JP2005173049A - Dry film photoresist - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dry film photoresist having high resolution, tent film strength and storage stability. <P>SOLUTION: The dry film photoresist comprises a support body and a photosensitive resin composition layer, containing at least (A) polyurethane resin, having a carboxyl group and no ethylenically unsaturated bond, (B) a polymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  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 producing a printed wiring board having a through hole or a via hole 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, a dry film photoresist comprising a wiring pattern comprising a support (particularly a flexible transparent film support) and a photosensitive resin composition layer formed on the support. It is performed by the photolithographic technique using this. 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 on the inner wall of the through hole, and then a photosensitive resin composition layer of a dry film photoresist on the substrate surface Are overlapped and closely adhered to each other, and the photosensitive resin composition layer is cured by irradiating light in a predetermined pattern on the wiring pattern forming region and the region including the through hole opening. Next, the support of the dry film photoresist is peeled off, and the uncured photosensitive resin composition region is removed. When this laminate is immersed in an etching solution for dissolving copper, the exposed metal layer portion is etched, and the same copper-clad pattern as the pattern irradiated with light can be obtained. Thereafter, the cured resin composition is removed to form a copper wiring pattern on the substrate surface.

In recent years, the demand for high-density printed wiring boards has increased, 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, however, as described above, the dry film photoresist also serves to protect and protect the metal layer on the inner wall surface of the through hole formed in the printed wiring board, and dissolves the uncured photosensitive resin composition region. There is a drawback that the cured resin composition on the through hole is broken in the removing step.
Although the cured resin composition on the through hole is referred to as a tent film, the following results have been disclosed as means for increasing the strength of the tent film.

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

  In Patent Document 2, a photosensitive resin composition layer as a photoresist having excellent tent film strength includes an alkali-soluble polymer compound, a polymerizable urethane compound having an ethylenically unsaturated bond, and three or more ethylenic monomers in one molecule. A dry film photoresist comprising a photopolymerizable monomer having an unsaturated group and a photopolymerization initiator is disclosed. In the examples of this patent document, a high molecular weight urethane compound and two low molecular weight urethane compounds are used as the polymerizable urethane compound.

Japanese Patent Laid-Open No. 10-142789 JP 2001-117225 A

In order to meet the demand for finer and higher density printed wiring boards, further improvements in the resolution and tent film strength of dry film photoresists are desired. To increase the resolution of the dry film photoresist, it is effective to reduce the thickness of the photosensitive resin composition layer, but if the thickness of the photosensitive resin composition layer is reduced, the tent film strength decreases. There is a problem.
As described above, it is effective to use a polymerizable urethane compound to improve the tent film strength of the dry film photoresist. However, according to the view of the present inventor, when the compounding amount of the polymerizable compound in the photosensitive resin composition layer of the dry film photoresist is increased, edge fusion that the photosensitive resin composition exudes from the roll during storage occurs. There are cases in which problems such as being easy to do occur. In addition, when a high molecular weight compound such as an oligomer or a polymer is used as the polymerizable compound, edge fusion can be prevented, but fogging may occur in the resist during storage and storage stability may be reduced. There is a limit to improving the tent film strength only by improving the polymerizable 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.

  The present inventor uses a polyurethane resin having a carboxyl group and having no ethylenically unsaturated bond as a binder in the photosensitive resin composition layer, so that the polymerizable compound can be reduced even if the thickness is reduced. The inventors have found that a tent film having high strength can be formed without adding excessively, and have reached the present invention.

  Accordingly, the present invention provides a support, (A) a polyurethane resin having a carboxyl group and no ethylenically unsaturated bond, (B) a polymerizable compound having an ethylenically unsaturated bond, and (C) photopolymerization. A dry film photoresist having a photosensitive resin composition containing an initiator.

Preferred embodiments of the present invention are as follows.
(1) 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.
(2) The mass average molecular weight of the polyurethane resin (A) having no ethylenically unsaturated bond is in the range of 5,000 to 300,000.
(3) The polymerizable compound (B) is a compound containing a urethane bond.
(4) The photosensitive resin composition layer is 10 to 90% by mass of the polyurethane resin (A) having no ethylenically unsaturated bond, 5 to 60% by mass of the polymerizable compound (B), and a photopolymerization initiator (C ) In an amount of 0.1 to 30% by mass.
(5) The thickness of the photosensitive layer resin composition layer is 5 μm or more and less than 35 μm.
(6) A protective film layer is provided on the photosensitive layer resin composition layer.
(7) For printed wiring board manufacture.

