of methacrylic acid, 75 parts of methyl methacrylate, 100 parts of carbitol acetate, 0.28 parts of cumyl dithiobenzoate, azo Add 0.68 part of bisisobutyronitrile, heat in a nitrogen stream, perform living radical polymerization by reversible addition-fragmentation chain transfer polymerization method at 70 ° C. for 4 hours, 50% by weight solution of alkali-soluble polymer (Alkali-soluble polymer (A-1) solution) was obtained.

  And the solvent of the said solution was removed and the alkali-soluble polymer (A-1) was obtained. This alkali-soluble polymer (A-1) had a number average molecular weight Mn of 31,500, a weight average molecular weight Mw of 45500, and a dispersity Mw / Mn of 1.44. The acid value was 163 mgKOH / g.

[Synthesis Example 2]
In a four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 parts of the alkali-soluble polymer (A-1) obtained in Synthesis Example 1 above, 14.2 parts glycidyl methacrylate, 114 carbitol acetate 114 .2 parts, 0.05 part of hydroquinone and 0.2 part of dimethylbenzylamine were added, and an addition reaction was performed at 100 ° C. for 5 hours to obtain a 50% solution of an alkali-soluble polymer (alkali-soluble polymer (A-2) solution). Got.

  And the solvent of the said solution was removed and the alkali-soluble polymer (A-2) was obtained. This alkali-soluble polymer (A-2) had a number average molecular weight Mn of 33,000, a weight average molecular weight Mw of 49500, and a dispersity Mw / Mn of 1.50. The acid value was 93 mgKOH / g.

[Synthesis Example 3]
In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer, 70 parts of glycidyl methacrylate, 30 parts of methyl methacrylate, 100 parts of carbitol acetate, 2.34 parts of ethyl 2-bromoisobutyrate, (-)-Spartein 2.84 g was added, and the inside of the reactor was purged with nitrogen. Subsequently, 0.17 parts of cuprous bromide was added and heated under a nitrogen stream, and after performing living radical polymerization by an atom transfer radical polymerization method at 70 ° C. for 4 hours, the nitrogen stream was stopped, and hydroquinone 0.05 Part, 37 parts of acrylic acid and 0.2 part of dimethylbenzylamine were added, followed by addition reaction at 100 ° C. for 24 hours. Subsequently, 38 parts of tetrahydrophthalic anhydride and 80.2 parts of carbitol acetate were added, It was made to react for time, and the 50 weight% solution (alkali-soluble polymer (A-3) solution) of the alkali-soluble polymer was obtained.

  And the solvent of the said solution was removed and the alkali-soluble polymer (A-3) was obtained. This alkali-soluble polymer (A-3) had a number average molecular weight Mn of 6520, a weight average molecular weight Mw of 8800, and a dispersity Mw / Mn of 1.35. The acid value was 77.8 mgKOH / g.

[Synthesis Example 4]
A four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer was mixed with 70 parts of glycidyl methacrylate, 30 parts of styrene, 100 parts of carbitol acetate, 5.3 parts of cumyl dithiobenzoate, azobis After adding 0.64 parts of isobutyronitrile and heating in a nitrogen stream, and performing living radical polymerization by reversible addition-fragmentation chain transfer polymerization at 70 ° C. for 4 hours, the nitrogen stream was stopped and hydroquinone 05 parts, 37 parts of acrylic acid and 0.2 parts of dimethylbenzylamine were added, followed by addition reaction at 100 ° C. for 24 hours, followed by addition of 38 parts of tetrahydrophthalic anhydride and 81.2 parts of carbitol acetate at 100 ° C. It was made to react for 3 hours, and the 50 weight% solution (alkali-soluble polymer (A-4) solution of the alkali-soluble polymer was obtained.

  And the solvent of the said solution was removed and the alkali-soluble polymer (A-4) was obtained. The number average molecular weight Mn of this alkali-soluble polymer (A-4) was 6830, the weight average molecular weight Mw was 8600, and the dispersity Mw / Mn was 1.26. The acid value was 77.4 mgKOH / g.

[Comparative Synthesis Example 1]
To a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen replacement and a stirrer, add 25 parts of methacrylic acid, 75 parts of methyl methacrylate, 100 parts of carbitol acetate, and 1 part of azobisisobutyronitrile. The mixture was heated under a nitrogen stream and polymerized at 70 ° C. for 4 hours to obtain a 50% solution of an alkali-soluble polymer (alkali-soluble polymer (A′-1) solution).

