KR20050056159A - Dry film photoresist - Google Patents

Abstract

An object of the present invention is to provide a dry film photoresist having high resolution, tent film strength, and storage stability.

A photosensitive resin composition layer which contains a support body and the polyurethane resin which has at least (A) carboxyl group and does not have ethylenically unsaturated bond, (B) polymeric compound which has ethylenically unsaturated bond, and (C) photoinitiator. Dry film photoresist.

Description

Dry Film Photoresist {DRY FILM PHOTORESIST}

The present invention relates to a dry film photoresist comprising a support and a photosensitive resin composition layer. The present invention also relates to a method for manufacturing a printed wiring board having through holes or via holes, such as a double-sided printed wiring board or a multilayer printed wiring board using the dry film photoresist.

In the field of manufacturing printed wiring boards, the wiring pattern is formed by a photolithography technique using a dry film photoresist comprising a support (particularly, a flexible transparent film support) and a photosensitive resin composition layer formed on the support. have. For example, in the case of a printed wiring board having a through hole, a through hole is formed in a copper-clad laminate, a metal layer is formed in the inner wall of the through hole, and then a photosensitive resin composition layer of a dry film photoresist is formed on the substrate surface. The photosensitive resin composition layer is cured by irradiating light in a predetermined pattern onto a region including the wiring pattern forming region and the through hole opening. Subsequently, the support of the dry film photoresist is removed to remove the uncured photosensitive resin composition region. When this laminated sheet is immersed in the etching liquid which melt | dissolves copper, the exposed metal layer part is etched and the same copper field pattern as the pattern which irradiated light can be obtained. Thereafter, the cured resin composition is removed and a copper wiring pattern is formed on the substrate surface.

In recent years, the demand for densification of printed wiring boards has been increasing, and a high resolution dry film photoresist capable of reproducing fine lines has been demanded. In order to increase the resolution of the dry film photoresist, it is effective to reduce the thickness of the photosensitive resin composition layer. On the other hand, as described above, the dry film photoresist also serves to protect the metal layer of the inner wall surface of the through hole formed in the printed wiring board, and through-hole hardening in the step of dissolving and removing the uncured photosensitive resin composition region. There is a drawback that the resin composition bursts.

Although the through-hole cured resin composition is called a tent film, the following results are disclosed as a means of increasing the strength of the tent film.

Patent Document 1 discloses a dry film photoresist in which a photosensitive resin composition layer is formed of a binder polymer having a carboxyl group, a polymerizable urethane compound having an ethylenically unsaturated bond, a polymerizable acrylate compound, and a photopolymerization initiator. According to this patent document, a polymeric urethane compound mainly contributes to the improvement of a tent film | membrane strength, and a polymeric acrylate compound mainly contributes to the improvement of a resolution.

Patent Literature 2 discloses that a photosensitive resin composition layer as a photoresist excellent in tent film strength includes an alkali-soluble polymer compound, a polymerizable urethane compound having an ethylenically unsaturated bond, a photopolymerizable monomer having three or more ethylenically unsaturated groups in one molecule, And a dry film photoresist comprising a photopolymerization initiator. In the Example of this patent document, a high molecular weight urethane compound and two urethane compounds of low molecular weight are used as a polymeric urethane compound.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-142789

Patent Document 2: Japanese Patent Application Laid-Open No. 2001-117225

In order to cope with thinning of printed wiring boards and high-density requirements, further improvement of the resolution and tent film strength of dry film photoresist is required. Regarding the high resolution of the dry film photoresist, it is effective to reduce the thickness of the photosensitive resin composition layer. However, when the thickness of the photosensitive resin composition layer is reduced, the tent film strength is lowered.

As mentioned above, it is effective to use a polymeric urethane compound for the improvement of the tent film strength of a dry film photoresist. However, according to the viewpoint of the present inventors, when the compounding quantity of the polymeric compound in the photosensitive resin composition layer of a dry film photoresist increases, the problem that the edge fusion which a photosensitive resin composition will seep out of a roll at the time of storage will generate | occur | produce easily, etc. May occur. Moreover, when high molecular weight compounds, such as an oligomer or a polymer, are used as a polymeric compound, edge fusion can be prevented, but a fading may arise in the resist at the time of storage, and storage stability may fall, and superposition | polymerization may be carried out. There is a limit to the improvement of the tent film strength only by the improvement of the compound.

An object of the present invention is to provide a dry film photoresist having high resolution, tent film strength, and storage stability. Another object of the present invention is to provide a method for producing a printed wiring board using the dry film photoresist.

MEANS TO SOLVE THE PROBLEM This inventor uses the polyurethane resin which has a carboxyl group as a binder and does not have an ethylenically unsaturated bond as a binder to the photosensitive resin composition layer, Even if the thickness is made thin, the polymerizable compound is not added excessively. The present inventors have found that they can form a high tent film.

Therefore, this invention is photosensitive containing the support body, the polyurethane resin which has a (A) carboxyl group, and does not have an ethylenically unsaturated bond, the polymeric compound which has (B) ethylenically unsaturated bond, and (C) photoinitiator. A dry film photoresist having a resin composition layer.

Preferable aspects of the present invention are as follows.

(1) A polyurethane resin (A) having no ethylenically unsaturated bonds comprises a reaction product of at least one diisocyanate compound and at least one diol compound containing a diol compound having a carboxyl group.

(2) The mass average molecular weight of the polyurethane resin (A) having no ethylenically unsaturated bond is in the range of 5000 to 300,000.

(3) A polymeric compound (B) is a compound containing a urethane bond.

(4) 10-90 mass% of polyurethane resins (A) which the photosensitive resin composition layer does not have an ethylenically unsaturated bond, 5-60 mass% of polymeric compounds (B), and 0.1-30 of photoinitiators (C) It contains in mass%.

(5) The thickness of the photosensitive resin composition layer is 5 micrometers or more and less than 35 micrometers.

(6) A protective film layer is formed on the photosensitive resin composition layer.

(7) It is for manufacturing a printed wiring board.

This invention also exists in the manufacturing method which consists of the following process of the printed wiring board which has the through-hole or via hole whose inner wall surface was covered with the metal layer.

(1) preparing a substrate for forming a printed wiring board having a through hole or via hole and whose surface is covered with a metal layer;

(2) The dry film photoresist of the present invention is pressed onto the surface of the substrate for forming a printed wiring board so that the photosensitive resin composition layer is in contact with the metal layer, and the substrate for forming a printed wiring board, the photosensitive resin composition layer and the support are in this order. A lamination step of obtaining a laminate laminated as such;

(3) Irradiating light in a pattern form from the surface on the support side of the laminate, and curing the photosensitive resin composition layer to a cured resin composition region for forming a wiring pattern and a cured resin composition region for protecting a metal layer of a through hole or via hole. An exposure step of forming a cured resin composition pattern formed;

(4) a support peeling step of removing the support from the laminate;

(5) a developing step of dissolving and removing the uncured region of the resin composition layer on the substrate for forming a printed wiring board and exposing the metal layer of the uncured region on the substrate surface;

(6) an etching step of dissolving and removing the metal layer of the exposed region with an etching solution; And

(7) The cured resin composition removing step of removing the cured resin composition from the substrate for forming a printed wiring board.

The present invention also provides a polyurethane resin having (A) a carboxyl group and no ethylenically unsaturated bond on a substrate for forming a printed wiring board having a through hole or via hole and whose surface is covered with a metal layer, and (B) ethylenically unsaturated. It exists also in the laminated body by which the photosensitive resin composition layer containing the polymeric compound which has a bond, and (C) photoinitiator is laminated | stacked.

1 is a cross-sectional view of an example of the dry film photoresist of the present invention.

In Fig. 1, in the dry film photoresist 11, a support (flexible transparent film support) 12, a photosensitive resin composition layer 13, and a protective film 14 are laminated in this order. The photosensitive resin composition layer 13 is a photosensitive resin containing (A) a polyurethane resin which has a carboxyl group and does not have an ethylenically unsaturated bond, (B) a polymeric compound which has an ethylenically unsaturated bond, and (C) a photoinitiator. Consists of a composition. Although the thickness of the photosensitive resin composition layer 13 is not specifically limited, Generally, it is 1-200 micrometers, It is preferable that it is 5 micrometers or more and less than 35 micrometers, More preferably, it is the range of 10-30 micrometers, More preferably, Is in the range of 10 to 25 µm.

[Polyurethane resin (A) having a carboxyl group and not having an ethylenically unsaturated bond]

Polyurethane resin (A) which has a carboxyl group and does not have an ethylenically unsaturated bond used in the dry film photoresist of this invention is at least 1 type containing at least 1 type or more of diisocyanate compounds and a diol compound which has a carboxyl group. It is preferably a reaction product of the diol compound of the phase.

The polyurethane resin used in the present invention may be an organic solvent soluble or an aqueous dispersion.

<Diisocyanate compound>

Preferable diisocyanate compounds are diisocyanate compounds represented by the following general formula (1).

OCN-X-NCO （1)

In formula (1), X represents the bivalent aliphatic or aromatic hydrocarbon group which may have a substituent. As needed, X may have another functional group which does not react with an isocyanate group, for example, ester group, urethane group, amide group, and ureido group.

Specific examples of the diisocyanate compound represented by the general formula (1) include those shown below. In other words, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diren diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-di Aromatic diisocyanate compounds such as phenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate and the like; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate and the like; Alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatemethyl) cyclohexane compound; Diisocyanate compounds which are reactants of diols and diisocyanates such as adducts of 1 mole of 1,3-butylene glycol and 2 moles of tolylene diisocyanate; Etc. can be mentioned. These diisocyanate compounds may be used independently or may use 2 or more types together.

