KR20220016178A - Reuse method of substrate for wiring board - Google Patents

Abstract

[Problem] When a defect is found in a part of the cured film when manufacturing a wiring board having a cured film formed on the substrate, only the cured film on the defective portion can be removed from the substrate, and the composition of the photosensitive resin composition is related There is provided a method capable of removing the cured coating film from the substrate without it.
[Solution Means] A method of reusing the base material by removing a part or all of the cured film from a wiring board having a cured film formed on the surface of the substrate, wherein the cured film is made of a cured product of a photosensitive resin composition, and the cured film is A step of irradiating part or all of the coating film with at least one of an active energy ray capable of generating active oxygen and an active energy ray capable of cleaving a CC carbon bond in an oxygen atmosphere; and cleaning the wiring board with a solvent. Thus, it is characterized by including a step of removing the cured film of the portion irradiated with the active energy ray.

Description

Reuse method of substrate for wiring board

The present invention relates to a method of recycling a substrate for a wiring board, and more particularly, to a method of reusing the substrate by removing a part or all of the cured film from a wiring board having a cured film formed on the surface of the substrate.

For the purpose of protecting a conductor circuit, preventing solder adhesion to places other than those requiring soldering, and the like, manufacturing a circuit board in which a cured film is formed only on a desired portion of the surface of a printed wiring board is performed. As a method for forming a cured film, a photosensitive resin composition is applied on a substrate, dried after exposure and development, and a method of forming a cured film only on a desired portion of the substrate surface, or a photosensitive resin layer called a dry film The method of sticking the provided film to a base material, and forming a cured film only on the desired part of the base material surface by exposure and image development is becoming mainstream.

However, in the process of forming a cured film on a base material, any defect which leads to deterioration of the quality of a product may generate|occur|produce. For example, printing defects when a photosensitive resin composition called solder resist ink is applied to a substrate, positional misalignment during exposure, color unevenness (color inhomogeneity), pinholes in the dry coating, mixing of foreign substances, poor printing of marking ink, etc. defects may occur. The defect in such a cured film formation process WHEREIN: If it is before exposure, it is possible to remove application|coating with a developing solution easily. In addition, even after exposure and development, if it is before curing the coating film by heat treatment, the coating film after development is peeled off using a suitable solvent, and the photosensitive resin composition is applied on the substrate again and dried, followed by exposure and development. Defects can be corrected by this. On the other hand, when the coating film after image development is heat-processed to form a cured film, it is not easy to completely peel a cured film from a base material with a solvent. This is because a crosslinked structure is formed by the crosslinking reaction of the photocurable component contained in the photosensitive resin composition.

When the above-mentioned defect arises during the formation process of a cured film, if a defective product is discarded, a base material will become useless, and productivity (yield) of a product will fall. In recent years, since circuit wiring boards using a base material with high added value are being manufactured, there is a potential hope of reusing the base material when a defect occurs.

Therefore, when a defect arises during the formation process of a cured film, the method of reusing a base material is proposed. For example, in Patent Document 1, when a defect is found in the coating film after development and exposure (before curing the coating film by heat treatment), the substrate on which the coating film is formed is immersed in a stripper made of a specific aqueous alkali solution, and the substrate is removed from the substrate. It is proposed that a base material can be reused by peeling a coating film. However, in this method, when defects are found in the cured coating film that has undergone the curing treatment after exposure and development, the cured coating film cannot be peeled from the substrate. Then, even after hardening the coating film after image development, various examination is made also about the peeling liquid which enables reuse of a base material. For example, in Patent Document 2, by using a stripper composed of a mixture of an alkali metal hydroxide and an aprotic solvent (eg, N-methylpyrrolidone), the cured coating film is described even after the coating film is cured after development. A method for peeling from it has been proposed.

However, in recent years, further improvement of cured film properties such as adhesion between the substrate and the cured film has been demanded, and those containing thermosetting components such as an epoxy resin in the photosensitive resin composition are starting to be used. Therefore, it is becoming increasingly difficult to peel the cured film in which the defect was discovered from a base material. Based on such a situation, for example, patent document 3 proposes that a cured film can be peeled from a base material also with aqueous alkali solution by mix|blending the curable component derived from specific polyester with the photosensitive resin composition.

JP H7-115048 A JP H11-145594 A JP 2015-28646 A

In the method proposed in Patent Document 2 described above, since the cured film is removed by immersing the wiring board on which the cured film is formed in a stripper, the entire cured film is peeled off even if only a part of the cured film is defective. This results in wastage of materials. For example, it can be said that a base material can be reused efficiently if only the location with a defect can remove a cured film.

Moreover, the recycling method of the base material proposed in patent document 3 paid attention to the composition of the photosensitive resin composition, and made it easy to peel a cured film from a base material by mix|blending a specific component. However, it is difficult to change a composition depending on the general photosensitive resin composition (The soldering resist ink containing a thermosetting component, etc.) which is starting to be used in recent years, and the method of patent document 3 may not be applicable.

Accordingly, an object of the present invention is that when a defect is found in a part of the cured film when manufacturing a wiring board having a cured film formed on the substrate, only the defective portion can remove the cured film from the substrate, and at the same time, the photosensitive resin It is to provide a method capable of removing the cured coating film from a substrate regardless of the composition of the composition.

With respect to the above problem, the present inventors have found that even for a cured film formed through curing treatment after exposure and development, by irradiating the cured film with a predetermined active energy ray in the presence of oxygen, the cured film can be easily removed from the substrate with a general-purpose solvent. I got the knowledge that it can be peeled off. The present invention has been completed based on these findings. That is, the summary of this invention is as follows.

[1] A method of reusing the substrate by removing part or all of the cured film from a wiring board having a cured film formed on the surface of the substrate, the method comprising:

The cured film is made of a cured product of the photosensitive resin composition,

A step of irradiating at least one of an active energy ray capable of generating active oxygen and an active energy ray capable of cleaving a C-C carbon bond to a part or all of the cured film in the presence of oxygen;

A step of washing the substrate on which the cured film is formed with a solvent and removing the cured film on the portion irradiated with active energy rays from the substrate

A method of recycling a substrate for a wiring board, comprising:

[2] The cured film is a dry film having a resin layer formed by coating and drying the photosensitive resin composition on the substrate to form a dry film, or by applying and drying the photosensitive resin composition to a support film, the substrate The method according to [1], wherein the dry film is bonded so that the resin layer is in contact with the dry film, and then the dried coating film or the resin layer of the dry film is exposed, developed, and patterned.

[3] The method according to [1] or [2], wherein the active energy ray includes ionizing radiation having a wavelength of 100 to 255 nm.