  And the solvent of the said solution was removed and the alkali-soluble polymer (A'-1) was obtained. The number average molecular weight Mn of this alkali-soluble polymer (A′-1) was 32000, the weight average molecular weight Mw was 81300, and the degree of dispersion Mw / Mn was 2.54. The acid value was 163 mgKOH / g.

[Comparative Synthesis Example 2]
In a four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 100 parts of an alkali-soluble polymer (A′-1), 14.2 parts of glycidyl methacrylate, 114.2 parts of carbitol acetate, 05 parts and 0.2 part of dimethylbenzylamine were added, and an addition reaction was performed at 100 ° C. for 5 hours to obtain a 50% solution of an alkali-soluble polymer (an alkali-soluble polymer (A′-2) solution).

  And the solvent of the said solution was removed and the alkali-soluble polymer (A'-2) was obtained. The number average molecular weight Mn of this alkali-soluble polymer (A-2) was 33800, the weight average molecular weight Mw was 86200, and the dispersity Mw / Mn was 2.55. The acid value was 93 mgKOH / g.

[Comparative Synthesis Example 3]
Add 70 parts of glycidyl methacrylate, 30 parts of methyl methacrylate, 100 parts of carbitol acetate, and 2 parts of azobisisobutyronitrile to a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer. The mixture was heated under a nitrogen stream, and thereafter 2 parts of azobisisobutyronitrile was added 4 times every hour for 4 hours at 70 ° C., then the nitrogen stream was stopped and 0.05 parts of hydroquinone, acrylic acid 37 And 0.2 part of dimethylbenzylamine are added, and an addition reaction is carried out at 100 ° C. for 24 hours. Subsequently, 38 parts of tetrahydrophthalic anhydride and 83.4 parts of carbitol acetate are added and reacted at 100 ° C. for 3 hours. A 50% by weight solution of a soluble polymer (an alkali-soluble polymer (A′-3) solution was obtained.

  And the solvent of the said solution was removed and the alkali-soluble polymer (A'-3) was obtained. The number average molecular weight Mn of this alkali-soluble polymer (A′-3) was 6730, the weight average molecular weight Mw was 14300, and the degree of dispersion Mw / Mn was 2.13. The acid value was 76.5 mgKOH / g.

[Comparative Synthesis Example 4]
To a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer, 70 parts of glycidyl methacrylate, 30 parts of styrene, 100 parts of carbitol acetate, and 2 parts of azobisisobutyronitrile are added, After heating in a nitrogen stream and adding 2 parts of azobisisobutyronitrile 4 hours every hour for 4 hours at 70 ° C., the nitrogen stream was stopped and 0.05 parts of hydroquinone and 37 parts of acrylic acid Then, 0.2 part of dimethylbenzylamine was added, and the addition reaction was carried out at 100 ° C. for 24 hours. Subsequently, 38 parts of tetrahydrophthalic anhydride and 83.6 parts of carbitol acetate were added, and the mixture was reacted at 100 ° C. for 3 hours. A 50% by weight solution of the polymer (an alkali-soluble polymer (A′-4) solution was obtained).

  And the solvent of the said solution was removed and the alkali-soluble polymer (A'-4) was obtained. The number average molecular weight Mn of this alkali-soluble polymer (A′-4) was 7020, the weight average molecular weight Mw was 15800, and the degree of dispersion Mw / Mn was 2.25. The acid value was 76.4 mgKOH / g.

[Preparation of liquid etching resist ink]
Each component shown in Table 1 was added to the alkali-soluble resin (A-1) solution, (A-2) solution, (A′-1) solution, and (A′-2) solution produced in the above synthesis example. The resist ink compositions (liquid etching resist ink) for printed wiring boards of Examples 1 and 2 and Comparative Examples 1 and 2 were obtained by kneading with three rolls.

  In Table 1, “Irgacure 907” (trade name) is a photopolymerization initiator manufactured by Ciba Specialty Chemicals, and “Kayacure DETX-S” (trade name) is a photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd. “Modaflow” (trade name) is a leveling agent manufactured by Monsanto. “Aronix M-309” (trade name) is trimethylolpropane triacrylate manufactured by Toagosei Co., Ltd., and Victoria View Blue BOH is a dye manufactured by Hodogaya Kogyo Co., Ltd.