<Diol compound>

Preferable diol compounds are diol compounds having a carboxyl group represented by the following General Formula (2).

HO-Y-OH (2)

In formula (2), Y represents the bivalent aliphatic or aromatic hydrocarbon group which has a carboxyl group.

The carboxyl group-containing diol compound is particularly preferably a compound obtained by ring-opening a diol compound represented by any one of the following General Formulas (3), (4) or (5) and / or tetracarboxylic dianhydride with a diol compound. .

In formula (3), R ¹ is a hydrogen atom, a substituent (for example, a cyano group, a nitro group, a halogen atom such as -F, -Cl, -Br, -I, -CONH ₂ , -COOR ² ,- OR ³ , -NHCONHR ⁴ , -NHCOOR ⁵ , -NHCOR ⁶ , -OCONHR ⁷ (wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each an alkyl group having 1 to 10 carbon atoms and a carbon atom number) And aralkyl groups of 7 to 15.) Each group such as a) is included.) An alkyl group, an aralkyl group, an aryl group, an alkoxy group or an aryloxy group which may have an alkyl group, preferably a hydrogen atom and a carbon atom having 1 to 8 carbon atoms. An alkyl group or an aryl group having 6 to 15 carbon atoms is represented.

In formula (4), Ar <^1> represents the trivalent aromatic hydrocarbon group which may have a substituent, Preferably it shows the C6-C15 aromatic hydrocarbon group.

In formula (3), formula (4), and formula (5), L <^1> , L <^2> and L <^3> may be same or different, respectively, and are a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group, and alkoxy) A divalent aliphatic or aromatic hydrocarbon group which may have a group, a halogen atom), preferably an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, more preferably alkyl having 1 to 8 carbon atoms Represents a Ren group. Moreover, as needed, you may have other functional groups which do not react with an isocyanate group in L <^1> , L <^2> and L <^3> , for example, carbonyl group, ester group, urethane group, amide group, ureido group, and ether group. Further, the formula (3) in R ^1, L ^1, L ² and L ^3, the formula (4) in L ^1, L ² and L ^3, the formula (5) of the L ^1, L ² and L ³ of 2 or 3 You may form a ring with a dog.

Specific examples of the diol compound having a carboxyl group represented by formula (3), formula (4) or formula (5) include those shown below. Namely, 3,5-dihydroxy benzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid , 2,2-bis (hydroxymethyl) butanoic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis ( 4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, and N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like.

As preferable tetracarboxylic dianhydride, what is represented by following General formula (6), Formula (7), or Formula (8) is mentioned.

In the formula, L ⁴ is a divalent aliphatic or aromatic group which may have a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogen atom, an ester group, or an amide group is preferable). A hydrocarbon group, -CO-, -SO-, -SO _2- , -O-, or -S-. Preferably, they are a single bond, a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, -CO-, -SO _2- , -O- or -S-.

R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or a halogen atom, and preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 6 to 15 carbon atoms Aryl group, alkoxy group having 1 to 8 carbon atoms or halogen atom.

Two of L ⁴ , R ⁸ and R ⁹ may be bonded to each other to form a ring.

In formula, L <^5> may be a bivalent aliphatic or aromatic which may have a single bond, a substituent (For example, each group of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogen atom, an ester group, and an amide group is preferable.). A hydrocarbon group, -CO-, -SO-, -SO _2- , -O- or -S-. Preferably, they are a single bond, a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, -CO-, -SO _2- , -O- or -S-.

L ⁶ and L ⁷ may be the same or different, and represent a single bond or a divalent aliphatic hydrocarbon group, and preferably a single bond or a methylene group.

R ¹⁰ and R ¹¹ may be the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogen atom, and preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms.

Two of L ⁵ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.

In the formula, the ring of A represents a mononuclear or multinuclear aromatic ring. Preferably it is an aromatic ring of 6-18 carbon atoms.

As a compound represented by Formula (6), Formula (7), or Formula (8), what is specifically shown below is included. That is, pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl tetracarboxylic dianhydride, 2,3, 6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis (3,4-di Carboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 '-[3,3'-(alkylphosphoryldiphenylene) -bis (iminocarbonyl)] di Aromatic tetracarboxylic dianhydrides such as phthalic dianhydride, adduct of hydroquinone diacetate and trimethic anhydride, adduct of diacetyldiamine and trimethic anhydride; 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (Dinipon Ink Kgaku Kogyo Co., Ltd., epicron B-4400) Cycloaliphatic tetracarboxes, such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and tetrahydrofurantetracarboxylic dianhydride Acid dianhydrides; And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butane tetracarboxylic dianhydride and 1,2,4,5-pentane tetracarboxylic dianhydride.

Specific diol compounds used in the ring-opening reaction of the tetracarboxylic dianhydride include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol , 1,3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydrate Roxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, bisphenol Propylene oxide adduct of F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinonedihydroxyethyl ether, p-xylylene glycol, Hydroxyethylsulfone, bis (2-hydroxyethyl) -2,4-tolylenedicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl ) -m-xylylenedicarbamate, bis (2-hydroxyethyl) isophthalate, etc. are mentioned.

A carboxyl group-containing diol compound can be used individually or in combination of 2 or more types.

The synthesis | combination of the said polyurethane resin can use together the other diol compound which does not have a carboxyl group and may use the other substituent which does not react with an isocyanate. The linking group connecting two hydroxyl groups of the other diol compound is a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, a carbonyl group (-CO-), an oxygen atom (-O-), or a sulfur atom ( It is preferable that the hydrogen atom of -S-), the imino group (-NH-), and the imino group is a substituted imino group substituted with a monovalent hydrocarbon group, or a group combining these.

As another diol compound, a polyetherdiol compound, a polyesterdiol compound, a polycarbonate diol compound, etc. are mentioned widely.

As a polyetherdiol compound, the compound represented by following General formula (9), formula (10), formula (11), formula (12) or formula (13), and the ethylene oxide and propylene oxide which have a hydroxyl group at the terminal The random copolymer of is mentioned.

R <^12> in Formula (9) and R <^13> in Formula (10) represent a hydrogen atom or a methyl group.

X <^1> and X <^2> in Formula (13) respectively independently represent the following groups.

A, b, c, d, e, f and g in Formulas (9) to (13) represent integers of 2 or more, and are preferably integers of 2 to 100.

Specifically as a polyetherdiol compound represented by Formula (9) or Formula (10), what is shown below is mentioned. That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, tetra- 1,2-propylene glycol, hexa-1,2-propylene glycol, di-1,3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol, di-1,3-butyl Lenglycol, tri-1,3-butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol of mass average molecular weight 1000, polyethylene glycol of mass average molecular weight 1500 polyethylene glycol, mass average molecular weight 2000, mass average molecular weight 3000 polyethylene glycol, mass average molecular weight 7500 polyethylene glycol, mass average molecular weight 400 polypropylene glycol, mass average molecular weight 700 polypropylene glycol, mass average molecular weight 1000 polypropylene glycol, mass average molecular weight 2000 polypropylene glycol, mass average molecular weight 3000 polypropylene glycol, mass average molecular weight 4000 polypropylene glycol, etc.

As a diol compound represented by Formula (11), what is shown below is mentioned specifically ,. Sanyo Kasei Co., Ltd. product (brand name) PTMG650, PTMG1000, PTMG2000, PTMG3000, etc.

Specifically as a polyetherdiol compound represented by Formula (12), what is shown below is mentioned. Sanyo Kasei Co., Ltd., (brand name) New Fall PE-61, New Fall PE-62, New Fall PE-64, New Fall PE-68, New Fall PE-71, New Fall PE-74, New Fall PE-75, New Fall PE-78 New Fall PE-108, New Fall PE-128, New Fall PE-61, etc.

Specifically as a polyetherdiol compound represented by Formula (13), what is shown below is mentioned. Sanyo Kasei Co., Ltd., (brand name) New Pole BPE-20, New Pole BPE-20F, New Pole BPE-20NK, New Pole BPE-20T, New Pole BPE-20G, New Pole BPE-40, New Pole BPE-60, New Pole BPE-100 , Newpole BPE-180, Newpole BPE-2P, Newpole BPE-23P, Newpole BPE-3P, Newpole BPE-5P etc.

As a random copolymer of ethylene oxide and propylene oxide which have a hydroxyl group at the terminal, what is specifically shown below is mentioned. Sanyo Kasei Kogyo Co., Ltd., (brand name) Newpole 50HB-100, Newpole 50HB-260, Newpole 50HB-400, Newpole 50HB-660, Newpole 50HB-2000, Newpole 50HB-5100, etc.

As a polyesterdiol compound, the compound represented by following General formula (14) or Formula (15) is mentioned.

In formula, L <^8> , L <^9> and L <^10> may be the same respectively, and may represent a divalent aliphatic or aromatic hydrocarbon group, and L <^11> represents a divalent aliphatic hydrocarbon group. Preferably, L ⁸ , L ⁹ and L ¹⁰ each represent an alkylene group and an arylene group, and L ¹¹ represents an alkylene group. In L ⁸ , L ⁹ , L ¹⁰ and L ¹¹ , other functional groups which do not react with isocyanate groups (for example, ether groups, carbonyl groups, ester groups, cyano groups, urethane groups, amide groups, ureido groups or halogen atoms, etc.) May exist.

n1 and n2 are integers 2 or more, respectively, Preferably the integer of 2-100 is represented.

As a polycarbonate diol compound, the diol compound represented by following General formula (16) is mentioned.