[4] The method according to any one of [1] to [3], further comprising a step of heating the wiring board from which the cured film has been removed.

[5] The method according to any one of [1] to [4], wherein the solvent is an aprotic polar solvent.

[6] In any one of [1] to [5], wherein the photosensitive resin composition comprises (A) a carboxyl group-containing resin, (B) a photopolymerizable monomer, (C) a photoinitiator, and (D) a thermosetting component described method.

[7] The method according to any one of [1] to [6], wherein at least one of heating and irradiation is performed after exposure and development of the resin layer and before irradiation with active energy rays to the cured film.

[8] The method according to any one of [1] to [7], wherein the cured film has a thickness of 1 to 1000 µm.

According to the present invention, even in a cured film made of a cured product of the photosensitive resin composition, at least one of an active energy ray capable of generating active oxygen and an active energy ray capable of cleaving a CC carbon bond in the presence of oxygen is cured film By irradiating to , the cured film can be removed from the substrate regardless of the composition of the photosensitive resin composition. In addition, since irradiation with active energy rays can be irradiated only to a portion where the cured film has defects, when a defect is found in a part of the cured film when manufacturing a wiring board, only the defective portion can be removed from the substrate .

A method for recycling a substrate for a wiring board according to the present invention is a method of reusing the substrate by removing a part or all of a cured film from a wiring board having a cured film formed on the surface of the substrate to reuse, (1) a part of the cured film or a step of irradiating at least any one of an active energy ray capable of generating active oxygen and an active energy ray capable of cleaving a CC carbon bond in the presence of oxygen;

(2) A step of washing the substrate on which the cured film is formed with a solvent and removing the cured film on the portion irradiated with active energy rays from the substrate

will include

In the present invention, by irradiating a part or all of the cured film made of the cured product of the photosensitive resin composition formed on the substrate with the above-described specific active energy ray, only the portion irradiated with the active energy ray can be easily coated with a solvent with a solvent. and can be easily removed. That is, even when the photosensitive resin composition contains a crosslinking component such as a photopolymerizable monomer or contains a thermosetting component such as an epoxy resin, active oxygen is generated in the cured film obtained by curing the photosensitive resin composition in the presence of oxygen. By irradiating an active energy ray capable of cleaving a CC carbon bond or an active energy ray capable of cleaving a CC carbon bond, the CC carbon bond of the polymer chain constituting the cured film (polymer of the photosensitive resin composition) is cleaved, or by irradiation with an active energy ray The CC carbon bonds of the polymer chain constituting the cured product are cleaved by the generated active oxygen. As a result, some of the cleaved hydrocarbon radicals combine with oxygen in the presence of oxygen, and vaporize as carbon dioxide or the like. In addition, hydrocarbon radicals recombine to form low molecular weight compounds in some cases, and some of these low molecular weight compounds are vaporized. Further, when the C-C carbon bond in the polymer chain is cleaved, the molecular weight is lowered, and thus the cured film itself is also brittle. Moreover, even if it is a polymer chain in which the crosslinked structure in the cured film is formed, since the C-C carbon bond of the crosslinked portion is cut by irradiation with active energy rays or active oxygen, it is in a soluble state in a solvent. In the prior art, attention was paid to preparing the solvent which peels easily, or to prepare the photosensitive composition from which the cured film which peels easily with a solvent is obtained, but this invention finds a completely new method different from any of the prior art. According to the present invention, the cured film can be removed from the base material regardless of the composition of the photosensitive resin composition, and the active energy ray can be irradiated only to the portion where the cured film is defective. When a defect is found in a part of the cured film, only the defective portion can be removed from the cured film from the substrate. Hereinafter, each process of the recycling method of the base material for wiring boards by this invention is demonstrated.

[wiring board]

The present invention provides a method of reusing the substrate by removing a part or all of the cured film from the wiring board provided with the cured film formed on the surface of the substrate as described above. That is, in the manufacturing process of the wiring board which forms a hardened film, when a defect is found in a part of hardened film, the method of removing only the hardened film with the said defect is provided. First, a hardened film is formed on a base material, and a wiring board is demonstrated.

As a process of forming a cured film on a base material to produce a wiring board, the method of hardening a coating film after exposure and development, such as a printed wiring board on which the soldering resist layer is formed, and forming a cured film can be applied without limitation. Hereinafter, the general method of forming a cured film on a base material is demonstrated.

First, a dry film having a resin layer formed by coating and drying a photosensitive resin composition on a substrate to form a dry film or by applying and drying the photosensitive resin composition to a support film is applied so that the substrate and the resin layer are in contact with each other. The dry film is pasted together. Next, the dry coating film or the resin layer of the dry film is exposed and developed to form a cured film on the substrate. When forming a cured film using a dry film, it is preferable to peel a support film from a resin layer in either before or after exposure.

<Reference>

Examples of the substrate include printed wiring boards and flexible printed wiring boards in which circuits are formed in advance with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin ·It uses materials such as copper clad laminate for high-frequency circuits using polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., and all grades (FR-4, etc.) of copper clad laminate, and other wafer substrates, metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like. Among these, a copper clad laminated board is especially preferable.

Moreover, when using a copper clad laminated board etc. as a base material, in order to improve the adhesiveness between a base material and a cured film, it is preferable to grind|polish the surface of copper foil. Examples of the polishing include physical polishing such as buff, scrub and brush, and chemical polishing such as CZ8101. Moreover, as for the arithmetic mean surface roughness (Ra) of the copper foil surface after grinding|polishing, 50-1000 nm is preferable. According to the method of the present invention, even a cured film having increased adhesion to a substrate can be easily removed with a solvent.

<Photosensitive resin composition>

The photosensitive resin composition is patterned by exposing and developing, and turns into a cured film formed on a base material. As such a photosensitive resin composition, although a conventionally well-known soldering resist ink etc. can be used without limitation, for example, Hereinafter, an example of the photosensitive resin composition which can be used suitably in this invention is demonstrated.

In this invention, the photosensitive resin composition containing (A) carboxyl group-containing resin, (B) photopolymerizable monomer, (C) photoinitiator, and (D) thermosetting component can be used suitably.

(A) As carboxyl group-containing resin, the conventionally well-known various photosensitive resin which has a carboxyl group in a molecule|numerator can be used. When the photosensitive resin composition contains (A) carboxyl group-containing resin, alkali developability can be provided with respect to the photosensitive resin composition. In particular, a carboxyl group-containing photosensitive resin having a (meth)acryloyl group in the molecule is preferable from the viewpoint of photocurability and develop resistance. The (meth)acryloyl group is preferably derived from acrylic acid, methacrylic acid, or derivatives thereof. (A) As a specific example of carboxyl group-containing resin, the following compounds (any of an oligomer and a polymer may be sufficient) is mentioned. In addition, in this specification, the (meth)acryloyl group is a term which generically names an acryloyl group, a methacryloyl group, and a mixture thereof, and it is the same also about other similar expression.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.