[Preparation of liquid solder resist ink]
Each component shown in Table 2 was added to the alkali-soluble resin (A-3) solution, the (A-4) solution, the (A′-3) solution, and the (A′-4) solution generated in the above synthesis example, By kneading with three rolls, resist ink compositions (liquid solder resist ink) for printed wiring boards of Examples 3 and 4 and Comparative Examples 3 and 4 were obtained.

  In Table 1, “Epiclon N-695” (trade name) is a cresol novolac epoxy resin manufactured by Dainippon Ink and Chemicals, and “Irgacure 907” (trade name) is a photopolymerization manufactured by Ciba Specialty Chemicals. “Kayacure DETX-S” (trade name) is a photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd., and “Modaflow” (trade name) is a leveling agent manufactured by Monsanto. “DPHA” is dipentaerythritol hexaacrylate.

[Performance evaluation of liquid etching resist ink]
[Production of test piece for evaluation]
In order to confirm the performance of the printed wiring boards manufactured with the liquid etching resist inks of Examples 1 and 2 and Comparative Examples 1 and 2, test pieces were prepared by sequentially performing the following steps.

<Application process>
Each liquid etching resist ink was applied by screen printing to a copper-clad laminate made of a glass epoxy base material of a copper foil having a thickness of 35 μm to form a resist ink layer on the substrate surface.

<Preliminary drying process>
After the coating step, preliminary drying was performed at 80 ° C. for 30 minutes in order to volatilize the solvent in the resist ink layer on the substrate surface, and a dry coating film having a thickness of 12 μm was obtained.

<Exposure process>
Then, with a reduced-pressure contact type double-side exposure machine (“ORC HMW-201GX” manufactured by Oak Manufacturing Co., Ltd.), a mask on which an evaluation pattern was drawn was directly applied to the dried coating film, and the contact was applied under reduced pressure, and ultraviolet rays of 100 mJ / cm ² Irradiated to selectively expose the dried coating on the substrate surface.

<Development process>
In the dried coating film after the exposure step, the selectively unexposed portion is removed by developing for 60 seconds using a 1% sodium carbonate aqueous solution at 30 ° C. as a developer, and the substrate is exposed and cured on the substrate. A coating pattern was formed.

[Performance evaluation of printed wiring boards]
The following evaluation was performed about the test piece obtained at the said process.

<Tackiness>
The films preliminarily dried under the above conditions are stacked so that the dried film surfaces are in contact with each other, applied with a weight of 1 kg / cm ² , left for 1 week in an environment of 25 ° C. and 55% RH, and then the contact surfaces are released to peel off the film. And abnormal surface conditions were observed with a 100 × microscope.
X: A state in which a contact mark is attached to the coating surface.
○: No contact mark on the coating surface.

<Developability>
The developed state of the unexposed part was visually evaluated after development. The evaluation method of developability is as follows.
X: The state in which the color of the resist can be confirmed in the unexposed area.
Δ: Resist color cannot be confirmed, but resist residue can be confirmed.
○: There is no resist residue.

<Remaining step level>
The number of remaining step steps after development with an exposure test mask (manufactured by Hitachi Chemical Co., Ltd., “Step Tablet PHOTEC 21 steps”) was determined, and thereby the exposure sensitivity was evaluated.

<Resolution>
The line width of a pattern formed by a mask pattern composed of parallel lines each having a line width of 100 μm between the lines was measured with a microscope, and the thickness from the original line width was evaluated. The closer to the original line width, the better the resolution.

  The above results are shown in Table 3.

[Performance evaluation of liquid solder resist ink]
[Production of test piece for evaluation]
In order to confirm the performance of the printed wiring board manufactured with the liquid photo solder resist inks of Examples 3 and 4 and Comparative Examples 3 and 4, test pieces were prepared by sequentially performing the following steps.

<Application process>
Each liquid photo solder resist ink is applied by screen printing to the entire surface of a copper-clad laminate made of a 35 μm thick copper foil glass epoxy base material and a printed wiring board that has been previously etched to form a pattern, A resist ink layer was formed on the substrate surface.

<Preliminary drying process>
After the coating step, preliminary drying was performed at 80 ° C. for 20 minutes in order to volatilize the solvent in the resist ink layer on the substrate surface, and a dried coating film having a thickness of 20 μm was obtained.