In the formula, L ¹² may be the same as or different from each other, and represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ¹² represents an alkylene group or an arylene group. In addition, other functional groups (for example, ether group, carbonyl group, ester group, cyano group, urethane group, amide group, ureido group, halogen atom, etc.) which do not react with isocyanate group may exist in L <^12> .

n3 is an integer of 2 or more, Preferably the integer of 2-100 is shown.

As a diol compound represented by Formula (14), Formula (15), or Formula (16), the exemplary compound (No. 1)-(No. 13) shown below are contained specifically ,. N in a specific example is an integer of 2 or more.

Moreover, as another diol compound, the diol compound represented by following General formula (17)-(27) can also be used preferably.

In the formula, L ¹³ and L ¹⁴ may be the same as or different from each other, and a halogen atom such as a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, -F, -Cl, -Br, or -I) Each group, such as etc. is included.), The bivalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or heterocyclic group which may have is shown. If necessary, L ¹³ and L other functional groups that do not react with isocyanate groups during the ¹⁴ may have a (e. G., A carbonyl group, an ester group, a urethane group, an amide group, an ureido group, etc.). It is also possible to form a ring in L ¹³ and L ^14.

As a specific example of a compound represented by said Formula (17) or Formula (18), exemplary compound (No. 14)-(No. 27) shown below are included.

In formula, n4 represents the integer of 2 or more, Preferably it is an integer of 2-100.

In the formula, R ¹⁴ and R ¹⁵ may be the same as or different from each other, and an alkyl group, an aralkyl group, an aryl group, -COOR ¹⁶ , -OR ¹⁷ , -NHCONHR ¹⁸ , -NHCOOR ¹⁹ , -NHCOR ²⁰ , -OCONHR ²¹ (here, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each an alkyl group having 1 to 20 carbon atoms (straight chain alkyl group, a branched alkyl group, a cyclic alkyl group), an aralkyl group having 7 to 20 carbon atoms, and having 6 to 20 carbon atoms. Aryl group.). Preferably, they are an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 15 carbon atoms, or -NHCOR ^20- .

As a diol compound represented by Formula (19) or Formula (20), what is specifically shown below is mentioned. That is, as Formula (19), ethylene glycol, 1, 3- propanediol, 1, 4- butanediol, 1, 5- pentanediol, 1, 6- hexanediol, 1, 7-heptane diol, and 1, 8- Octanediol and the like. As Formula (20), they are exemplary compounds (No.28)-(No.33) shown below.

In formula, L <^15> and L <^16> may be same or different, respectively, and is a substituent (for example, alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, halogen atom (-F, -Cl, -Br, -I)). Each group, such as etc. is included.), The bivalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or heterocyclic group which may have is shown. As needed, you may have other functional groups (for example, carbonyl group, ester group, urethane group, amide group, ureido group, etc.) which do not react with an isocyanate group in L <^15> and L <^16> . In addition, you may form a ring by L <^15> and L <^16> .

Specific examples of the compound represented by formula (21) or formula (22) include those shown below.

In formula, L <^17> represents the bivalent aliphatic hydrocarbon group which may have a substituent (For example, each group of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom is preferable.). If necessary, L ¹⁷ in the other functional group which does not react with isocyanate groups may have a (e. G., An ester group, a urethane group, an amide group, a ureido group).

Ar ² and Ar ³ may be the same or different and represent a divalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms.

n5 represents the integer of 0-10.

As a diol compound represented by said Formula (23) or Formula (24), what is specifically shown below is included. That is, catechol, resorcin, hydroquinone, 4-methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4-methylresorcin, 4-ethylresorcin, 4-t-butylresorcin, 4-hexyl resorcin, 4-chlororesorcin, 4-benzylesorcin, 4-acetylresorcin, 4-carbomethoxyresorcin, 2-methylresor Lecin, 5-methylresorcin, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylcar Boaminohydroquinone, methylureidohydroquinone, methylthiohydroquinone, benzonorbornene-3,6-diol, bisphenol A, bisphenol S, 3,3'-dichlorobisphenol S, 4,4'-dihydroxybenzo Phenone, 4,4'-dihydroxybiphenyl, 4,4'-thiodiphenol, 2,2'-dihydroxydiphenylmethane, 3,4-bis (p-hydroxyphenyl) hexane, 1, 4-bis (2- (p-hydroxyphenyl) propyl) benzene, bis (4-hi Hydroxyphenyl) methylamine, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,5-dihydroxyanthra Quinone, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxyphenethyl alcohol, 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenyl acetate, resorcin mono-2-hydroxyethyl ether, and the like. .

In formula (25), R ²² represents a hydrogen atom, a substituent (for example, cyano, nitro, halogen atom (-F, -Cl, -Br, -I), -CONH ₂ , -COOR ²³ , -OR ²⁴ , -NHCONHR ²⁵ , -NHCOOR ²⁶ , -NHCOR ²⁷ , -OCONHR ²⁸ , -CONHR ²⁹ (wherein R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each having 1 to 3 carbon atoms). Each group is included.) An alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group, which may have an alkyl group, an aralkyl group having 7 to 15 carbon atoms, is included. An alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms;

In formulas (25), (26) and (27), L ¹⁸ , L ¹⁹ and L ²⁰ may be the same as or different from each other, and may be a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, halogen). Each group is preferred.), A divalent aliphatic or aromatic hydrocarbon group which may have a carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and preferably 1 to 8 carbon atoms An alkylene group is shown. If necessary, L ^18, L ^19, and it does not react with isocyanate groups in L ²⁰ different functional groups, for example, a carbonyl group, may have an ester group, a urethane group, an amide group, a ureido group, an ether. In addition, equation (25) of R ^22, L ^18, L ¹⁹ and L ^20, equation (26) of L ^18, L ¹⁹ and L ^20, L ¹⁸ in the formula (27), L ¹⁹ and L ²⁰ 2 out of the or You may form a ring with three.

Ar ⁴ in formula (26) represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms.

In Formulas (25), (26) and (27), Z ¹ represents the following group.

Here, R <^30> , R <^31> may be same or different, respectively, and represents a hydrogen atom, sodium, potassium, an alkyl group, or an aryl group, Preferably they represent a hydrogen atom, an alkyl group of 1-8 carbon atoms, or an aryl group of 6-15 carbon atoms. .

Another diol compound can be used combining 2 or more types independently.

The polyurethane resin which can be used for this invention is synthesize | combined by adding the said isocyanate compound and the diol compound in an aprotic solvent, the well-known catalyst of the activity according to each reactivity, and heating. The molar ratio of the diisocyanate to be used and the diol compound is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the polymer terminal, the molar ratio of the diisocyanate to be used is treated with alcohols or amines, so that the isocyanate group does not remain. Are synthesized.

It is preferable that the carboxyl group is contained in the range of 0.3-3.5 meq / g, and, as for the polyurethane resin used in this invention, More preferably, it is the range of 0.5-3.3 meq / g. The molecular weight of the polyurethane resin is in the range of 5000 to 300,000, more preferably in the range of 10000 to 250000, still more preferably in the range of 20000 to 200000 as the mass average molecular weight (polystyrene standard).

The polyurethane resin content of the photosensitive resin composition layer is generally 10 to 90 mass%, Preferably it is 40 to 80 mass%, Especially preferably, it is 45 to 65 mass%.

[Polymerizable Compound (B)]

It is preferable that the polymeric compound used in the dry film photoresist of this invention has two or more ethylenically unsaturated bonds. Examples of the polymerizable compound include esters of unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and aliphatic polyhydric amine compounds And amides thereof. Moreover, the polymeric compound which has a urethane bond can also be used.

As a specific example of ester [(meth) acrylic acid ester] of acrylic acid and methacrylic acid, and an aliphatic polyhydric alcohol compound, it is (meth) acrylic acid ester as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimetholpropane tree ( Ta) acrylate, trimetholpropanedi (meth) acrylate, trimetholpropane tri ((meth) acryloyloxypropyl) ether, trimetholethane tri (meth) acrylate, 1,3-butanedioldi (Meth) acrylate, 1, 6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1, 4- cyclohexanediol di (meth) acrylate, pentaerythritol di (meth) acryl Latex, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (Meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, polyester (meth) acrylate Ytt oligomer, bis [p- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis [p-((meth) acryloxyethoxy) phenyl] dimethylmethane and the like.

Examples of esters (itaconic acid esters) of itaconic acid and aliphatic polyhydric alcohol compounds include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, and tetramethylene glycol Diitaconate, pentaerythritol dietaconate, sorbitol tetrataconate, and the like.

Examples of esters of crotonic acid and aliphatic polyhydric alcohol compounds (crotonic acid esters) include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of esters of isocrotonic acid and aliphatic polyhydric alcohol compounds (isocrotonic acid esters) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

Examples of esters of maleic acid and aliphatic polyhydric alcohol compounds (maleic acid esters) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramalate, and the like.

Specific examples of the amide of the unsaturated carboxylic acid and the aliphatic polyamine compound include methylenebis- (meth) acrylamide, ethylenebis (meth) acrylamide, 1,6-hexamethylenebis- (meth) acrylamide, and diethylenetriamine tris. (Meth) acrylamide, xylylenebis (meth) acrylamide, etc. are mentioned.

As a polymeric compound which has a urethane bond, what is represented by following General formula (28), formula (29) or formula (30) is preferable.

In Formula (28), R ³² and R ³³ each independently represent a hydrogen atom or a methyl group.

L ²¹ and L ²² each independently represent a group of a combination of a divalent aliphatic hydrocarbon group (number of carbon atoms 1 to 15) and an oxygen atom (-O-). Examples of L ²¹ and L ²² are shown below. The left side is bonded to the oxygen atom and the right side is bonded to the carbon atom.