(2) Diisocyanates, such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, dimethylol propionic acid, and dimethylol butanoic acid Carboxyl group-containing dial alcohol compounds, such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, phenolic hydroxyl groups and alcoholic hydroxyls A carboxyl group-containing urethane resin by polyaddition reaction of a diol compound such as a compound having an actual group.

(3) Diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, etc. A carboxyl group-containing photosensitive urethane resin by polyaddition reaction of a (meth)acrylate of a functional epoxy resin or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(4) During the synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl group is added in a molecule such as hydroxyalkyl (meth)acrylate, and the terminal A (meth)acrylated carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin of (2) or (3), one isocyanate group and one or more (meth) ) A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having an acryloyl group to terminal (meth)acrylate.

(6) A photosensitive resin containing a carboxyl group in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, and dibasic acid anhydride is added to the hydroxyl group present in the side chain.

(7) A carboxyl group-containing photosensitive resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and dibasic acid anhydride is added to the resulting hydroxyl group .

(8) Dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride with primary hydroxyl groups produced by reacting dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid with a bifunctional oxetane resin A carboxyl group-containing polyester resin to which was added.

(9) In an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and unsaturation such as (meth)acrylic acid The reaction product obtained by reacting the group-containing monocarboxylic acid contains a carboxyl group obtained by reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with the alcoholic hydroxyl group of the reaction product photosensitive resin.

(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a monocarboxylic acid containing an unsaturated group, and a polybasic acid anhydride is reacted with the reaction product obtained A carboxyl group-containing photosensitive resin obtained by making it

(11) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is reacted with the resulting reaction product A carboxyl group-containing photosensitive resin obtained by making it

(12) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl group in one molecule to the resin of the above (1) to (11).

(A) Carboxyl group-containing resin which can be used for this invention is not limited to what was enumerated above.

In addition, (A) carboxyl group-containing resin enumerated above may be used individually by 1 type, and may mix and use multiple types.

(A) Although the weight average molecular weight of carboxyl group-containing resin changes with resin skeleton, it is the range of 2,000-150,000 generally, and it is preferable to exist in the range of 5,000-100,000. By using (A) carboxyl group-containing resin having a weight average molecular weight of 2,000 or more, resolution and tack-free performance can be improved. Moreover, developability and storage stability can be improved by using (A) carboxyl group containing resin whose weight average molecular weight is 150,000 or less.

(A) When the compounding quantity of carboxyl group-containing resin makes the total amount of (A) carboxyl group-containing resin and (D) thermosetting component 100 mass parts in conversion of solid content, it is preferable that it is 50-90 mass parts. (A) By carrying out the compounding quantity of carboxyl group-containing resin into the said range, the state change by time-lapse|temporality of the coating-film surface becomes an appropriate thing, and adhesiveness with a base material can be improved more. According to the method of the present invention, even a cured film having increased adhesion to a substrate can be easily removed with a solvent.

The (B) photopolymerizable monomer contained in the photosensitive resin composition is a monomer which has an ethylenically unsaturated double bond. (B) As a photopolymerizable monomer, for example, well-known and usual polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, epoxy (meth) Acrylates etc. are mentioned.

Specifically, hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; acrylamides such as N,N-dimethyl acrylamide, N-methylolacrylamide, and N,N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone additions polyvalent acrylates such as water; polyvalent acrylates such as phenoxyacrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; polyvalent acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Not limited to the above, polyol such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, and polyester polyol is directly acrylated or urethane acrylated through diisocyanate. Any of the methacrylates corresponding to the acrylates and melamine acrylates and the acrylates can be appropriately selected from at least one type and used. Such (B) photopolymerizable monomer can be used also as a reactive diluent.

Epoxy acrylate resin in which acrylic acid is reacted with polyfunctional epoxy resin such as cresol novolak type epoxy resin, or hydroxyl acrylate such as pentaerythritol triacrylate and isophorone die in the hydroxyl group of the epoxy acrylate resin You may use the epoxy urethane acrylate compound etc. which made the half urethane compound of diisocyanate, such as isocyanate, react as (B) a photopolymerizable monomer. Such an epoxy acrylate-based compound can improve photocurability without reducing dry-to-touch properties.

(B) It is preferable that it is 10-50 mass parts with respect to 100 mass parts of (A) carboxy-containing resin, and, as for the compounding quantity of a photopolymerizable monomer, it is more preferable that it is 15-45 mass parts in conversion of solid content. (B) By making the compounding quantity of a photopolymerizable monomer into 10 mass parts or more, the photocurability of the photosensitive resin composition improves. Moreover, the resolution of a cured film can be improved by a compounding quantity being 50 mass parts or less.

(B) The photopolymerizable monomer is effective because it is necessary to use the (B) photopolymerizable monomer together in order to make the composition photocurable, particularly when a carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond is used.

The (C) photoinitiator contained in the photosensitive resin composition is for making the above-mentioned (A) carboxyl group-containing resin and (B) photopolymerizable monomer react by exposure. (C) As a photoinitiator, any well-known thing can be used. (C) A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) Specific examples of the photopolymerization initiator include, for example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide and bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine. Pinoxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6- Dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2 Bisacylphosphine oxides, such as 5-dimethylphenyl phosphine oxide and bis-(2,4,6- trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine monoacylphosphine oxides such as oxide, isopropyl ester of pivaloylphenylphosphinic acid, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinate, 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1- hydroxyacetophenones such as one and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, mihirazketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone , 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane one-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylamino acetophenones such as acetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4- thioxanthone such as diisopropyl thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- oxime esters such as carbazol-3-yl]-,1-(O-acetyl oxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl) titanocenes such as )-bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; Phenyldisulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned.

Examples of commercially available α-aminoacetophenone-based photopolymerization initiators include Omnirad 907, 369, 369E, and 379 manufactured by IGM Resins. Moreover, as a commercial item of an acyl phosphine oxide type|system|group photoinitiator, IGM Resins company Omnirad TPO H, 819, etc. are mentioned. Commercially available oxime ester-based photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan, N-1919 manufactured by ADEKA Corporation, NCI-831, NCI-831E manufactured by ADEKA Corporation, and TR- manufactured by Sangju Strong Electronic New Materials. PBG-304 etc. are mentioned.