<Exposure process>
Then, with a reduced-pressure contact type double-sided exposure machine (“ORC HMW680GW” manufactured by Oak Manufacturing Co., Ltd.), a mask on which an evaluation pattern was drawn was directly applied to the dried coating film and brought into close contact under reduced pressure, and irradiated with 150 mJ / cm ² ultraviolet rays. Selective exposure of the dried coating on the substrate surface was performed.

<Development process>
In the dried coating film after the exposure step, the selectively unexposed portion is removed by developing for 60 seconds using a 1% sodium carbonate aqueous solution at 30 ° C. as a developer, and the substrate is exposed and cured on the substrate. A coating pattern was formed.

<Post-bake process>
The substrate on which the pattern of the exposure-cured dry coating film formed in the development process was formed was heated at 150 ° C. for 30 minutes to cure the dry coating film, thereby obtaining a test piece.

[Performance evaluation of printed wiring boards]
The following evaluation was performed about the test piece obtained at the said process.

<Tackiness>
The films preliminarily dried under the above conditions are stacked so that the dried film surfaces are in contact with each other, applied with a weight of 1 kg / cm ² , left for 1 week in an environment of 25 ° C. and 55% RH, and then the contact surfaces are released to peel off the film. And abnormal surface conditions were observed with a 100 × microscope.
X: A state in which a contact mark is attached to the coating surface.
○: No contact mark on the coating surface.

<Developability>
The developed state of the unexposed part was visually evaluated after development. The evaluation method of developability is as follows.
X: The state in which the color of the resist can be confirmed in the unexposed area.
Δ: Resist color cannot be confirmed, but resist residue can be confirmed.
○: There is no resist residue.

<Remaining step stage>
The number of remaining step steps after development with an exposure test mask (manufactured by Hitachi Chemical Co., Ltd., “Step Tablet PHOTEC 21 steps”) was determined, and thereby the exposure sensitivity was evaluated.

<Resolution>
The line width of a pattern formed by a mask pattern composed of parallel lines each having a line width of 100 μm between the lines was measured with a microscope, and the thickness from the original line width was evaluated. The closer to the original line width, the better the resolution.

<Solder heat resistance>
LONCO 3355-11 (water-soluble flux manufactured by London Chemical Co., Ltd.) was used as the flux. First, the flux was applied to the test piece, and then immersed in a molten solder bath at 260 ° C. for 15 seconds, and then washed with water. The degree of surface whitening after performing this cycle once or five times was observed. Moreover, the cellophane adhesive tape peeling test by the cross cut was done based on JISD0202, and the change of the adhesion state was observed.

The evaluation method of surface whitening is as follows.
X: Remarkably whitened.
Δ: Slight whitening was observed.
○: No abnormality occurred.

Moreover, the evaluation method of adhesiveness is as follows.
X: Resist swelling or peeling occurred without performing a cross-cut test.
(Triangle | delta): Partial peeling occurred in the crosscut part at the time of tape peeling.
○: No peeling of the crosscut portion occurred.

<Pencil hardness>
The pencil hardness was measured and evaluated according to JIS K 5600.

  The results are shown in Table 4.

  As is clear from Table 3, in Examples 1 and 2, all evaluation items of tack property, developability, remaining step level, and resolution were all good.

Further, as is apparent from Table 4, in Examples 3 and 4 , in addition to tackiness, developability, remaining step level, and resolution, solder heat resistance, adhesion, pencil, which are characteristics required for solder resist Each evaluation item of hardness was satisfactory.

Claims (16)