The present invention also resides in a method for manufacturing a printed wiring board having a through hole or a via hole whose inner wall surface is covered with a metal layer.
(1) A step of preparing a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer;
(2) The dry film photoresist of the present invention is pressure-bonded to the surface of the printed wiring board forming substrate so that the photosensitive layer resin composition layer is in contact with the metal layer, and the printed wiring board forming substrate and photosensitive layer resin composition A layering step of obtaining a layered body in which the physical layer and the support are laminated in this order;
(3) Irradiate light from the surface of the laminate on the support side to cure the photosensitive resin composition layer, and protect the metal layer of the cured resin composition region for forming the wiring pattern and the through hole or via hole. An exposure step of forming a cured resin composition pattern comprising a cured resin composition region for use;
(4) a support peeling process for peeling the support from the laminate;
(5) A development step of dissolving and removing the uncured region of the resin composition layer on the printed wiring board forming substrate to expose the metal layer of the uncured region on the substrate surface;
(6) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(7) A cured resin composition removing step of removing the cured resin composition from the printed wiring board forming substrate.

  The present invention further includes (A) a polyurethane resin having a carboxyl group and having no ethylenically unsaturated bond on a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer, There is also a laminate in which a photosensitive resin composition layer containing (B) a polymerizable compound having an ethylenically unsaturated bond and (C) a photopolymerization initiator is laminated.

  The dry film photoresist of the present invention can form a high-strength tent film even if the thickness is reduced 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.

FIG. 1 is a cross-sectional view of an example of the dry film photoresist of the present invention.
In FIG. 1, a dry film photoresist 11 includes a support (flexible transparent film support) 12, a photosensitive resin composition layer 13, and a protective film 14 laminated in this order. The photosensitive resin composition layer 13 includes (A) a polyurethane resin having a carboxyl group and no ethylenically unsaturated bond, (B) a polymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. A photosensitive resin composition containing The thickness of the photosensitive resin composition layer 13 is not particularly limited, but is generally 1 to 200 μm, preferably 5 μm or more and less than 35 μm, more preferably 10 to 30 μm, and still more preferably 10 It is in the range of ˜25 μm.

[Polyurethane resin having carboxyl group and no ethylenically unsaturated bond (A)]
The polyurethane resin (A) having a carboxyl group and having no ethylenically unsaturated bond used in the dry film photoresist of the present invention is at least one or more containing at least one diisocyanate compound and a diol compound having a carboxyl group. It is preferable that it is a reaction product with this diol compound.
The polyurethane resin used in the present invention may be soluble in an organic solvent or an aqueous dispersion.

<Diisocyanate compound>
A preferable diisocyanate compound is a diisocyanate compound represented by the following general formula (1).
OCN-X-NCO (1)
In formula (1), X represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, X may have another functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.

  Specific examples of the diisocyanate compound represented by the general formula (1) include those shown below. That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate Aromatic diisocyanate compounds such as 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. Aliphatic diisocyanate compounds; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate And alicyclic diisocyanate compounds such as 1,3- (isocyanatomethyl) cyclohexane; reaction of diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate A diisocyanate compound which is a product; These diisocyanate compounds may be used alone or in combination of two or more.

<Diol compound>
A preferable diol compound is a diol compound having a carboxyl group represented by the following general formula (2).
HO-Y-OH (2)
In formula (2), Y represents a divalent aliphatic or aromatic hydrocarbon group having a carboxyl group.

  The carboxyl group-containing diol compound is obtained by ring-opening a diol compound and / or tetracarboxylic dianhydride represented by any one of the following general formula (3), formula (4) or formula (5) with a diol compound. Particularly preferred is a 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, etc.), —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, Each group such as an aralkyl group having 7 to 15 carbon atoms is included.) May be an alkyl group, an aralkyl group, an aryl group, an alkoxy group or an aryloxy group, preferably a hydrogen atom. And an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms.
In formula (4), Ar < ¹ > shows the trivalent aromatic hydrocarbon group which may have a substituent, Preferably it shows a C6-C15 aromatic hydrocarbon group.

In formula (3), formula (4) and formula (5), L ¹ , L ² and L ³ may be the same or different, and each may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, An aryl group, an alkoxy group, a halogen atom) which may have a divalent aliphatic or aromatic hydrocarbon group, preferably an alkylene group having 1 to 20 carbon atoms or 6 to 15 carbon atoms An arylene group, more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, L ¹ , L ² and L ³ may have other functional groups that do not react with the isocyanate group, such as carbonyl group, ester group, urethane group, amide group, ureido group, and ether group. Good. Incidentally, the formula (3) R ¹ in, L ^1, L ² and L ^3, L ¹ in Formula (4), L ² and L ^3, Equation (5) in L ^1, L ² and L ³ of Two or three of them may form a ring.

  Specific examples of the diol compound having a carboxyl group represented by formula (3), formula (4) or formula (5) include the following. 3,5-dihydroxybenzoic 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.