In addition, Japanese Unexamined Patent Publication No. 2004-359639, Japanese Unexamined Patent Publication No. 2005-097141, Japanese Unexamined Patent Publication No. 2005-220097, Japanese Unexamined Patent Publication No. 2006-160634, Japanese Laid-Open The carbazole oxime ester compound of patent 2008-094770, Japanese Unexamined-Japanese-Patent No. 2008-509967, Japanese Patent 2009-040762, Unexamined-Japanese-Patent No. 2011-80036, etc. are mentioned. .

(C) It is preferable that the compounding quantity of a photoinitiator is 1-20 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin in conversion of solid content. When it is 1 mass part or more, the photocurability of the photosensitive resin composition becomes favorable, and film characteristics, such as chemical-resistance, also become favorable. Moreover, when it is 20 mass parts or less, the reduction effect of an outgas is acquired, the light absorption in the hardened-film surface further becomes favorable, and deep part sclerosis|hardenability is hard to fall. More preferably, it is 2-15 mass parts.

Moreover, in this invention, it may use together with (C) a photoinitiator, and may use a photoinitiation adjuvant or a sensitizer. As a photoinitiator or a sensitizer, a benzoin compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, a xanthone compound, etc. are mentioned. In particular, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone It is preferable to use When a thioxanthone compound is contained, deep hardening property can be improved. Although these compounds can be used as (C) a photoinitiator in some cases, it is preferable to use them together with (C) a photoinitiator. In addition, a photoinitiation adjuvant or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

Since these (C) photoinitiator, photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, a sensitivity may become low in some cases, and may function as a ultraviolet absorber. However, these are not used for the purpose of only improving the sensitivity of the photosensitive resin composition. By absorbing light of a specific wavelength as needed, the photoreactivity of the surface can be improved, the line shape and aperture of the resist pattern can be changed to vertical, tapered shape, or reverse tapered shape, and the precision of line width or aperture diameter can be improved. have.

It is preferable that the (D) thermosetting component is contained in the photosensitive resin composition. (D) By including a thermosetting component, while the barrier property (for example, etching resistance, etc.) of the cured film in a post process improves, resolution and peelability can be made compatible with a high dimension. (D) As a thermosetting component, all well-known things can be used. For example, melamine resin, benzoguanamine resin, melamine derivative, amino resin such as benzoguanamine derivative, isocyanate compound, block isocyanate compound, cyclocarbonate compound, epoxy compound, oxetane compound, episulfide Well-known compounds, such as resin, bismaleimide, and carbodiimide resin, can be used. Particularly preferably, a compound having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter, abbreviated as cyclic (thio)ether groups) in the molecule can be used. These thermosetting components can be used individually by 1 type or in combination of 2 or more type.

The compound having a plurality of cyclic (thio)ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio)ether groups in the molecule, for example, a compound having a plurality of epoxy groups in the molecule; That is, polyfunctional epoxy compounds, compounds having a plurality of oxetanyl groups in the molecule, i.e., polyfunctional oxetane compounds, compounds having a plurality of thioether groups in the molecule, i.e., episulfide resin, etc. are mentioned.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol. A novolak-type epoxy resin, a novolak-type epoxy resin of bisphenol A, a biphenyl-type epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenylmethane-type epoxy resin, etc. are mentioned.

Examples of commercially available epoxy resins include jER 828, 806, 807, YX8000, YX8034, 834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059, ST-3000 manufactured by Nittetsu Chemical & Materials Co., Ltd.; EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Corporation.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4 -bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetane Yl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate In addition to polyfunctional oxetanes such as acrylates, oligomers or copolymers thereof, oxetane alcohol, novolac resins, poly(p-hydroxystyrene), cardo type bisphenols, calixarenes, An ether product with resin which has hydroxyl groups, such as calixresorcinarenes or silsesquioxane, etc. are mentioned. In addition, the copolymer etc. of the unsaturated monomer which have an oxetane ring, and alkyl (meth)acrylate are mentioned.

Bisphenol A-type episulfide resin etc. are mentioned as a compound which has a some cyclic thioether group in a molecule|numerator. Moreover, an episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis|combining method can also be used.

As amino resins, such as a melamine derivative and a benzoguanamine derivative, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned.

As an isocyanate compound, a polyisocyanate compound can be mix|blended. Examples of the polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1, aromatic polyisocyanates such as 5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer; Tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis(cyclohexylisocyanate) and isophorone aliphatic polyisocyanates such as diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and adducts, biurets and isocyanurates of the isocyanate compounds listed above.

As a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the polyisocyanate compound etc. mentioned above are mentioned, for example. As an isocyanate blocking agent, For example, a phenol type blocking agent; lactam block agent; active methylene-based blocking agent; alcohol-based blocking agent; oxime-based blocking agent; mercaptan-based blocking agent; acid amide block agent; imide block agent; amine blocking agent; imidazole-based blocking agents; An immigration-based block system, etc. are mentioned.

(D) As for the compounding quantity of a thermosetting component, 0.8-2.5 mol of the functional groups of (D) thermosetting component which react with respect to 1.0 mol of carboxyl groups contained in (A) carboxyl group-containing resin are preferable, More preferably, 1.0 to 2.0 mol.

In particular, when using an epoxy resin as (D) thermosetting component, it is preferable that the epoxy group of an epoxy resin is 1.0-2.0 mol per 1.0 mol of carboxyl groups of (A) carboxyl group-containing resin. By setting it as 1 mol or more, residual|survival of the carboxyl group in a cured film can be prevented, and favorable heat resistance, alkali resistance, electrical insulation, etc. can be acquired. In addition, by setting the compounding amount to 2 mol or less, it is possible to prevent the low molecular weight cyclic (thio)ether group from remaining in the dry coating film, and to ensure satisfactory strength and the like of the cured coating film.

The photosensitive resin composition may contain the (E) thermosetting catalyst for promoting hardening of the above-mentioned (D) thermosetting component. (E) Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenyl. imidazole derivatives such as imidazole, 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-di amine compounds such as methylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. In addition, as commercially available ones, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., Sanapuro U-CAT 3513N (trade name of a dimethylamine compound) manufactured by Corporation, DBU, DBN, U-CAT SA 102 (all are bicyclic amidine compounds and salts thereof), and the like.

It is not limited to the above-mentioned compounds, and (E) a thermosetting catalyst for an epoxy resin or an oxetane compound, or anything that promotes the reaction of at least any one of an epoxy group and an oxetanyl group with a carboxyl group, Or you may mix and use 2 or more types. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocya S-triazine derivatives, such as a nuric acid adduct, can also be used, Preferably, the compound which functions also as these adhesion-imparting agents is used together with the (E) thermosetting catalyst.