Z ² represents a divalent organic group. It is preferable that it is a group which has a C1-C25 alkylene group, an arylene group, and these combined.

p1 and p2 respectively independently represent the integer of 1-25.

In formula (29), R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom or a methyl group.

L ²³ , L ²⁴ and L ²⁵ each independently represent a group of a combination of a divalent aliphatic hydrocarbon group (number of carbon atoms 1 to 15) and an oxygen atom (-O-). Examples of L ²³ , L ^24, and L ²⁵ are shown below. The left side is bonded to the oxygen atom and the right side is bonded to the carbon atom.

It is preferable that Z <^3> , Z <^4> and Z <^5> are group which combined the C1-C25 alkylene group, arylene group, and these.

q1, q2, and q3 respectively independently represent the integer of 1-25.

In formula (30), R ³⁷ represents a hydrogen atom or a methyl group.

L ²⁶ and L ²⁷ each independently represent a group of a combination of a divalent aliphatic hydrocarbon group (number of carbon atoms 1 to 15) and an oxygen atom (-O-). Examples of L ²⁶ and L ²⁷ are shown below. The left side is bonded to the oxygen atom and the right side is bonded to the carbon atom or A.

Z ⁶ represents a divalent organic group. It is preferable that it is a group which has a C1-C25 alkylene group, an arylene group, and these combined.

r1 and r2 represent the integer of 1-50 each independently.

r3 represents the integer of 3-6. From the viewpoint of raw material supplyability for synthesizing the polymerizable monomer, r3 is preferably 3, 4 or 6.

A represents an organic group of r 3 -valent (3- to 6-valent). A is preferably an aliphatic hydrocarbon group which may be via an ether bond in the course of r3 valence of 1 to 100 carbon atoms.

In addition to the compound containing the urethane group, the urethane compounds described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, and Japanese Patent Application Laid-open No. Hei 7-7208, for example, Polyisocyanate compounds having two or more isocyanate groups in one molecule (for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, norbornene diisocyanate or trimers thereof, And vinyl monomers (eg, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth)) containing a hydroxyl group in the molecule and these and polyfunctional alcohols such as trimetholpropane). Acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol Add colmono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.) The urethane compound containing two or more polymerizable vinyl groups in 1 molecule obtained by making it use can also be used.

Furthermore, polyester acrylates, epoxy resins and (meth) acrylic acids described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 Polyfunctional acrylates and methacrylates, such as the epoxy acrylates which were made to react, can also be used. In addition, phthalic acid, trimellitic acid, and the like and esterified products obtained from vinyl monomers containing a hydroxyl group in the above-mentioned molecules may also be mentioned. Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesion association vol.20, No. 7, page 300-308 (1984).

These polymeric compounds can be used individually or in combination of 2 or more types.

The content of the polymerizable compound in the photosensitive resin composition layer is generally in the range of 5 to 60 mass%, preferably in the range of 10 to 50 mass%, particularly preferably in the range of 20 to 45 mass%. When the content of the polymerizable compound is less than the above range, the strength of the cured film (tent film) tends to decrease, while when the content of the polymerizable compound is large, the edge fusion (extrusion failure from the roll end) during storage tends to occur.

[Photopolymerization Initiator (C)]

As the photopolymerization initiator used in the dry film photoresist of the present invention, any compound having the capability of initiating the polymerization of the above-mentioned polymerizable compound can be used. have. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within the range of about 300 to 800 nm (more preferably, 330 to 500 nm). The photoinitiator may be an activator which generates a predetermined radical by generating a predetermined action with a photoexcited sensitizer.

As a photoinitiator used preferably with the dry film photoresist of this invention, a halogenated hydrocarbon derivative (preferably thing which has a triazine skeleton), hexaaryl biimidazole, a ketooxime derivative, an organic peroxide, thio A compound, a keto oxime ester, a ketone compound, an aromatic onium salt, a keto oxime ether, etc. are mentioned. Among them, halogenated hydrocarbons having a triazine skeleton, ketooxime derivatives, hexaarylbiimidazoles, ketooxime esters, and ketone compounds are used to form the photosensitive resin composition layer and the photosensitive resin composition layer and the printed wiring board. It is preferable from the viewpoint of the adhesiveness of the substrate for a solvent.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds.

Wakabayashi et al., Compounds based on Bull. Chem. Soc. Japan, 42, 2924 (1969), for example 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine , 2- (p-crophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (α, α , β-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine;

Compounds described in British Patent 1388492, such as 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (p-methylstyryl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-1,3,5-triazine;

Compounds described in Japanese Patent Application Laid-Open No. 53-133428, for example 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl ) -Naphtho-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphtho-1-yl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine ;

Compounds described in German Patent 3337024, for example 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-p- Methoxystyrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophene-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2- (4-furan-2-vinylene phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2 -Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine;

29, 1527 (1964) by FCSchaefer et al., Compounds such as 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino- 4-methyl-6-tri (bromomethyl) -1,3,5-triazine, and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine;

Japanese Patent Application Laid-Open No. 62-58241, for example, 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-naphthyl) -1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-p-tolylethynylphenyl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-p-methoxyphenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine , 2- (4-p-isopropylphenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-p- (ethylphenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine;

Compounds described in JP-A-5-281728, for example 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2 , 6-difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine;

2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1,3, described in Japanese Patent Application Laid-Open No. 5-34920; 5-triazine; And

The halogenated hydrocarbon compound which has the triazine skeleton of the electrophoretic start system described in Unexamined-Japanese-Patent No. 2001-305734.

These can all be used preferably.

As a ketooxime derivative used preferably by this invention, the compound represented by following General formula (31) is mentioned.

In formula (31), ^R38 and ^R39 are the same or different, and may represent a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group.

R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, a substituent which may have a hydrogen atom, an unsaturated bond, and may represent a hydrocarbon group, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, and a substituted thio group. . R ⁴⁰ and R ⁴¹ combine with each other to form a ring, and -O-, -NR ^44- (R ⁴⁴ is hydrogen or a hydrocarbon group which may have a substituent), -O-CO-, -NH. An alkylene group having 2 to 8 carbon atoms which may contain -CO-, -S-, and / or -SO ₂ -in the linking chain of the ring.

R <^42> and R <^43> represents the hydrocarbon group which may have a hydrogen atom and a substituent, and may contain the unsaturated bond, or a substituted carbonyl group.

Specific examples of the ketooxime derivatives include p-methoxyphenyl2-N, N-dimethylaminopropylketone oxime-O-allyl ether, p-methylthiophenyl2-morpholinopropyl ketone oxime-O-allyl ether, and p- Methylthiophenyl 2-morpholinopropyl ketone oxime-O-benzyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-On-butyl ether, p-morpholinophenyl 2-morpholinopropyl ketone oxime -O-allyl ether, p-methoxyphenyl2-morpholinopropyl ketone oxime-On-dodecyl ether, p-methylthiophenyl2-morpholinopropyl ketone oxime-O-methoxyethoxyethyl ether, p -Methylthiophenyl2-morpholinopropyl ketone oxime-Op-methoxycarbonylbenzyl ether, p-methylthiophenyl2-morpholinopropyl ketone oxime-O-methoxycarbonylmethyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O-ethoxycarbonylmethyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O-4-butoxy P-methylthiophenyl 2-morpholinopropyl ketone oxime-O-2-ethoxycarbonylethyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O-methoxycarbonyl Although 3-propenyl ether and p-methylthio phenyl 2-morpholino propyl ketone oxime-O-benzyloxycarbonyl methyl ether are mentioned, it is not limited to this.

As hexaarylbiimidazole used for this invention, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole and 2,2'-bis (o- Bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimi Dazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4', 5,5 ' -Tetraphenylbiimidazole, etc. are mentioned. These biimidazoles can be easily synthesized by, for example, the methods disclosed in Bull. Chem. Soc. Japan, 33,565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). Can be.

Examples of the ketooxime esters include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan) -2-one and 2-acetoxyiminopentan-3-one. , 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, and 2-e And oxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of ketone compounds include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4 '-Dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthhraquinone, xanthone, thioxanthone , 2-chloro-thioxanthone, 2,4-diethyl thioxanthone, fluolenone, acridon, and the like.

In addition, benzoin or benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, etc.), polyhalogen compounds, ( For example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzoproyl) -7-diethylaminocoumarin, 3- ( 2-benzoproyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (o-methoxybenzoyl) -7-diethylaminocoumarin, 3- (p -Dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin ), 3-benzoyl-7-methoxycoumarin, 3- (2-proyl) -7-diethylaminocoumarin, 3- (p-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-meth Methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxy Coumarins, etc.), amines (for example, p-dimethylamino benzoic acid ethyl, p-dimethylamino benzoic acid n-butyl, p-dimethylamino benzoic acid phenethyl, p-dimethylamino benzoic acid 2-phthalimide ethyl, p-dimethylamino 2-methacryloyloxyethyl benzoate, pentamethylenebis (p-dimethylaminobenzoate), phenethyl and pentamethylene esters of m-dimethylamino benzoic acid, p-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde , p-dimethylaminobenzyl alcohol, ethyl (p-dimethylamino) benzoyl acetate, p-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-p-toluidine, N, N-diethyl- m-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, p-bromine-N, N-dimethylaniline, tridodecylamine, leucocrystal violet, etc.), Japanese Patent Publication JP-A-53-133428, JP-A-57-1819, And compounds disclosed in US Pat. No. 57-6096, US Patent 3615455, and the like.

These photoinitiators can be used individually or in combination of 1 or 2 types. In addition, it is also possible to use two or more compounds in combination. The usage-amount of a photoinitiator exists in the range of 0.1-30 mass% with respect to the whole component of the photosensitive resin composition layer, Preferably it is the range of 0.5-20 mass%, Especially preferably, it is the range of 1-15 mass%.