  Preferred tetracarboxylic dianhydrides include those represented by the following general formula (6), formula (7) or formula (8).

In the formula, L ⁴ may have a single bond or 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). valent aliphatic or aromatic hydrocarbon group, -CO -, - SO -, - SO 2 -, - indicating O- or -S-. Preferably a single bond, a divalent aliphatic hydrocarbon group having a carbon number of _{1~15, -CO -, - SO 2} -, - a O- or -S-.
R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or a halogen atom, preferably a hydrogen atom or a carbon atom having 1 to 8 carbon atoms. An alkyl group, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom;
Two of L ⁴ , R ⁸ and R ⁹ may be bonded to form a ring.

In the formula, L ⁵ may have a single bond or 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). valent aliphatic or aromatic hydrocarbon group, -CO -, - SO -, - SO 2 -, - indicating O- or -S-. Preferably a single bond, a divalent aliphatic hydrocarbon group having a carbon number of _{1~15, -CO -, - SO 2} -, - a O- or -S-.
L ⁶ and L ⁷ may be the same or different and each represents a single bond or a divalent aliphatic hydrocarbon group, preferably a single bond or a methylene group.
R ¹⁰ and R ¹¹ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogen atom, preferably a hydrogen atom, an alkyl having 1 to 8 carbon atoms or the number of carbon atoms 6-15 aryl groups are shown.
Two of L ⁵ , R ¹⁰ and R ¹¹ may combine to form a ring.

  In the formula, a circle of A represents a mononuclear or polynuclear aromatic ring. An aromatic ring having 6 to 18 carbon atoms is preferred.

  Specific examples of the compound represented by formula (6), formula (7), or formula (8) include those shown below. That is, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis (3 , 4-Dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-[3,3 ′-(alkylphosphoryldiphenylene) -bis (iminocarbonyl) Aromatic tetracarboxylic dianhydrides such as diphthalic dianhydride, adducts of hydroquinone diacetate and trimet acid anhydride, adducts of diacetyldiamine and trimet acid anhydride; 5- (2,5- Oxotetrahydrofuryl) -3-methyl-3-cyclohexsi-1,2-dicarboxylic anhydride (Dainippon Ink Chemical Co., Ltd., Epicron B-4400), 1,2,3,4-cyclopentane Cycloaliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride; 1,2,3,4- Aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,4,5-pentanetetracarboxylic 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, neo Pentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4.trimethyl-1,3-pentanediol, 1,4-bis-β- Hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide of bisphenol A , Ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxy Ethyl sulfone, bis (2-hydroxyethyl) -2,4-tolylene dicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylene dicarbamate, and bis (2-hydroxyethyl) isophthalate and the like.

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

  For the synthesis of the polyurethane resin, other diol compounds that do not have a carboxyl group and may have other substituents that do not react with isocyanate can be used in combination. The linking group that connects two hydroxyl groups of other diol compounds includes a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, a carbonyl group (—CO—), oxygen Atom (—O—), sulfur atom (—S—), imino group (—NH—), a substituted imino group in which a hydrogen atom of imino group is substituted with a monovalent hydrocarbon group, or a combination thereof It is preferable.

As other diol compounds, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound and the like are widely used.
Examples of the polyether diol compound include compounds represented by the following general formula (9), formula (10), formula (11), formula (12) or formula (13), and ethylene oxide and propylene oxide having a hydroxyl group at the terminal. Of the random copolymer.

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 the formula (13) each independently represent the following group.

  A, b, c, d, e, f and g in the formulas (9) to (13) represent an integer of 2 or more, preferably an integer of 2 to 100.

  Specific examples of the polyether diol compound represented by formula (9) or formula (10) include the following. 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-butylene glycol, Tri-1,3-butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol having a weight average molecular weight of 1000, polyethylene glycol having a weight average molecular weight of 1500, poly having a weight average molecular weight of 2,000 Tylene glycol, polyethylene glycol having a weight average molecular weight of 3000, polyethylene glycol having a weight average molecular weight of 7500, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, polypropylene glycol having a weight average molecular weight of 1000, polypropylene glycol having a weight average molecular weight of 2000 , Polypropylene glycol having a weight average molecular weight of 3000, polypropylene glycol having a weight average molecular weight of 4000, and the like.

  Specific examples of the diol compound represented by the formula (11) include those shown below. Sanyo Chemical Industries, Ltd. (trade name) PTMG650, PTMG1000, PTMG2000, PTMG3000, etc.

  Specific examples of the polyether diol compound represented by the formula (12) include those shown below. Sanyo Chemical Industries, Ltd. (trade name) New Pole PE-61, New Pole PE-62, New Pole PE-64, New Pole PE-68, New Pole PE-71, New Pole PE-74, New Pole PE-75, New Pole PE-78, New Pole PE-108, New Pole PE-128, New Pole PE-61, etc.