The above-mentioned (E) thermosetting catalyst can be used individually by 1 type or in combination of 2 or more type. (E) the compounding amount of the thermosetting catalyst, from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the cured film, in terms of solid content, (A) It is preferable that it is 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, It is more preferable that it is 0.05-1 mass part.

A filler can be mix|blended with the photosensitive resin composition as needed in order to raise the physical strength of a cured film, etc. As the filler, a known inorganic or organic filler can be used, and in particular, barium sulfate, spherical silica, hydrotalcite and talc are preferably used. In addition, in order to obtain flame retardancy, a metal hydroxide such as a metal oxide or aluminum hydroxide can be used as an extender pigment filler.

Among the above-mentioned fillers, spherical silica can be preferably used. As the spherical silica, it is preferable to use spherical silica having an average particle diameter of 1 nm to 100 nm, and more preferably, an average particle diameter of 2 nm to 50 nm. Also by blending the spherical silica having the average particle diameter as described above, the surface states Ra1 and Ra2 of the cured coating film described above can be adjusted. In addition, the average particle diameter is an average particle diameter (D50) including not only the particle diameter of primary particles but also the particle diameter of secondary particles (aggregates), and is a value of D50 measured by laser diffraction method. The average particle diameter can be calculated|required using the measuring apparatus (For example, Microtrac MT3300EXII by MicrotracBEL Corp.) by a laser diffraction method.

Moreover, in order to improve the dispersibility in the photosensitive resin composition, the surface-treated thing may be sufficient as the filler mentioned above. Aggregation can be suppressed by using the filler by which the surface treatment has been carried out. The surface treatment method is not particularly limited, and a known and conventional method may be used, but it is preferable to treat the surface of the inorganic filler with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group. .

As a coupling agent, coupling agents, such as a silane type, a titanate type, an aluminate type, and a zircoaluminate type, can be used. Among them, a silane-based coupling agent is preferable. Examples of such a silane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are mentioned, These can be used individually or in combination. have. It is preferable that these silane coupling agents are previously immobilized on the surface of a filler by adsorption|suction or reaction. Here, it is preferable that the processing amount of the coupling agent with respect to 100 mass parts of spherical silica is 0.5-10 mass parts.

The photosensitive resin composition may contain the coloring agent as needed. As the colorant, well-known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and dyes may be used, but from the viewpoint of reducing environmental load and having little effect on the human body, a colorant containing no halogen It is preferable to be

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. The same color-index (CI; published by The Society of Dyers and Colorists) is assigned a number.

As a monoazo red colorant, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146 , 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269. Moreover, Pigment Red 37, 38, 41 etc. are mentioned as a disazo system red coloring agent. In addition, as a monoazolake-based red colorant, Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53: 1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68, and the like. Moreover, Pigment Red 171, 175, 176, 185, 208 etc. are mentioned as a benzimidazolone type|system|group red coloring agent. Moreover, as a perylene-type red coloring agent, Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224, etc. are mentioned. Moreover, as a diketopyrrolopyrrole type|system|group red coloring agent, Pigment Red 254, 255, 264, 270, 272, etc. are mentioned. Moreover, Pigment Red 220, 144, 166, 214, 220, 221, 242 etc. are mentioned as a condensed azo red colorant. Moreover, as an anthraquinone system red coloring agent, Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207, etc. are mentioned. Moreover, Pigment Red 122, 202, 206, 207, 209 etc. are mentioned as a quinacridone type|system|group red coloring agent.

Examples of the blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as pigments are exemplified, for example, Pigment Blue 15, 15:1, 15:2, 15 :3, 15:4, 15:6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used as a dye type. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the anthraquinone yellow colorant include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like. Pigment Yellow 110, 109, 139, 179, 185, etc. are mentioned as an isoindolinone type yellow coloring agent. Examples of the condensed azo yellow colorant include Pigment Yellow 93, 94, 95, 128, 155, 166, 180 and the like. Pigment Yellow 120, 151, 154, 156, 175, 181 etc. are mentioned as a benzimidazolone type yellow coloring agent. Moreover, as a monoazo type yellow colorant, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104. , 105, 111, 116, 167, 168, 169, 182, 183 and the like. In addition, as a disazo yellow colorant, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. can be heard

In addition, you may add colorants, such as purple, orange, brown, black, and white. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23,25, Carbon Black , titanium oxide, and the like.

Although the compounding quantity of the coloring agent in the photosensitive resin composition is not specifically limited, It is preferable that it is 0.1-5 mass % of the photosensitive resin composition whole quantity.

You may mix|blend the organic solvent with the photosensitive resin composition of this invention from a viewpoint of preparation easiness and applicability|paintability. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol glycol ethers such as monomethyl ether acetate and tripropylene glycol monomethyl ether; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butylcellosolve acetate, carbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate Ryu; aliphatic hydrocarbons such as octane and decane; A well-known and usual organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used individually by 1 type or in combination of 2 or more type.

The compounding quantity of the organic solvent in the photosensitive resin composition can be suitably changed according to the component which comprises the photosensitive resin composition, For example, in conversion of solid content, (A) 30-300 mass with respect to 100 mass parts of carboxyl group-containing resin. it can be done with wealth

In the photosensitive resin composition of the present invention, if necessary, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, a copper poison inhibitor, an antioxidant, a rust inhibitor, an organic bentonite , at least one of a thickener such as montmorillonite, a silicone-based, fluorine-based, polymer-based defoaming agent, and a leveling agent; can For these, a well-known thing can be used in the field|area of an electronic material.

The photosensitive resin composition of this invention may be used as a dry film, or may be used as a liquid. In addition, when using as a liquid phase, one-component or two-component or more may be sufficient.

<Dry Film>

In this invention, the said photosensitive resin composition can also be made into the form of a dry film provided with the resin layer which consists of a support film and the said photosensitive resin composition formed on the said support film. Here, when laminating so that the resin layer side of a dry film may contact on a base material with the support film in this invention, it refers to what is adhere|attached to curable resin layer at least. The support film may be peeled from a curable resin layer in the process after lamination. In dry film formation, the photosensitive resin composition of the present invention is diluted with an organic solvent, adjusted to an appropriate viscosity, comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray A film can be obtained by applying it to a uniform thickness on a support film with a coater or the like, and drying it at a temperature of 50 to 130° C. for 1 to 30 minutes. Although there is no restriction|limiting in particular about the coating film thickness, Generally, it is 1-150 micrometers as a film thickness after drying, Preferably it selects suitably in the range of 10-60 micrometers.