The following (A) component thru | or (C) component are contained, and the following (A) component is a part of the carboxyl group in the polymer (A1) which has a carboxyl group in a side chain, and at least 1 ethylenic 2 in a molecule | numerator. double bond and the compound (d) is reacted, characterized in der Rukoto those obtained printed wiring board manufacturing for alkali development type photosensitive resist ink composition having a reactive group capable of reacting with at least one carboxyl group .
(A) Alkali-soluble polymer (B) photopolymerizable monomer (C) photopolymerization initiator having a dispersity of 1.8 or less obtained by living radical polymerization by reversible addition-fragmentation chain transfer polymerization The following (A) component thru | or (C) component are contained, and the following (A) component is a saturated or unsaturated monocarboxylic acid (e in a part or all of the epoxy group in the polymer which has an epoxy group in a side chain. ) were reacted to further the reaction polybasic acid anhydride (f) the printed wiring board manufacturing for alkali development type photosensitive resist, characterized in der Rukoto those obtained by reacting a part of the generated hydroxyl group by Ink composition.
(A) Alkali-soluble polymer (B) photopolymerizable monomer (C) photopolymerization initiator having a dispersity of 1.8 or less obtained by living radical polymerization by reversible addition-fragmentation chain transfer polymerization An alkali development type photosensitive resist ink composition for producing a printed wiring board, comprising the following components (A) to (C) and the following component (G):
(A) Alkali-soluble polymer (B) photopolymerizable monomer (C) photopolymerization initiator having a dispersity of 1.8 or less obtained by living radical polymerization by reversible addition-fragmentation chain transfer polymerization
(G) Polyfunctional epoxy compound The following (A) component and (C) component are contained, and the following (A) component has a carboxyl group in the side chain, a part of the carboxyl group in the polymer (A1), and at least one ethylenic diene in the molecule. It is obtained by reacting a compound (d) having a heavy bond and a reactive group capable of reacting with at least one carboxyl group, and undergoes a polymerization reaction upon irradiation with energy rays in the presence of a photopolymerization initiator. An alkali development type photosensitive resist ink composition for producing a printed wiring board.
(A) Alkali-soluble polymer having a dispersity of 1.8 or less obtained by a living radical polymerization method (C) Photopolymerization initiator A saturated or unsaturated monocarboxylic acid (e ) is contained in part or all of the epoxy group in the polymer containing the following component (A) and component (C) and the component (A) having an epoxy group in the side chain: ), And a polybasic acid anhydride (f) is further reacted with a part of the hydroxyl group produced by the above reaction, and a polymerization reaction is caused by irradiation with energy rays in the presence of a photopolymerization initiator. An alkali development type photosensitive resist ink composition for producing a printed wiring board.
(A) Alkali-soluble polymer having a dispersity of 1.8 or less obtained by a living radical polymerization method (C) Photopolymerization initiator The alkali-developable photosensitive resist ink composition for producing a printed wiring board according to claim 4, comprising the following component (B):
(B) Photopolymerizable monomer The following (A) component and (C) component and the following (G) component are contained, and the following (A) component is subjected to irradiation with an energy ray in the presence of a photopolymerization initiator to cause a polymerization reaction. An alkali development type photosensitive resist ink composition for producing a printed wiring board.
(A) Alkali-soluble polymer having a dispersity of 1.8 or less obtained by a living radical polymerization method (C) Photopolymerization initiator
(G) Polyfunctional epoxy compound The alkali developing type photosensitive resist ink composition for producing a printed wiring board according to claim 7 , which comprises the following component (B):
(B) Photopolymerizable monomer A reactive group capable of reacting at least one ethylenic double bond and at least one carboxyl group in the molecule with a part of the carboxyl group in the polymer (A1) in which the component (A) has a carboxyl group in the side chain. The alkali-developable photosensitive resist ink composition for producing a printed wiring board according to any one of claims 3, 7, and 8, which is obtained by reacting a compound (d) having: One or more of the epoxy groups in the polymer having an epoxy group in the side chain as the component (A) are reacted with a saturated or unsaturated monocarboxylic acid (e), and one hydroxyl group produced by the reaction is added. 9. The alkali-developable photosensitive resist ink composition for producing a printed wiring board according to claim 3, wherein the composition is obtained by reacting a polybasic acid anhydride (f) with a part. object. The alkali-developable photosensitive resist ink composition for producing a printed wiring board according to any one of claims 1, 2, 4, 5, and 6, comprising the following component (G):
(G) Polyfunctional epoxy compound 9. The alkali development type photosensitive resist ink composition for producing a printed wiring board according to claim 3 , wherein the component (A) has a carboxyl group in the molecule. The alkali-developable photosensitive resist ink composition for producing a printed wiring board according to any one of claims 3, 7 , and 8 , wherein the component (A) has an ethylenic double bond in the molecule. The alkali-developable photosensitive resist ink composition for producing a printed wiring board according to any one of claims 1 to 13 , comprising the following component (H).
(H) Diluent A cured product obtained by curing and molding the alkali development type photosensitive resist ink composition for producing a printed wiring board according to any one of claims 1 to 14 on a substrate. A printed wiring board comprising a layer made of the cured product according to claim 15 .