  Specific examples of the polyether diol compound represented by the formula (13) include those shown below. Sanyo Chemical Industries, Ltd. (trade 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, New Pole BPE-180, New Pole BPE-2P, New Pole BPE-23P, New Pole BPE-3P, New Pole BPE-5P, etc.

  Specific examples of the random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal include the following. Sanyo Chemical Industries, Ltd. (trade name) New Pole 50HB-100, New Pole 50HB-260, New Pole 50HB-400, New Pole 50HB-660, New Pole 50HB-2000, New Pole 50HB-5100, and the like.

  Examples of the polyester diol compound include compounds represented by the following general formula (14) or formula (15).

In the formula, L ⁸ , L ⁹ and L ¹⁰ may be the same or different and each represents 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 that 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 be present.
n1 and n2 are each an integer of 2 or more, and preferably an integer of 2 to 100.

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

（１６）

(16)

In the formula, L ¹² may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ¹² represents an alkylene group or an arylene group. In addition, other functional groups that do not react with isocyanate groups (for example, ether groups, carbonyl groups, ester groups, cyano groups, urethane groups, amide groups, ureido groups, halogen atoms, etc.) may be present in L ^12. .
n3 is an integer of 2 or more, preferably an integer of 2 to 100.

  Specific examples of the diol compound represented by formula (14), formula (15) or formula (16) include the following exemplified compounds (No. 1) to (No. 13). N in the specific examples is an integer of 2 or more.

  Furthermore, as other diol compounds, diol compounds represented by the following general formulas (17) to (27) can also be suitably used.

^{HO-L 13 -O-CO-} L 14 -CO-O-L 13 -OH (17)
^{HO-L 14 -CO-O-} L 13 -OH (18)

In the formula, each of L ¹³ and L ¹⁴ may be the same or different, and may be a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, —F, —Cl, —Br, — And a divalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group which may have a halogen atom such as I.). If necessary, L ¹³ and L ¹⁴ may have another functional group that does not react with the isocyanate group (for example, carbonyl group, ester group, urethane group, amide group, ureido group, etc.). Note that L ¹³ and L ¹⁴ may form a ring.

  Specific examples of the compound represented by the above formula (17) or formula (18) include the following exemplified compounds (No. 14) to (No. 27).

  In formula, n4 shows an integer greater than or equal to 2, 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 are an alkyl group, an aralkyl group, an aryl group, —COOR ¹⁶ , —OR ¹⁷ , —NHCONHR ¹⁸ , —NHCOOR ¹⁹ , —NHCOR ²⁰ , —OCONHR. ²¹ (where 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, branched alkyl group, cyclic alkyl group), carbon atom And an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.). Preferably, it is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 15 carbon atoms, or —NHCOR ²⁰ .

  Specific examples of the diol compound represented by formula (19) or formula (20) include those shown below. That is, as formula (19), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1 , 8-octanediol and the like. Examples of the formula (20) include the following exemplary compounds (No. 28) to (No. 33).

^{HO-L 15 -NH-CO-} L 16 -CO-NH-L 15 -OH (21)
^{HO-L 16 -CO-NH-} L 15 -OH (22)

In the formula, L ¹⁵ and L ¹⁶ may be the same as or different from each other, and each may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom (—F, —Cl, — And a divalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group which may have a group such as Br, -I). If necessary, L ¹⁵ and L ¹⁶ may have another functional group that does not react with an isocyanate group (for example, a carbonyl group, an ester group, a urethane group, an amide group, and a ureido group). Note that L ¹⁵ and L ¹⁶ may form a ring.

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

^{HO-Ar 2 - (L 17} -Ar 3) n5 -OH (23)
^{HO-Ar 2 -L 17 -OH (} 24)

In the formula, L ¹⁷ is a divalent aliphatic hydrocarbon group which may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom is preferable). Indicates. If necessary, L ¹⁷ may have another functional group that does not react with an isocyanate group (for example, an ester group, a urethane group, an amide group, or 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, preferably an aromatic group having 6 to 15 carbon atoms. .
n5 represents an integer of 0 to 10.