As the support film, any known support film can be used without particular limitation, for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamidoimide film, a polypropylene film, or a thermoplastic resin such as a polystyrene film. A film consisting of can be suitably used. Among these, a polyester film is preferable from a viewpoint of heat resistance, mechanical strength, handleability, etc. Moreover, it is also possible to use the laminated body of these films as a support film.

The thermoplastic resin film as described above is preferably a film stretched in the uniaxial direction or the biaxial direction from the viewpoint of improving the mechanical strength.

Although the thickness in particular of a support film is not restrict|limited, For example, it can be 10 micrometers - 150 micrometers.

After forming the resin layer of the photosensitive resin composition of the present invention on the support film, for the purpose of preventing dust from adhering to the surface of the resin layer, a peelable protective (cover) film on the surface of the resin layer It is preferable to laminate. Here, when laminating so that the resin layer side of a dry film may contact on a base material with the protective film in this invention and integrally molding, it refers to peeling from a resin layer before lamination. As a peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used, When peeling a protective film, the resin layer rather than the adhesive force of a resin layer and a support film. And the adhesive force of a protective film should just be a smaller thing.

Although the thickness of a protective film is not specifically limited, For example, it can be 10 micrometers - 150 micrometers.

The above-mentioned photosensitive resin composition is adjusted to a viscosity suitable for a coating method using the organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, etc. After application by the method of, the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100° C. to form a tack-free resin layer. Moreover, when the photosensitive resin composition contains the organic solvent, after apply|coating the photosensitive resin composition, it is preferable to volatilize and dry. The volatilization drying is a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven, etc. (a method of bringing the hot air in the drying machine into countercurrent contact using a heat source of an air heating method by steam, and a nozzle It can be carried out using the method of blowing from the to the support).

On the other hand, when using a dry film, after sticking a dry film on a base material so that a resin layer may contact with a base material with a laminator etc., in either before or after the exposure process mentioned later, by peeling off a support film, on a base material A resin layer is formed. Moreover, when using the dry film provided with a protective film, after peeling a protective film from a dry film, bonding to a base material is performed. It is preferable to perform bonding to the base material of a dry film under pressure and heating using a vacuum laminator etc. By using such a vacuum laminator, when a circuit-formed substrate is used, even if there are irregularities on the circuit board surface, the dry film adheres to the circuit board, so there is no mixing of air bubbles, and the hole filling properties of the recesses on the substrate surface are also improved. . It is preferable that pressurization conditions are about 0.1-2.0 MPa, and it is preferable that heating conditions are 40-120 degreeC.

After forming a dry coating film of the photosensitive resin composition on a substrate or using a dry film to form a resin layer, it is passed through a photomask having a predetermined pattern and selectively exposed to active energy rays, It develops with aqueous alkali solution (for example, 0.3-3 mass % sodium carbonate aqueous solution), and forms the pattern of hardened|cured material. In the case of a dry film, the hardened|cured material patterned on a base material is formed by developing and peeling a support film from a dry film after exposure. Moreover, if it is a range which does not impair a characteristic, a support film may be peeled from a dry film before exposure, and you may expose and develop the exposed resin layer.

In addition, in this invention, you may perform at least any one of heating and irradiation to the resin layer after image development after the exposure and image development mentioned above, and before irradiation of the active energy ray mentioned later. For example, by heat curing (100 to 220° C.) or light irradiation of a resin layer formed by exposure and development, or by final curing (main curing) using a combination of heat curing and light irradiation, adhesiveness, hardness, etc. A cured film with excellent properties is formed. According to the method of the present invention, even a cured film having increased adhesion to a substrate can be easily removed with a solvent.

As the exposure machine used for irradiation with the active energy ray, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted, and any device irradiating ultraviolet 1 in the range of 350 to 450 nm is sufficient, and A direct drawing apparatus (for example, a laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer) can also be used. As a lamp light source or a laser light source of a straight drawing machine, what is necessary is just to exist in the range of 350-450 nm of maximum wavelength. The exposure amount for image formation varies depending on the film thickness and the like, but can be generally within the range of 10 to 1000 mJ/cm 2 , preferably 20 to 800 mK/cm 2 . In addition, from the viewpoint of the wavelength, the active energy ray is distinguished from at least any one of an active energy ray capable of generating active oxygen and an active energy ray capable of cleaving a CC carbon bond in the presence of oxygen, which will be described later. it can be In addition, the presence of oxygen means that the oxygen flow rate in the atmosphere is at least 0.2 sccm or more, and is generally 0.5 sccm or more.

The developing method may be a dipping method, a shower method, a spraying method, a brush method, etc., and as a developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines may be used. can

Although what is necessary is just to set the thickness of the hardened film formed suitably according to the use of a wiring board, it is preferable that it is the range of 1-1000 micrometers. When the cured film is too thick, it may take time to remove the cured film described later. Moreover, the confirmation method of whether a hardened film was formed can be confirmed with the following method. That is, under an environment of 25 ° C. 50% RH, a cloth containing isopropyl alcohol (IPA) is placed on the surface of the cured film, and a 500 g weight is placed thereon and left for 1 minute, then the cloth is removed, A state in which all or a part of the resin layer has not adhered to the surface that has been in contact with the cured film of the rag is judged as a "hardened state".

As described above, the cured film formed on the substrate is in close contact with the substrate. The degree of adhesion between the substrate and the cured film depends on the surface condition of the substrate on which the cured film is formed, the composition of the photosensitive resin composition, and curing conditions. It is preferable that it is 3 N/cm or more, and, as for the peeling strength measured based on (test piece width 10 mm, 90 degree direction, speed 50 mm/min), it is more preferable that it is 5 N/cm or more. Moreover, as an upper limit, it is preferable that it is 10 N/cm or less. According to the method of the present invention, even when the adhesion between the substrate and the cured film is high, the cured film can be easily removed with a solvent.

[Irradiation process of active energy ray]

The cured film obtained as mentioned above may generate|occur|produce a defect in some cases. For example, printing defects when applying a photosensitive resin composition such as solder resist ink to a substrate, positional misalignment during exposure, color unevenness (color non-uniformity), pinholes in the dry coating film, mixing of foreign substances, poor printing of marking ink, etc. defects may occur. Also in such a case, according to the method of this invention, a hardened film is peeled from a base material only at the location with a defect, and a base material can be reused.