[Sensitizer]

What is called a sensitizer can be added when using visible light, an ultraviolet-ray laser, etc. as a light ray (active energy ray). As a sensitizer, well-known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrocin, rhodamine B, rosebengal), cyanines (E.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g. merocyanine, carbomerocyanine), thiazines (e.g. thionine, methylene blue, toluidine Blue), acridines (e.g., acridine orange, chloroflavin, acrylflavin, alkylacridine), anthraquinones (e.g., anthraquinones), squarias (e.g., Squaria), acridones (e.g., N-methylacridone, N-butyl-2-chloroacridone), and coumarins (e.g., coumarin-1, coumarin-102, coumarin-152 ) Can be preferably used.

The addition amount of a sensitizer is 0.05-30 mass% with respect to the whole component of the photosensitive resin composition layer, Preferably it is 0.1-20 mass%, Especially preferably, it is 0.2-10 mass%. When the addition amount of the sensitizer is too large, it may be precipitated at the time of storage from the photosensitive resin composition layer, and when too little, the sensitivity to an active energy ray will fall, the exposure process will take time, and productivity of a printed wiring board will fall. There is this.

[Other Ingredients]

In the dry film photoresist of the present invention, a thermal polymerization inhibitor, a plasticizer, a color change agent, a dye (coloring agent), an adhesion promoter to a substrate surface for manufacturing a printed wiring board, and other preparations are used as needed for the photosensitive resin composition layer. You may add. By adding these, properties, such as stability, photography, printing out property, and film | membrane property of the target dry film photoresist, can be adjusted.

[Thermal polymerization inhibitor]

A thermal polymerization inhibitor is added in order to prevent thermal superposition | polymerization or time-lapse superposition | polymerization of the polymeric compound of the photosensitive resin composition layer. Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydride. Roxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, picric acid, p- Toluidine, methylene blue, organocopper, methyl salicylate, phenothiazine and the like can be used.

It is preferable that the addition amount of a thermal polymerization inhibitor exists in the range of 0.001-5 mass% with respect to the polymeric compound content of the photosensitive resin composition layer, More preferably, it is the range of 0.01-2 mass%, Especially preferably, it is 0.05 It is the range of -1 mass%. When the amount of the thermal polymerization inhibitor added exceeds this range, the sensitivity to the active energy ray tends to decrease, while when the amount exceeds this range, the stability during storage tends to deteriorate.

[Plasticizer]

The plasticizer is added to control the film properties (flexibility) of the photosensitive resin composition layer. Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, and diallyl phthalate. Phthalic acid esters such as these; Glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycosphthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, and triethylene glycol dicarblic acid ester Ryu; Phosphoric acid esters such as tricredyl phosphate and triphenyl phosphate; amides such as p-toluenesulfonamide, benzenesulfonamide, and N-n-butylacetamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl acelate, and dibutyl maleate; Triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid dioctyl and the like can be used.

It is preferable that the addition amount of a plasticizer exists in the range of 0.1-50 mass% with respect to the whole component of the photosensitive resin composition layer, More preferably, it is the range of 0.5-40 mass%, Especially preferably, the range of 1-30 mass% to be.

[Tarnishing agent]

The color change agent is added in order to give a visual image (printing out function) to the photosensitive resin composition layer after exposure. Examples of the color change agent include tris (p-dimethylaminophenyl) methane (leucocrystal violet), tris (p-diethylaminophenyl) methane, tris (p-dimethylamino-o-methylphenyl) methane and tris (p -Diethylamino-o-methylphenyl) methane, bis (p-dibutylaminophenyl)-[p- (2-cyanoethyl) methylaminophenyl] methane, bis (p-dimethylaminophenyl) -2-quinolyl Aminotriaryl methanes such as methane and tris (p-dipropylaminophenyl) methane; Aminoxanthines such as 3,6-bis (dimethylamino) -9-phenylxanthine and 3-amino-6-dimethylamino-2-methyl-9- (o-chlorophenyl) xanthine; Aminothioxanthenes such as 3,6-bis (diethylamino) -9- (o-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9-phenylacridine, and 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine and the like Amino-9,10-dihydroacridines; Aminophenoxazines such as 3,7-bis (diethylamino) phenoxazine; Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; Aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; Aminophenylmethanes such as bis (p-dimethylaminophenyl) anilinomethane; Aminohydro cinnamic acids such as 4-amino-4'-dimethylaminodiphenylamine and 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; Hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; Amino-2,3-dihydroanthraquinones of 1,4-bis (ethylamino) -2,3-dihydroanthraquinones; Phenethylanilines such as N, N-diethyl-p-phenethylaniline; Acyl derivatives of leuco pigments containing basic NH such as 10-acetyl-3,7-bis (dimethylamino) phenothiazine; Leuco-type compounds which do not have oxidizable hydrogen, such as tris (4-diethylamino-o-tolyl) ethoxycarbonylmentane, but which can be oxidized to a coloring compound; Leucoindigo dye; Organic amines that can be oxidized to the color forms described in US Pat. No. 3042515 and US Pat. No. 3042517 (eg, 4,4'-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4, 4'-methylenediaminetriphenylamine, N-vinylcarbazole) can be used. Especially preferable is a leuco crystal violet.

It is preferable that the addition amount of a color change agent exists in the range of 0.01-20 mass% with respect to the whole component of the photosensitive resin composition layer, More preferably, it is the range of 0.05-10 mass%, Especially preferably, it is 0.1-5 mass Range of%.

Dye (Colorant)

In the present invention, a dye may be added to the photosensitive resin composition layer for the purpose of coloring the composition or imparting storage stability for improving handleability. Examples of preferred dyes include brilliant green sulfate, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsia, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymol phthalein, methyl violet 2B, Quinalidine red, Rosebengal, Methyl yellow, thymolsulfophthalein, xylenol blue, methyl orange, orange IV, diphenyl tyrocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red , Benzofurfurin 4B, α-naphthyl-red, nile blue A, phenacetalin, methyl violet, marachite green oxalate, parafuxin, oil blue # 603 (product of Orient Kagaku Kogyo Co., Ltd.), rhodamine B, rhodamine 6G, etc. are mentioned. Particularly preferred dyes are marachite green oxalate.

The addition amount of dye is the range of 0.001-10 mass% with respect to all the components of the photosensitive resin composition layer. More preferably, it is the range of 0.01-5 mass%, Especially preferably, it is the range of 0.1 mass%-2 mass%.

[Adhesive Promoter]

In the dry film photoresist of this invention, in order to improve the adhesiveness to the board | substrate for printed wiring board manufacture, a well-known so-called adhesion promoter can be added to the photosensitive resin composition layer. As an adhesion promoter, the thing of each specification of Unexamined-Japanese-Patent No. 5-11439, Unexamined-Japanese-Patent No. 5-341532, and Unexamined-Japanese-Patent No. 6-43638 can be used preferably. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxanol, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl -Triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mer Capto-5-methylthio thiadiazole etc. are mentioned. Among these, 3-morpholinomethyl-1-phenyltriazole-2-thione is especially preferable.

The preferable addition amount of an adhesion promoter is the range of 0.001-20 mass% with respect to the photosensitive resin composition layer. More preferably, it is the range of 0.01-10 mass%, Especially preferably, it is the range of 0.1 mass%-5 mass%.

[Production of Dry Film Photoresist]

In the dry film photoresist of the present invention, for example, the above-mentioned various components are dissolved in a solvent to prepare a photosensitive resin composition solution, which is coated on a support (flexible transparent film) by a known method and dried. It can manufacture by doing. There is no restriction | limiting in particular in the coating method of the photosensitive resin composition solution, For example, a spray method, the roll coating method, the rotary coating method, the slit coating method, the extrusion coating method, the curtain coating method, the die coating method, the wire bar coating method, And various methods such as a knife coating method can be adopted. Although the conditions of drying of the photosensitive resin composition solution differ with each component, the kind of solvent, its compounding ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60-110 degreeC.

As a solvent of the photosensitive resin composition solution, For example, Alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol; Dimethyl formamide, dimethyl sulfooxide, etc. are mentioned.

[Support and Protective Film]

It is necessary for the support to be flexible, to peel off the photosensitive resin composition layer, and to have good light transmittance. Moreover, it is preferable that surface smoothness is favorable. Examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, And various plastic films such as polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene. . Moreover, the composite material which consists of two or more of these can also be used. Among the above, polyethylene terephthalate film is particularly preferable. As for the thickness of a support body, 5-150 micrometers is common and 10-100 micrometers is preferable.

The dry film resist of this invention can form a protective film further on the photosensitive resin composition layer on a support body. As an example of a protective film, what was used for the said support | support, and what laminated | stacked the plastic film, such as a polyethylene film or a polypropylene film, on paper or paper, etc. are mentioned. In particular, a polyethylene film and a polypropylene film are preferable. It is common that the thickness of a protective film exists in the range of 5-100 micrometers, and it is preferable to exist in the range which is 10-50 micrometers.

The support and the protective film preferably have a relationship (A> B) in which the adhesive force A of the photosensitive resin composition layer and the support becomes stronger than the adhesive force B of the photosensitive resin composition layer and the protective film. Examples of the combination of the support / protective film include polyethylene terephthalate film / polypropylene film, polyethylene terephthalate film / polyethylene film, polyvinyl chloride film / cellophane film, and polyimide film / polypropylene film. Thus, by carrying out surface treatment of at least one of a support body or a protective film other than the method of selecting a support body and a protective film from a heterogeneous thing, the relationship of the above adhesive force can be satisfied. The surface treatment of the support is generally carried out in order to increase the adhesive strength with the photosensitive resin composition layer. For example, coating of the primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, Active plasma irradiation treatment, laser beam irradiation treatment, and the like.