  Specific examples of the diol compound represented by the above formula (23) or formula (24) include those shown below. That is, catechol, resorcin, hydroquinone, 4-methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4-methylresorcin, 4-ethylresorcin, 4-t-butyl Resorcin, 4-hexyl resorcin, 4-chloro resorcin, 4-benzyl resorcin, 4-acetyl resorcin, 4-carbomethoxy resorcin, 2-methyl resorcin, 5-methyl resorcin, t-butyl hydroquinone, 2,5-di- t-butylhydroquinone, 2,5-di-t-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylcarboaminohydroquinone, methylureidohydroquinone, methylthiohydroquinone, benzonor Runene-3,6-diol, bisphenol A, bisphenol S, 3,3′-dichlorobisphenol S, 4,4′-dihydroxybenzophenone, 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-hydroxyphenyl) methylamine, 1,3 -Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,5-dihydroxyanthraquinone, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxy-3, 5-di-t-butyl Benzyl alcohol, 4-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxyphenethyl alcohol, 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenyl acetate, and resorcin mono -2-hydroxyethyl ether and the like.

In the 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 each} have 1 to 10 alkyl groups, aralkyl groups having 7 to 15 carbon atoms, etc.) are included.) An alkyl group, aralkyl group, aryl group, alkoxy group or aryloxy group which may have , Preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms.

In the formula (25), the formula (26) and the formula (27), L ¹⁸ , L ¹⁹ and L ²⁰ may be the same or different, and each may be a single bond, a substituent (for example, alkyl, aralkyl, aryl, alkoxy). A divalent aliphatic or aromatic hydrocarbon group optionally having a halogen group, preferably an alkylene group having 1 to 20 carbon atoms or 6 to 15 carbon atoms. An arylene group, more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, L ¹⁸ , L ¹⁹ and L ²⁰ may have other functional groups that do not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, and an ether group. . Incidentally, R ²² of formula (25), L ^18, L ¹⁹ and L ^20, L ^18, L ¹⁹ and L ²⁰ of the formula (26), two of L ^18, L ¹⁹ and L ²⁰ of the formula (27) Or three may form a ring.

Ar ⁴ in the formula (26) represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably an aromatic group having 6 to 15 carbon atoms.
In Formula (25), Formula (26), and Formula (27), Z ¹ represents the following group.

Here, R ³⁰ and R ³¹ may be the same or different and each represents a hydrogen atom, sodium, potassium, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a carbon atom. An aryl group having 6 to 15 atoms is shown.

  Other diol compounds can be used alone or in combination of two or more.

  The polyurethane resin that can be used in the present invention is synthesized by adding the above-mentioned isocyanate compound and diol compound in an aprotic solvent to a known catalyst having an activity corresponding to the reactivity and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, it is finally treated by treatment with alcohols or amines. In the form in which no isocyanate group remains.

  The polyurethane resin used in the present invention preferably contains a carboxyl group in the range of 0.3 to 3.5 meq / g, more preferably in the range of 0.5 to 3.3 meq / g. The molecular weight of the polyurethane resin is in the range of 5,000 to 300,000, more preferably in the range of 10,000 to 250,000, and still more preferably in the range of 20,000 to 200,000 as the mass average molecular weight (polystyrene standard).

  The polyurethane resin content of the photosensitive resin layer is generally in the range of 10 to 90% by mass, preferably in the range of 40 to 80% by mass, and particularly preferably in the range of 45 to 65% by mass.

[Polymerizable compound (B)]
The polymerizable compound used in the dry film photoresist of the present invention preferably has two or more ethylenically unsaturated bonds. Examples of the polymerizable compound include an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid, Examples include amides with aliphatic polyvalent amine compounds. Moreover, the polymeric compound which has a urethane bond can also be used.

  Specific examples of esters [(meth) acrylic acid esters] of acrylic acid and methacrylic acid and aliphatic polyhydric alcohol compounds include (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, 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, tetrapropyl Pyrene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meta ) Acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate 1,4-cyclohexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, 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 oligomer, bis [p- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, and bis [p-((meth)) Acryloxyethoxy) phenyl] dimethylmethane and the like.

Examples of ebester (itaconic acid ester) of itaconic acid and an aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, and 1,4-tandiol. Examples include diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.
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 (isocrotonate) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of esters of maleic acid and aliphatic polyhydric alcohol compounds (maleic acid esters) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Specific examples of amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound include methylene bis- (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis- (meth) acrylamide, diethylenetriamine tris ( Examples include meth) acrylamide and xylylene bis (meth) acrylamide.

  As the polymerizable compound having a urethane bond, those represented by the following general formula (28), formula (29) or formula (30) are preferable.

In formula (28), R ³² and R ³³ each independently represents a hydrogen atom or a methyl group.
L ²¹ and L ²² each independently represent a group in which a divalent aliphatic hydrocarbon group (having 1 to 15 carbon atoms) and an oxygen atom (—O—) are combined. Examples of L ²¹ and L ²² are shown below. The left side is bonded to an oxygen atom, and the right side is bonded to a carbon atom.
L-1: —CH ₂ —CH ₂ —O—
L-2: —CH ₂ —CH (CH ₃ ) —O—
L-3: —CH (CH ₃ ) —CH ₂ —O—
L-4: —CH ₂ —CH ₂ —CH ₂ —O—,
L-5: —CH (CH ₃ ) —CH ₂ —CH ₂ —O—
L-6: —CH ₂ —CH (CH ₃ ) —CH ₂ —O—
L-7: —CH ₂ —CH ₂ —CH (CH ₃ ) —O—
L-8: —CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—

Z ² represents a divalent organic group. An alkylene group having 1 to 25 carbon atoms, an arylene group, and a group obtained by combining these are preferable.
p1 and p2 each independently represent an integer of 1 to 25.