The active energy ray used in the present invention is at least any one of an active energy ray capable of generating active oxygen and an active energy ray capable of cleaving a CC carbon bond in the presence of oxygen, and has a wavelength of 100 to 255 nm. Radiation can be preferably used. When ionizing radiation with a wavelength of 100 to 255 nm is irradiated in the presence of oxygen, some oxygen molecules in the atmosphere become active oxygen (including ozone). The C-C carbon bond of the polymer chain constituting the cured product is cleaved by active oxygen. As a result, a part of the cleaved hydrocarbon radical is combined with oxygen and is vaporized as carbon dioxide or the like. In addition, hydrocarbon radicals recombine to form low molecular weight compounds in some cases, and some of these low molecular weight compounds are vaporized. Further, since the ionizing radiation having a wavelength of 100 to 255 nm is an ionizing radiation having an energy higher than the C-C carbon bonding energy, the polymer chain constituting the cured film can be cut and the molecular weight can be reduced. As a result, residues (such as hydrocarbons remaining without vaporization) remaining on the substrate can be easily removed with a solvent or the like.

As an apparatus capable of irradiating ionizing radiation with a wavelength of 100 to 255 nm, for example, a UV ozone cleaner (the distance from the UV lamp light source to the irradiation surface is 1 cm, type: low pressure mercury lamp (melted quartz), shape: high density high power and apparatuses such as a grid lamp and ultraviolet intensity: 28 mW/cm 2 ). Moreover, when an ionizing radiation is an ultraviolet-ray, as the intensity|strength, 3-50 mW/cm<2> is preferable.

[Cure film removal process]

Next, the substrate on which the cured film is formed is washed with a solvent, and the cured film on the portion irradiated with active energy rays is removed from the substrate. As a method of cleaning the cured film on the substrate, it may be by a method using a dipping method, a spraying method, a single-wafer method, or the like. In particular, in the case where the cured film is removed only from defective portions, a spraying method or the like is suitable.

As the solvent, various organic solvents can be used. Among them, an aprotic polar solvent can be suitably used in consideration of the effect on the manufactured wiring board. Examples of the aprotic polar solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetramethylurea, 1,3-dimethyl- 2-imidazolidinone, dimethyl propylene urea, dimethyl sulfoxide, γ-butyrolactone, β-propiolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and the like; , These can be used individually by 1 type or in combination of 2 or more type. Among these, N-methylpyrrolidone can be used suitably.

Even when the residue on the upper surface of the substrate is cleaned with a solvent, the residue may remain on the substrate in a very trace amount. It is preferable to exist in the range of 80-200 degreeC, and, as for heating temperature, it is more preferable to exist in the range of 100-150 degreeC.

The method of this invention can be used when manufacturing electronic components, such as a printed wiring board. Since the cured film can be removed from the base material regardless of the composition of the photosensitive resin composition, it is particularly advantageous, for example, when a base material with high added value is used. In addition, since irradiation of active energy rays can be irradiated only to a portion where the cured film is defective, when a defect is found in a part of the cured film when manufacturing a wiring board, only the defective portion can be removed from the substrate. , can improve production efficiency (yield).

[Example]

The present invention will be described in detail by presenting examples and comparative examples below, but the present invention is not limited to the following examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.

[Prepared in photosensitive resin composition]

First, the photosensitive resin composition was prepared. The photosensitive resin composition is 2,4,6-trimethyl as 13 parts (value as solid content) of the following carboxyl group containing resin varnish 1 as 30 parts (value as solid content) of the following carboxyl group containing resin varnish 1, and a photoinitiator 4 parts of benzoyldiphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins), 11 parts of tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Kogyo Co., Ltd.) as a photopolymerizable monomer, as a thermosetting component 27 parts of bisphenol A epoxy resin (jER 828, manufactured by Mitsubishi Chemical Co., Ltd.) and 0.3 parts of an imidazole-based epoxy resin curing agent (Qazole 1B2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a thermosetting catalyst were blended and prepared with a stirrer. After mixing, it kneaded with a three roll mill, and the photosensitive resin composition was prepared.

<Carboxyl group-containing resin varnish 1>

In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device and a stirring device, 119.4 g of novolak-type cresol resin (Aika Kogyo Co., Ltd. product, trade name “Shonol CRG951”, OH equivalent: 119.4), 1.19 g of potassium hydroxide and 119.4 g of toluene was poured, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Then, 63.8 g of propylene oxide was dripped gradually, and it was made to react at 125-132 degreeC and 0-4.8 kg/cm<2> for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added and mixed to the reaction solution to neutralize potassium hydroxide. Propylene oxide reaction of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. A solution was obtained. In this case, 1.08 moles of alkylene oxides were added on average per equivalent of phenolic hydroxyl groups. Next, 293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methyl hydroquinone, and 252.9 g of toluene were added to a reactor equipped with a stirrer, a thermometer and an air blowing tube. , air was blown in at a rate of 10 ml/min, and reacted at 110° C. for 12 hours while stirring. Water produced by the reaction was an azeotrope with toluene, and 12.6 g of water was distilled off. Thereafter, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Then, it distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate for toluene in an evaporator, and the novolak-type acrylate resin solution was obtained. Then, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were injected into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown in at a rate of 10 ml/min, While stirring, 60.8 g of tetrahydrophthalic anhydride was added gradually, and it was made to react at 95-101 degreeC for 6 hours. In this way, the resin solution of the carboxyl group-containing photosensitive resin having a solid content acid value of 88 mgKOH/g, a solid content of 71%, and a weight average molecular weight of 2,000 was obtained. Let this be carboxyl group containing resin varnish 1.

<Carboxyl group-containing resin varnish 2>

In a flask equipped with a stirrer, thermometer and condenser, 848.8 g of γ-butyrolactone, 57.5 g (0.23 mol) of MDI (diphenylmethane diisocyanate), and DMBPDI (4,4'-diisocyanate) -3,3'-dimethyl-1,1'-biphenyl) 59.4 g (0.225 mol) and TMA (trimellitic anhydride) 67.2 g (0.35 mol) and TMA-H (cyclohexane-1,3,4 -Tricarboxylic acid-3,4-anhydride) 29.7 g (0.15 mol) was injected, and while stirring, the temperature was raised to 80° C. paying attention to heat generation, and dissolved and reacted at this temperature for 1 hour, followed by a further 2 hours After raising the temperature to 160°C over a period of time, the reaction was conducted at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide gas, and the inside of the system became a brown transparent liquid. In this way, a solution of carboxyl group-containing amidimide resin having a viscosity of 7 Pa·s at 25°C, a solid content of 17% and a solution acid value of 5.3 (KOH mg/g) (resin composition in which the resin is dissolved in γ-butyrolactone) ) was obtained. Moreover, the solid content acid value of resin was 31.2 (KOHmg/g), and the weight average molecular weight was 34,000. Let this be carboxyl group containing resin varnish 2.