For example, when producing a long dry film photoresist and storing and transporting it as a roll, the static friction coefficient of the support and the protective film is also important. It is preferable that this static friction coefficient exists in the range of 0.3-1.4, and the range of 0.5-1.2 is especially preferable. If it is less than 0.3, it slips too much, and when it is set as a roll, winding shift may generate | occur | produce. Moreover, when it exceeds 1.4, it may become difficult to wind up in roll shape.

Moreover, you may surface-treat a protective film. Surface treatment is performed in order to reduce the adhesiveness of a protective film and the photosensitive resin composition layer. For example, on the surface of the protective film, a primer layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and polyvinyl alcohol is formed. Formation of a primer layer is generally performed by apply | coating the said coating liquid of the said polymer to the surface of a protective film, and drying for 1 to 30 minutes at the temperature of 30-150 degreeC (especially 50-120 degreeC).

Moreover, you may form the layer which has various functions, such as a primer layer, an adhesive bond layer, a peeling layer, and a protective layer, or may form 2 or more types of photosensitive resin composition layers from which a film property and a sensitivity differ.

[Manufacture of Printed Wiring Boards]

The dry film photoresist of the present invention can be suitably used for producing printed wiring boards having through holes or via holes.

The manufacturing method of the printed wiring board which has a through hole using the dry film photoresist of this invention is demonstrated, referring FIG. 2 of an accompanying drawing.

As shown in Fig. 2A, a printed circuit board manufacturing substrate 21 having a through hole 22 and whose surface is covered with a metal layer 23 is prepared. As the substrate 21 for manufacturing a printed wiring board, a substrate on which a copper plating layer is formed on an insulating substrate such as a copper clad laminated substrate and a glass-epoxy or a substrate (laminated substrate) on which an interlayer insulating film is laminated on these substrates and a copper plating layer is formed is used. Can be.

Next, as shown in FIG. 2 (B), the photosensitive resin composition layer 13 of the dry film photoresist 11 of the present invention is pressed onto the surface of the substrate 21 for forming a printed wiring board, and the pressing roller 31 is pressed. It is crimped | bonded and used, and the laminated body which the board | substrate 21 for forming a printed wiring board, the photosensitive resin composition layer 13, and the support body 12 were laminated | stacked in this order is obtained (lamination process). A well-known thing, such as a metal roller and a rubber roller, can be used for the crimping roller 31. At the time of crimping, it is preferable to heat the substrate 21 for forming a printed wiring board and the crimping roller 31, respectively. It is preferable to make heating temperature of the board | substrate 21 for printed wiring board formation into the temperature of 50-100 degreeC. It is preferable to make heating temperature of the press roller 31 into the temperature of 60-120 degreeC. The roller pressure of the pressing roller is preferably in the range of 2 to 5 kg / cm 2. It is preferable to make a crimping speed into the speed | rate of 1-3 m / min.

Next, as shown in Fig. 2C, light (active energy) is irradiated in a pattern form from the surface of the support 12 side of the laminate, and the photosensitive resin composition layer 13 is cured to form a wiring pattern. The hardened | cured material pattern 17 which consists of the area | region of the cured resin composition 15 for dragons, and the area | region of the cured resin composition 16 for metal layer protection of a through hole is formed (exposure process). As a method of irradiating light in a pattern form, it is preferable to carry out by irradiating ultraviolet light to the entire surface via a photomask or by irradiating a pattern signal with a laser scanning exposure apparatus having a wavelength in the ultraviolet to visible region. Do. In particular, the method of using the latter laser scanning exposure apparatus can be formed without using an expensive photomask, and thus eliminates problems in the process due to the photomask, and thus is suitable for producing small quantities of various kinds.

Next, as shown in Fig. 2D, the support 12 is peeled from the laminate (support release step).

Next, as shown in Fig. 2E, the weak alkali aqueous solution (pH: 9 to 11) is brought into contact with the resin composition layer 13 to dissolve and remove the uncured region of the resin composition layer on the substrate for forming a printed wiring board. The metal layer 23 on the substrate surface is exposed (development process). As the weak alkaline aqueous solution, an aqueous sodium carbonate solution can be used.

Next, as shown in Fig. 2F, the exposed metal plating 23 is dissolved in an etching solution (etching step). Since the opening of the through hole 22 is covered with the cured resin composition (tent film) 16, the etching liquid does not enter the through hole to corrode the metal layer in the through hole, and the metal layer of the through hole remains in a predetermined shape. . By this etching, the wiring pattern 24 of a printed wiring board is formed.

And finally, as shown in FIG.2 (G), a strong alkali aqueous solution (pH: 13-14) is made to contact hardened resin pattern, the hardened | cured material pattern is crushed finely, and it is set as the peeling piece 18, and a printed wiring board formation It removes from the substrate 21 for hardening (hardening removal process). As a strong alkali aqueous solution, the sodium hydroxide aqueous solution can be used.

The dry film photoresist of the present invention may be used not only for the above etching process but also for the plating process. As the plating method, for example, copper plating such as copper sulfate plating, copper pyrophosphate plating, high-slow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as sulfamic acid nickel plating, hard gold plating, soft gold There is gold plating such as plating.

(Example)

Synthesis Example 1 (Polyurethane solution having a carboxyl group and no ethylenically unsaturated bond: Polyurethane solution 1)

25.0 parts by mass of 4,4-diphenylmethane diisocyanate was dissolved in 20.0 parts by mass of N, N-dimethylacetamide. To this was added a mixed solution of 13.4 parts by mass of 2,2-bis (hydroxymethyl) propionic acid and 37.8 parts by mass of N, N-dimethylacetamide, and 0.1 parts by mass of dibutyltin dilaurylate was further added. It stirred by heating for 7 hours at the temperature of ° C. Then, the polyurethane solution 1 (solid content 35 mass%) which has a carboxyl group and does not have an ethylenically unsaturated bond was obtained by adding 13.7 mass parts of 1-methoxy-2-propanol. The molecular weight of the polymer was measured by gel permeation chromatography (GPC), and was 45000 in terms of mass average molecular weight (polystyrene equivalent).

[Synthesis example 2 (polyurethane solution having a carboxyl group and no ethylenically unsaturated bond: polyurethane solution 2)]

25.0 parts by mass of 4,4-diphenylmethane diisocyanate was dissolved in 20.0 parts by mass of N, N-dimethylacetamide. To this was added a mixed solution of 12.1 parts by mass of 2,2-bis (hydroxymethyl) propionic acid, 10 parts by mass of both terminal diols (average molecular weight 1000) of polypropylene glycol, and 50.8 parts by mass of N, N-dimethylacetamide, Furthermore, 0.1 mass part of dibutyltin dilauryllates were added, and it heat-stirred for 7 hours at the temperature of 90 degreeC. Then, the polyurethane solution 2 (35 mass% of solid content) which has a carboxyl group and does not have ethylenically unsaturated bond was obtained by adding 15.6 mass part of 1-methoxy-2-propanol. The molecular weight of the polymer was measured by gel permeation chromatography (GPC) and found to be 52000 in terms of mass average molecular weight (polystyrene equivalent).

[Synthesis example 3 (polyurethane solution having a carboxyl group and no ethylenically unsaturated bond: polyurethane solution 3)]

25.0 parts by mass of 4,4-diphenylmethane diisocyanate was dissolved in 20.0 parts by mass of N, N-dimethylacetamide. 10.7 parts by mass of 2,2-bis (hydroxymethyl) propionic acid, 8.0 parts by mass of both terminal diols (average molecular weight 400) of polypropylene glycol, and 45.7 parts by mass of N, N-dimethylacetamide are added thereto. Furthermore, 0.1 mass part of dibutyltin dilauryllates were added, and it heat-stirred for 7 hours at the temperature of 90 degreeC. Then, the polyurethane solution 3 (35 mass% of solid content) which has a carboxyl group and does not have ethylenically unsaturated bond was obtained by adding 15.6 mass part of 1-methoxy-2-propanol. The molecular weight of the polymer was measured by gel permeation chromatography (GPC) and found to be 50000 in terms of mass average molecular weight (polystyrene equivalent).

[Synthesis example 4 (polyurethane solution having a carboxyl group and no ethylenically unsaturated bond: polyurethane solution 4)]

20.0 parts by mass of 4,4-diphenylmethane diisocyanate and 3.4 parts by mass of 1,6-hexamethylene diisocyanate were dissolved in 20.0 parts by mass of N, N-dimethylacetamide. To this was added 12.1 parts by mass of 2,2-bis (hydroxymethyl) propionic acid, 10 parts by mass of both terminal diols (average molecular weight 1000) of polypropylene glycol, and a mixed solution of 48.4 parts by mass of N, N-dimethylacetamide, Furthermore, 0.1 mass part of dibutyltin dilauryllates were added, and it heat-stirred for 7 hours at the temperature of 90 degreeC. Then, the polyurethane solution 4 (35 mass% of solid content) which has a carboxyl group and does not have an ethylenically unsaturated bond was obtained by adding 16.3 mass parts of 1-methoxy-2-propanol. The molecular weight of the polymer was measured by gel permeation chromatography (GPC) and found to be 44000 in terms of mass average molecular weight (polystyrene equivalent).