In the 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 in which a divalent aliphatic hydrocarbon group (having 1 to 15 carbon atoms) and an oxygen atom (—O—) are combined. Examples of L ²³ , L ²⁴ and L ²⁵ are shown below. The left side is bonded to an oxygen atom, and the right side is bonded to a carbon atom.
L-9: —CH ₂ —CH ₂ —O—
L-10: —CH ₂ —CH (CH ₃ ) —O—
L-11: —CH (CH ₃ ) —CH ₂ —O—
L-12: —CH ₂ —CH ₂ —CH ₂ —O—,
L-13: —CH (CH ₃ ) —CH ₂ —CH ₂ —O—
L-14: —CH ₂ —CH (CH ₃ ) —CH ₂ —O—
_{L-15: -CH 2 -CH 2} -CH (CH 3) -O-
L-16: —CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—

Z ³ , Z ⁴ and Z ⁵ are preferably an alkylene group having 1 to 25 carbon atoms, an arylene group and a group obtained by combining these.
q1, q2 and q3 each independently represents an integer of 1 to 25.

In the formula (30), R ³⁷ represents a hydrogen atom or a methyl group.
L ²⁶ and L ²⁷ each independently represent a group in which a divalent aliphatic hydrocarbon group (having 1 to 15 carbon atoms) and an oxygen atom (—O—) are combined. Examples of L ²⁶ and L ²⁷ are shown below. The left side is bonded to an oxygen atom, and the right side is bonded to a carbon atom or A.
L-17: —CH ₂ —CH ₂ —O—
L-18: —CH ₂ —CH (CH ₃ ) —O—
L-19: —CH (CH ₃ ) —CH ₂ —O—
L-20: —CH ₂ —CH ₂ —CH ₂ —O—,
L-21: —CH (CH ₃ ) —CH ₂ —CH ₂ —O—
L-22: —CH ₂ —CH (CH ₃ ) —CH ₂ —O—
_{L-23: -CH 2 -CH 2} -CH (CH 3) -O-
L-24: —CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—

Z ⁶ represents a divalent organic group. An alkylene group having 1 to 25 carbon atoms, an arylene group, and a group obtained by combining these are preferable.
r1 and r2 each independently represents an integer of 1 to 50.
r3 represents an integer of 3 to 6. From the standpoint of feedability for synthesizing the polymerizable monomer, r3 is preferably 3, 4 or 6.
A represents an r3-valent (3-6 valent) organic group. A is preferably an aliphatic hydrocarbon group which may have an ether bond in the middle of the r3 valence having 1 to 100 carbon atoms.

  In addition to the above compounds containing urethane groups, urethane compounds described in JP-B-48-41708, JP-A-51-37193, and JP-B-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 A vinyl monomer containing a hydroxyl group in the molecule (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy, etc.) and a trimer thereof, and adducts thereof with polyfunctional alcohols such as trimethylolpropane). Propyl (meth) acrylate, 4-H Roxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol A urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a mono (meth) acrylate or the like can also be used.

Further, polyester acrylates and epoxy resins as described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490 were reacted with (meth) acrylic acid. Polyfunctional acrylates and methacrylates such as epoxy acrylates can also be used. In addition, esterified products obtained from phthalic acid, trimellitic acid and the like and a vinyl monomer containing a hydroxyl group in the molecule are also included. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984) as photocurable monomers and oligomers can also be used.
These polymerizable compounds can be used alone or in combination of two or more.

  The content of the polymerizable compound in the photosensitive resin composition layer is generally in the range of 5 to 60% by mass, preferably in the range of 10 to 50% by mass, and particularly preferably in the range of 20 to 45% by mass. If the content of the polymerizable compound is less than the above range, the strength of the cured film (tent film) tends to decrease, and if it is large, edge fusion during storage (exudation failure from the end of the roll) is likely to occur. There is a tendency.

[Photoinitiator (C)]
As the photopolymerization initiator used in the dry film photoresist of the present invention, any compound having the ability to initiate the polymerization of the above-described polymerizable compound can be used, and is particularly sensitive to violet light from the ultraviolet region. Any material can be suitably used. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm). The photopolymerization initiator may be an activator that generates an active radical by generating some action with the photoexcited sensitizer.