The surface of FR-4 copper-clad laminate (100mm×150mm×0.8mmf, double-sided copper foil, the thickness of copper foil is 18㎛ on both sides) was subjected to an arithmetic mean surface roughness (Ra) by CZ8101, a product of MEC COMPANY LTD. After chemical polishing to 400 nm, the photosensitive resin composition obtained as described above is applied to the chemically polished surface of the substrate by screen printing so that the film thickness after drying is 20 to 25 μm. It was dried for minutes and cooled slowly to room temperature.

Next, for the coating film, L/S=100/100, 80/80, 60/60, 40/40, 20/20, 10/10, 7/7, 5/5, 4/4, 3/3, Using a metal halide lamp through a photomask having a line pattern of 2/2 and 1/1 (units are all in μm), UV rays with a wavelength of 365 nm at an exposure amount of 1,000 mJ/cm2 are irradiated in an atmospheric atmosphere, and the Then, development was performed for 180 second using 30 degreeC and ₁ weight% of _Na2CO3 aqueous solution, and the cured film was formed. Whether a cured film was formed is determined by placing a rag containing isopropyl alcohol (IPA) on the surface of the cured film under an environment of 25 ° C. 50% RH, and placing a 500 g weight on it and leaving it to stand for 1 minute, The mop was removed, and it was judged by being in the state in which all or part of the resin layer has not adhered to the surface which was in contact with the cured film of the mop. In addition, in the formed cured film, the peel strength measured in accordance with JIS-C-6481 copper clad laminate test method and peel strength measurement method (test piece width 10 mm, 90° direction, speed 50 mm/min) was, It confirmed that they were 3 N/cm or more and 10 N/cm or less.

[Example 1]

Two board|substrates with the cured film obtained as mentioned above were prepared. For one cured film-forming substrate, apply a UV ozone cleaner (distance from the UV lamp light source to the irradiation surface is 1 cm) to the entire surface of the cured film formation surface, type: low pressure mercury lamp (melted quartz), shape: high-density high-power grid Using a type lamp, ultraviolet intensity: 28 mW/cm 2 ), at an exposure dose of 25.2 J/cm 2 , active energy rays of wavelength 185 nm (10%) + 254 nm (90%) were applied in the presence of oxygen (oxygen flow rate of 0.5 sccm). under atmospheric conditions).

About the other cured film formation board|substrate, the active energy ray was irradiated on the conditions similar to the above through the light-shielding mask so that it might be irradiated only to the location where the line pattern was formed with the photomask.

Then, for the cured film-forming substrate that was irradiated over the entire surface, the substrate was immersed in an N-methylpyrrolidone solvent and left at 55° C. for 20 minutes, after which the solvent was removed. Moreover, about the cured film formation board|substrate which was partially irradiated, the N-methylpyrrolidone solvent was dripped at the site|part irradiated with the active energy ray of this board|substrate, and after leaving it to stand at 55 degreeC for 20 minutes, the solvent was removed.

When the obtained board|substrate was confirmed visually, also in any board|substrate, the hardened film of the location irradiated with an active energy ray was completely removed.

[Comparative Example 1]

Except not irradiating the active energy ray with a low pressure mercury lamp, it carried out similarly to Example 1, and processed using the N-methylpyrrolidone solvent with respect to each of two cured-film formation board|substrates. When the obtained board|substrate was confirmed visually, in either board|substrate, the cured film did not peel from the board|substrate.

[Comparative Example 2]

In the same manner as in Example 1, except that irradiation of active energy rays by a low-pressure mercury lamp was replaced from the presence of oxygen (under the atmosphere) to the nitrogen atmosphere, for each of the two cured film-forming substrates, N-methylpyrrol The treatment was performed using a money solvent. When the obtained board|substrate was confirmed visually, in either board|substrate, although the cured film of the part irradiated with the active energy ray partially peeled from the board|substrate, it did not peel completely from the base material, but the cured film remained.

From the experimental results of Example 1 and Comparative Examples 1 and 2, it can be seen that the cured film can be effectively peeled off by irradiating an active energy ray in the presence of oxygen.

[Comparative Example 3]

Example 1, except that the low-pressure mercury lamp was replaced by irradiation with active energy rays (main wavelength 365 nm) by a UV conveyor (Oak Manufacturing Co., Ltd. type: QRM-2082, ultraviolet intensity: 80 mW/cm2) using a high-pressure mercury lamp Similarly, treatment was performed using the N-methylpyrrolidone solvent for each of the two cured film-forming substrates. When the obtained board|substrate was confirmed visually, in either board|substrate, although the cured film of the part irradiated with an active energy ray partially peeled from the board|substrate, it did not peel completely from the base material, but the cured film remained.

From the experimental results of Example 1 and Comparative Example 3, it can be seen that, in the ultraviolet irradiation using a high-pressure mercury lamp, active oxygen is not generated and C-C carbon bonds are not cleaved.

Claims (8)

A method of reusing the substrate by removing a part or all of the cured film from a wiring board having a cured film formed on the surface of the substrate, the method comprising:
The cured film is made of a cured product of the photosensitive resin composition,
A step of irradiating at least one of an active energy ray capable of generating active oxygen and an active energy ray capable of cleaving a CC carbon bond to a part or all of the cured film in the presence of oxygen;
A step of washing the substrate on which the cured film is formed with a solvent and removing the cured film of the portion irradiated with active energy rays from the substrate
A method of recycling a substrate for a wiring board, comprising: The dry film according to claim 1, wherein the cured film has a resin layer formed by coating and drying the photosensitive resin composition on the substrate to form a dry film, or applying and drying the photosensitive resin composition to a support film. , wherein the dry film is bonded so that the substrate and the resin layer are in contact, and then the dried coating film or the resin layer of the dry film is exposed, developed, and patterned. The method for recycling a substrate for a wiring board according to claim 1 or 2, wherein the active energy ray contains ionizing radiation having a wavelength of 100 to 255 nm. The method for recycling a substrate for a wiring board according to any one of claims 1 to 3, further comprising a step of heating the wiring board from which the cured film has been removed. The method for recycling a substrate for a wiring board according to any one of claims 1 to 4, wherein the solvent is an aprotic polar solvent. The wiring according to any one of claims 1 to 5, wherein the photosensitive resin composition contains (A) a carboxyl group-containing resin, (B) a photopolymerizable monomer, (C) a photoinitiator, and (D) a thermosetting component. A method of recycling a substrate for a substrate. The method of recycling a substrate for wiring boards according to claim 6, wherein at least one of heating and ultraviolet irradiation is performed after exposure and development of the resin layer and before irradiation with active energy rays to the cured film. The reuse method of the base material for wiring boards in any one of Claims 1-7 whose thickness of the said cured film is 1-1000 micrometers.