[Synthesis example 5 (polyurethane solution having a carboxyl group and no ethylenically unsaturated bond: polyurethane solution 5)]

22.5 parts by mass of 4,4-diphenylmethane diisocyanate and 2.2 parts by mass of isophorone diisocyanate were dissolved in 20.0 parts by mass of N, N-dimethylacetamide. To this was added a mixture solution of 12.1 parts by mass of 2,2-bis (hydroxymethyl) propionic acid, 10 parts by mass of both terminal diols (average molecular weight 1000) of polypropylene glycol, and 50.4 parts by mass of N, N-dimethylacetamide, Furthermore, 0.1 mass part of dibutyltin dilauryllates were added, and it heat-stirred for 7 hours at the temperature of 90 degreeC. Then, the polyurethane solution 5 (35 mass% of solid content) which has a carboxyl group and does not have ethylenically unsaturated bond was obtained by adding 16.7 mass parts of 1-methoxy- 2-propanol. The molecular weight of the polymer was measured by gel permeation chromatography (GPC) and found to be 51000 in terms of mass average molecular weight (polystyrene equivalent).

Synthesis Example 6 (Polyurethane solution having carboxyl group and ethylenically unsaturated bond: Polyurethane solution 6)

200 parts by mass of polyurethane solution 2 (solid content 35% by mass) synthesized in Synthesis Example 2, 1.36 parts by mass of glycidyl methacrylate, 0.014 parts by mass of methoxyhydroquinone, 0.109 parts by mass of triethylbenzyl ammonium chloride, N, N 2.7 parts by mass of -dimethylacetamide was dissolved and mixed and reacted at 80 ° C. for 24 hours to obtain a polyurethane solution 6 having a carboxyl group and an ethylenically unsaturated bond (solid content% by mass). It was 51000 in average molecular weight (polystyrene conversion).

Example 1

The photosensitive resin composition solution of the composition shown below was apply | coated to the 25-micrometer-thick polyethylene terephthalate film, and it dried, and formed the photosensitive resin composition layer of 15 micrometers in thickness. Subsequently, a 12 micrometer thick polypropylene film was laminated on the photosensitive resin composition layer, and dry film photoresist was produced.

Composition of Photosensitive Resin Composition Solution

Polyurethane solution 1 shown in Synthesis Example 1 (solid content concentration: 35 mass%). 51.9 parts by mass

Polymerizable compound (M-1 below). 10.9 parts by mass

4,4'-bis (diethylamino) benzophenone; 0.06 parts by mass

2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole. 1.4 parts by mass

Phenyltribromomethylsulfone 0.02 parts by mass

Loikako Crystal Violet 0.02 parts by mass

Marachite Green Oxalate 0.02 parts by mass

Ｐ-toluenesulfonamide... 0.63 parts by mass

Methyl ethyl ketone... 9.3 parts by mass

1-methoxy-2-propanol... 5.9 parts by mass

Table 1 shows the results of (1) shortest developing time, (2) resolution, (3) adhesion, and (4) tent film strength (tent film rupture number) of the dry film photoresist thus produced. In addition, the shortest developing time, the resolution, the adhesiveness, and the tent film strength were measured by the following method.

(1) Measuring method of shortest developing time

The photosensitive resin composition layer is laminated with a laminator (MODEL 8B-720-PH, Daisei Laminator Co., Ltd.) while fronting the surface and peeling off the polypropylene film of the dry film photoresist on the surface of the dried copper-clad laminate (no through hole). Product) to produce a laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The crimping conditions are the laminate plate temperature of 70 ° C, the pressing roller temperature of 105 ° C, the pressing roller pressure of 3 kg / cm 2, and the pressing speed of 1.2 m / min. A polyethylene terephthalate film is peeled off from a laminated body, and 30 mass% 1 mass% sodium carbonate aqueous solution is sprayed at 0.1 Mpa on the whole surface of the photosensitive resin composition layer on a copper clad laminated board. The time taken until the photosensitive resin composition layer on the copper clad laminated board was dissolved and removed from the spray start of the sodium carbonate aqueous solution was measured, and this is made into the shortest developing time.

(2) How to measure resolution

Under the same conditions as in the evaluation method of the shortest developing time of (1), a laminate composed of a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was produced, and left standing at room temperature (23 ° C., 55% RH) for 10 minutes. do. Ultra-high pressure mercury lamp (3kW ultra-high pressure mercury lamp double-sided simultaneous exposure apparatus HMW-6-N type) via a photomask (line / space = 1/1, line width 10 µm to 100 µm) on the surface of the polyethylene terephthalate film of the laminate; 40 mJ / cm <2> light is irradiated using oak Co., Ltd. product, and the photosensitive resin composition layer is exposed. After standing at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. A 30-degree aqueous solution of 1% by mass sodium carbonate was sprayed at a spray pressure of 0.1 MPa for 1.5 times the shortest developing time obtained in the above (1) on the entire surface of the resin composition layer on the copper clad laminate, and the uncured resin composition was dissolved and removed. The cured resin pattern is developed. Thereafter, water at 20 ° C. is sprayed at a spray pressure of 0.05 MPa for 80 seconds, the cured resin pattern is washed with water, and dried. The surface of the copper clad laminate in which the cured resin pattern thus obtained was formed was observed with an optical microscope, and the minimum line width without abnormalities such as clogging or twisting in the lines of the cured resin pattern was measured, and this was taken as the resolution. It is excellent that the value of the resolution is small, and shows high resolution (high resolution).

(3) Close measuring method

The same operation as the evaluation method of the resolution (2) above was carried out except that a line / space = 1/3 and a line width of 10 µm to 100 µm was used for the photomask, and abnormalities such as peeling and twisting were applied to the lines of the cured resin pattern. Measure the minimum line width without this, and make this a close contact. A close contact value shows that a small thing is excellent.

(4) Measuring method of tent film strength (tent film rupture number)

The copper clad laminate and the photosensitive resin composition layer were subjected to the same conditions as the evaluation method of the shortest developing time of (1) above, except that the copper clad laminate having 200 copper plated through holes having a diameter of 3 mm was used instead of the copper clad laminate having no through holes. And the laminated body which consists of a polyethylene terephthalate film is produced, and it stands still for 10 minutes at room temperature (23 degreeC, 55% RH). 50 mJ / cm <2> light is irradiated to the surface of the polyethylene terephthalate film of a laminated body using an ultrahigh pressure mercury lamp, and the whole surface of the photosensitive resin composition layer is exposed. After leaving at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. The aqueous solution of sodium carbonate was sprayed on the entire surface of the resin composition layer on the copper clad laminate to develop a cured resin pattern, except that the spray pressure of the aqueous solution of sodium carbonate was 0.2 MPa. Wash with water and dry. A copper chloride aqueous solution (etching liquid) at 45 ° C. is sprayed at a spray pressure of 0.1 MPa for 60 seconds on the surface of the copper clad laminate having the cured resin pattern thus obtained, and the copper clad laminate is etched. By the process so far, the total number of odd-numbered tears of the tent film was counted. (The smaller the number is, the higher the tent film strength is).

[Examples 2 to 5]

Instead of the polyurethane solution 1 in Example 1, except that the same amount of the polyurethane solutions 2 to 5 (35 mass% solution) shown in Synthesis Examples 2 to 5 shown in Table 1 below was used in the same manner as in Example 1 A dry film photoresist was prepared. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6

A dry film photoresist was produced in the same manner as in Example 1 except that the same amount of the polymerizable compound (M-2) was used instead of the polymerizable compound (M-1) in Example 1. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

EXAMPLES 7-10

Instead of the polyurethane solution 1 in Example 6, as shown in Table 1, except that the same amount of the polyurethane solutions 2 to 5 (35% by mass solution) shown in Synthesis Examples 2 to 5 was used. To prepare a dry film photoresist. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 11

A dry film photoresist was produced in the same manner as in Example 2 except that the same amount of the polymerizable compound (M-3) was used instead of the polymerizable compound (M-1) in Example 2. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Examples 12 to 22]

Dry film photoresist was produced in the same manner as in Examples 1 to 11 except that the thickness of the photosensitive resin composition layers of Examples 1 to 11 was 20 μm. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1

Instead of the polyurethane solution 1 (35 mass% solution) in Example 1, the monomer / 2-ethylhexyl meta which made methacrylic acid / methyl methacrylate / 2-isocyanate ethyl methacrylate, and n-butyl alcohol react 35% by mass solution of methacrylate / benzyl methacrylate copolymer (copolymer composition: 29/25/30/12/4 mol%, mass average molecular weight: 80000) (solvent is methylethylketone / 1-methoxy-2- A dry film photoresist was produced in the same manner as in Example 1 except that the same amount of propanol = 2/1 (mass ratio) was used. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 2-3

Instead of the polymeric compound (M-1) in the comparative example 1, except having used the same amount of the said polymeric compounds (M-2-M-3) as shown in following Table 1, it carried out similarly to the comparative example 1 A dry film photoresist was prepared. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4

A dry film photoresist was produced in the same manner as in Example 1 except that the same amount of Polyurethane Solution 6 (35 mass% solution) as that of Polyurethane Solution 2 in Example 2 was used. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5

A dry film photoresist was produced in the same manner as in Example 1 except that the same amount of Polyurethane Solution 6 (35 mass% solution) as that of Polyurethane Solution 2 in Example 7 was used. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 6

A dry film photoresist was produced in the same manner as in Example 1 except that the same amount of Polyurethane Solution 6 (35 mass% solution) as that of Polyurethane Solution 2 in Example 11 was used. The shortest developing time, resolution, adhesion, and tent film strength of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 23

In order to forcibly evaluate the preservation stability of the dry film photoresist manufactured similarly to Example 2, it stored for 72 hours in the dark room of 50 degreeC. The shortest developing time, resolution, adhesion, and tent film strength of the dry film photoresist after storage were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 24

In order to forcibly evaluate the preservation stability of the dry film photoresist manufactured similarly to Example 7, it stored for 72 hours in the dark room of 50 degreeC. The shortest developing time, resolution, adhesion, and tent film strength of the dry film photoresist after storage were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 25

In order to forcibly evaluate the preservation stability of the dry film photoresist manufactured similarly to Example 11, it stored for 72 hours in the dark room of 50 degreeC. The shortest developing time, resolution, adhesion, and tent film strength of the dry film photoresist after storage were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 7

In order to forcibly evaluate the preservation stability of the dry film photoresist manufactured similarly to the comparative example 4, it stored for 72 hours in the dark room of 50 degreeC. The shortest developing time, resolution, adhesion, and tent film strength of the dry film photoresist after storage were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 8

In order to forcibly evaluate the preservation stability of the dry film photoresist manufactured similarly to the comparative example 5, it stored for 72 hours in the dark room of 50 degreeC. The shortest developing time, resolution, adhesion, and tent film strength of the dry film photoresist after storage were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 9

In order to forcibly evaluate the preservation stability of the dry film photoresist manufactured similarly to the comparative example 6, it stored for 72 hours in the dark room of 50 degreeC. The shortest developing time, resolution, adhesion, and tent film strength of the dry film photoresist after storage were evaluated in the same manner as in Example 1. The results are shown in Table 2.