  Examples of the photopolymerization initiator preferably used in the dry film photoresist of the present invention include halogenated hydrocarbon derivatives (preferably those having a triazine skeleton), hexaarylbiimidazoles, ketoxime derivatives, and organic peroxides. Thio compounds, ketoxime esters, ketone compounds, aromatic onium salts, ketoxime ethers and the like. Of these, the use of a halogenated hydrocarbon having a triazine skeleton, a ketoxime derivative, a hexaarylbiimidazole, a ketoxime ester, and a ketone compound is particularly sensitive to the sensitivity, storage stability, and photosensitive resin composition of the photosensitive resin composition layer. This is preferable from the viewpoint of adhesion between the layer and the printed wiring board forming substrate.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds.
Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (p- Chlorophenyl) -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 - triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine;

Compounds described in GB 1388492, such as 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (p-methylstyryl) -4,6-bis (trichlor) Methyl) -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 JP-A-53-133428, for example, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-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 DE 33 37 024, 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-vinylenepheny ) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5- Triazine;

FC Schaefer et al., J. Org. Chem .; 29, 1527 (1964) described 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;
Compounds described in JP-A-62-258241, 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-triazi ;

Compounds described in JP-A-5-281728, such as 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] -1,3,5-triazine described in JP-A-5-34920; and A halogenated hydrocarbon compound having a triazine skeleton of an electron transfer type initiation system described in JP-A No. 2001-305734.
All of these can be suitably used.

  Examples of the ketoxime derivative suitably used in the present invention include compounds represented by the following general formula (31).

In the formula (31), R ³⁸ and R ³⁹ are the same or different and each represents a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group.
R ⁴⁰ and R ⁴¹ are each independently a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, And a substituted thio group. R ⁴⁰ and R ⁴¹ are bonded to each other to form a ring, and —O—, —NR ⁴⁴ — (R ⁴⁴ is hydrogen or a hydrocarbon group which may have a substituent), —O It represents an alkylene group having 2 to 8 carbon atoms, which may contain —CO—, —NH—CO—, —S—, and / or —SO ₂ — in the connecting main chain of the ring.
R ⁴² and R ⁴³ represent a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a substituted carbonyl group.

  Specific examples of ketoxime derivatives include p-methoxyphenyl 2-N, N-dimethylaminopropylketone oxime-O-allyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-allyl ether, 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-methoxyphenyl 2-morpholinopropylketone oxime-O-n-dodecyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-methoxyethoxyethyl ether, p-methylthiol Nyl 2-morpholinopropyl ketone oxime-Op-methoxycarbonylbenzyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O-methoxycarbonyl methyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O -Ethoxycarbonylmethyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-4-butoxycarbonylbutyl ether, p-methylthiophenyl 2-morpholinopropylketone oxime-O-2-ethoxycarbonylethyl ether, p-methylthio Phenyl 2-morpholinopropyl ketone oxime-O-methoxycarbonyl-3-propenyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxy It can be mentioned -O- benzyloxycarbonyl ether is not limited thereto.

  Examples of the hexaarylbiimidazole used in the present invention include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (o-bromo). Phenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl)- 4,4 ', 5 '- tetraphenyl biimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4', 5,5'-tetraphenyl biimidazole. These biimidazoles can be easily synthesized by the methods disclosed in, for example, Bull. Chem. Soc. Japan, 33,565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). it can.

  Examples of ketoxime esters include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2 -Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, and 2-ethoxycarbonyloxyimino Examples include -1-phenylpropan-1-one.

  Examples of the ketone compound 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, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4-diethylthioxanthone, fluorenone , And acridone.

  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, Bromomethyl sulfone, phenyltrichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -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-furoyl) -7-diethylaminocoumarin, 3- (p-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, etc.), amines (for example, ethyl p-dimethylaminobenzoate, p-dimethyl) N-butyl aminobenzoate, phenethyl p-dimethylaminobenzoate, 2-phthalimidoethyl p-dimethylaminobenzoate, 2-methacryloyloxyethyl p-dimethylaminobenzoate, pentamethylenebis (p-dimethylaminobenzoate), m -Phenethyl of dimethylaminobenzoic acid And pentamethylene ester, 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-bromo-N, N-dimethylaniline , Tridodecylamine, leucocrystal violet, etc.), compounds disclosed in JP-A Nos. 53-133428, 57-1819, 57-6096, and US Pat. No. 3,615,455. Also mentioned.

  These photopolymerization initiators can be used alone or in combination of two or more. It is also possible to use two or more compounds in combination between different species. The usage-amount of a photoinitiator exists in the range of 0.1-30 mass% with respect to all the components of the photosensitive resin composition layer, Preferably it is the range of 0.5-20 mass%, Most preferably It is in the range of 1 to 15% by mass.