(*) Although the image development process was performed for 120 second, since the resin composition of the unexposed part was hardened | cured, evaluation could not be performed.

(**) Value evaluated using the shortest developing time as 120 seconds.

From the results of Table 1 and Table 2, the dry film photoresist (Comparative Examples 1 to 3) having a photosensitive resin composition containing no polyurethane resin had a significantly low tent film strength and had an ethylenically unsaturated bond. The dry film photoresist (Comparative Examples 4-9) having a photosensitive resin composition containing a polyurethane resin is excellent in resolution and tent film strength but poor in storage stability (because it hardens even in an unexposed portion), The shortest developing time is significantly long, resulting in problems such as deterioration of resolution and adhesion (not evaluated). On the other hand, the dry film photoresist (Examples 1 to 22) provided with the photosensitive resin composition containing the polyurethane resin which does not have an ethylenically unsaturated bond showed the outstanding performance in resolution, tent film strength, and storage stability.

Example 26

(Formation of Cured Resin Pattern by Laser Exposure)

The front surface is pressed and the photosensitive resin composition layer of the dry film photoresist prepared in Example 1 is pressed onto the surface of the dried copper-clad laminate while peeling off the polypropylene film on the photosensitive resin composition layer, and the copper clad laminate and the photosensitive resin composition The laminated body which consists of a layer and a polyethylene terephthalate film was produced. In the polyethylene terephthalate film of this laminate, using a laser exposure apparatus having a laser light source having a wavelength of 400 to 415 nm, a pattern having a line / space = 1/1, a line width of 10 μm to 100 μm, and a line / space = 1 The photosensitive resin composition layer was exposed by irradiating the laser beam of 105 mJ / cm <2> with the pattern of line width 10 micrometers-100 micrometers / 3. After leaving still at room temperature for 10 minutes, the polyethylene terephthalate film was peeled off from the laminate. A 30-degree 1 mass% sodium carbonate aqueous solution was sprayed at a pressure of 0.1 MPa for 17 seconds on the entire surface of the resin composition layer on the copper clad laminate, and the uncured resin composition was dissolved and removed to develop a cured resin pattern. Thereafter, water at 20 ° C. was sprayed at a spray pressure of 0.05 MPa for 80 seconds, and the cured resin pattern was washed with water and dried. As a result of observing the surface of the copper clad laminate in which the cured resin pattern thus obtained was formed with an optical microscope, the line width of the cured resin pattern formed by the line / space = 1/1 has no abnormality such as clogging and twisting (resolution). ) Is the minimum line width (adhesion) without abnormality such as peeling or twisting in the line of the cured resin pattern formed at 25 μm and line / space = 1/3 is 10 μm, compared with the case of exposure with light of ultra-high pressure mercury lamp. Resolution and closeness have improved respectively.

Example 26

(Formation of tent film by laser exposure)

The photosensitive resin composition layer of the dry film photoresist prepared in Example 1 was prepared on the surface of a copper clad laminate having 200 copper plated through holes with a diameter of 3 mm, and the polypropylene film on the photosensitive resin composition layer. It crimp | bonded, peeling, and produced the laminated body which consists of a copper clad laminated board, the photosensitive resin composition layer, and a polyethylene terephthalate film. 105 mJ / cm <2> of laser beams were irradiated to the whole surface of the polyethylene terephthalate film of this laminated body using the laser exposure apparatus which has a laser light source of wavelength 400-415 nm, and the photosensitive resin composition layer was exposed. After leaving still at room temperature for 10 minutes, the polyethylene terephthalate film was peeled off from the laminate. A 30-degree 1 mass% sodium carbonate aqueous solution was sprayed at a pressure of 2 MPa for 17 seconds on the entire surface of the resin composition layer on the copper clad laminate, and the uncured resin composition was dissolved and removed, the cured resin pattern was developed, washed with water and dried. The copper copper-clad aqueous solution (etching liquid) of 45 degreeC was sprayed at 0.1 Mpa for 60 second on the surface of the copper clad laminated board in which the obtained cured resin pattern was formed, and the copper clad laminated board was etched. As a result of counting the total number of odd numbers of the tent films ruptured by the processing up to this point, the tent film strength (tent film rupture number) was three, which was better than the exposure with light such as an ultra-high pressure mercury lamp.

The dry film photoresist of the present invention can be advantageously used for the production of printed wiring boards, particularly printed wiring boards having through holes or via holes.

The dry film photoresist of the present invention can form a tent film with high strength even if the thickness thereof is made thin without excessively increasing the compounding amount of the polymerizable compound. Therefore, the dry film photoresist of the present invention is excellent in resolution, tent film strength, and storage stability.

1 is a cross-sectional view of an example of a dry film photoresist according to the present invention.

2 is a schematic view showing a method of manufacturing a printed wiring board having a metal plated through hole according to the present invention.

(Explanation of the sign)

11: dry film photoresist 12: support (flexible transparent film support)

13: photosensitive resin composition layer 14: protective film

15, 16: cured resin composition 17: cured pattern

18: peeling piece 21: substrate for forming a printed wiring board

22: through hole 23: metal layer

24: Wiring pattern 31: Press roller

Claims (12)

A photosensitive resin composition layer which contains a support body and the polyurethane resin which has at least (A) carboxyl group and does not have ethylenically unsaturated bond, (B) polymeric compound which has ethylenically unsaturated bond, and (C) photoinitiator. Dry film photoresist, characterized in that. The polyurethane resin (A) having no ethylenically unsaturated bond comprises a reaction product of at least one diisocyanate compound and at least one diol compound containing a diol compound having a carboxyl group. Dry film photoresist. The dry film photoresist according to claim 1 or 2, wherein the mass average molecular weight of the polyurethane resin (A) having no ethylenically unsaturated bond is in the range of 5000 to 300,000. The dry film photoresist according to claim 1 or 2, wherein the polymerizable compound (B) is a compound containing a urethane bond. The photosensitive resin composition layer is a 10-90 mass% of polyurethane resins (A) which do not have an ethylenically unsaturated bond, 5-60 mass% of polymeric compounds (B), and a photoinitiator of Claim 1 or 2 0.1-30 mass% of (C) is contained, The dry film photoresist characterized by the above-mentioned. The dry film photoresist according to claim 1 or 2, wherein the photosensitive resin composition layer has a thickness of 5 µm or more and less than 35 µm. The dry film photoresist according to claim 1 or 2, wherein a protective film layer is formed on the photosensitive resin composition layer. The dry film photoresist according to claim 1 or 2, which is for manufacturing a printed wiring board. As a manufacturing method of a printed wiring board having a through hole or via hole, (1) preparing a substrate for forming a printed wiring board having a through hole or via hole and whose surface is covered with a metal layer; (2) The dry film photoresist according to any one of claims 1 to 6 is pressed onto the surface of the substrate for forming a printed wiring board so that the photosensitive resin composition layer is in contact with the metal layer, and the substrate for forming a printed wiring board and photosensitive A lamination step of obtaining a resin composition layer and a laminate in which a support is laminated in this order; (3) Irradiating light in a pattern form from the surface on the support side of the laminate, and curing the photosensitive resin composition layer to a cured resin composition region for forming a wiring pattern and a cured resin composition region for protecting a metal layer of a through hole or via hole. An exposure step of forming a cured resin composition pattern formed; (4) a support peeling step of removing the support from the laminate; (5) a developing step of dissolving and removing the uncured region of the resin composition layer on the substrate for forming a printed wiring board and exposing the metal layer of the uncured region on the substrate surface; (6) an etching step of dissolving and removing the metal layer of the exposed region with an etching solution; And (7) A method for producing a printed wiring board, comprising the step of removing the cured resin composition from the cured resin composition from the substrate for forming a printed wiring board. 10. The method for manufacturing a printed wiring board according to claim 9, wherein the light used in the step (3) is laser light. Polyurethane resin which has a (A) carboxyl group, does not have ethylenically unsaturated bond, and (B) polymerizable unsaturated bond on the board | substrate for forming a printed wiring board which has a through-hole or via-hole, and whose surface was covered with the metal layer. The photosensitive resin composition layer containing a compound and (C) photoinitiator is laminated | stacked, The laminated body characterized by the above-mentioned. The laminate according to claim 11, wherein a support is laminated on the photosensitive resin composition layer.