[Sensitizer]
A so-called sensitizer can be added when a visible ray or ultraviolet laser is used as the ray (active energy ray). Examples of the sensitizer include known polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxaxene). Carbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine, alkylacridine), anthraquinones (eg, , Anthraquinone), squariums (eg, squalium), acridones (eg, N-methylacridone, N-butyl-2-chloroacridone), and coumarins (eg, coumarin-1, bear) Down -102, coumarin -152) it can be suitably used.

  The addition amount of the sensitizer is in the range of 0.05 to 30% by mass, preferably in the range of 0.1 to 20% by mass, and particularly preferably 0.2% with respect to all the components of the photosensitive resin composition layer. It is the range of -10 mass%. If the amount of the sensitizer added is too large, it may precipitate from the photosensitive resin composition layer during storage, and if it is too small, the sensitivity to active energy rays will be reduced, and the exposure process will take a long time. Productivity may be reduced.

[Other ingredients]
In the dry film photoresist of the present invention, if necessary, the photosensitive resin composition layer, thermal polymerization inhibitor, plasticizer, color change agent, dye (colorant), further promote adhesion to the substrate surface for printed wiring board production Agents and other auxiliaries may be added. By adding these, properties such as the stability, photographic properties, print-out properties, and film properties of the desired dry film photoresist can be adjusted.

[Thermal polymerization inhibitor]
The thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in 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, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Use chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, picric acid, p-toluidine, methylene blue, organic copper, methyl salicylate, phenothiazine, etc. Can do.

  The addition amount of the thermal polymerization inhibitor is preferably in the range of 0.001 to 5 mass%, more preferably 0.01 to 2 mass% with respect to the polymerizable compound content of the photosensitive resin composition layer. It is a range, Especially preferably, it is the range of 0.05-1 mass%. When the addition amount of the thermal polymerization inhibitor exceeds this range, the sensitivity to active energy rays tends to decrease, and when it exceeds this range, the stability during storage tends to deteriorate.

[Plasticizer]
The plasticizer is added to control the film physical properties (flexibility) of the photosensitive resin composition layer. Examples of the plasticizer include phthalates such as dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, and diallyl phthalate; Glycol esters such as diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, and triethylene glycol dicabrylate; Phosphate esters such as diphosphate and triphenyl phosphate; p-toluenesulfonamide Amides such as benzenesulfonamide and Nn-butylacetamide; aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl sepacate, dioctyl azelate, and dibutyl malate Class: Triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, and dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate can be used.

  The addition amount of the plasticizer is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, particularly preferably relative to all components of the photosensitive resin composition layer. It is the range of 1-30 mass%.

[Discoloring agent]
The color changing agent is added to give a visible image (printing function) to the photosensitive resin composition layer after exposure. Examples of the color changing agent include tris (p-dimethylaminophenyl) methane (leuco crystal 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-quinolylmethane, and tris (p-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, and 3-amino-6-dimethylamino-2-methyl-9- (o-chlorophenyl) xanthine Aminoxanthines such as 3,6-bis (die Aminothioxanthenes such as (lamino) -9- (o-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9 -Amino-9,10-dihydroacridine such as phenylacridine and 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; amino such as 3,7-bis (diethylamino) phenoxazine Phenoxazines; aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (p- Aminophenylmethanes such as dimethylaminophenyl) anilinomethane; 4 Aminohydrocinnamic acids such as amino-4′-dimethylaminodiphenylamine and 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis (ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-p-phenethylaniline; 10-acetyl-3, Acyl derivatives of leuco dyes containing basic NH such as 7-bis (dimethylamino) phenothiazine; have no oxidizable hydrogen such as tris (4-diethylamino-o-tolyl) ethoxycarbonylmentane, but can oxidize to chromogenic compounds Leuco-like compound; leucoin digoid dye; US Pat. No. 3,425,515 And organic amines (for example, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylene which can be oxidized to a colored form as described in US Pat. No. 3,425,517. Diamine triphenylamine, N-vinylcarbazole) can be used. Particularly preferred is leuco crystal violet.

  The addition amount of the color changing agent is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass with respect to all the components of the photosensitive resin composition layer. Especially preferably, it is the range of 0.1-5 mass%.

[Dye (colorant)]
In the present invention, a dye can be added to the photosensitive resin composition layer for the purpose of coloring the composition for improving handleability or imparting storage stability. Examples of suitable dyes include brilliant green sulfate, eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl Violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green oxalate, parafuchsin, oil blue # 603 (Orient Manufactured by Manabu Industry Co., Ltd.), it may be mentioned rhodamine B, and Rhodamine 6G and the like. A particularly preferred dye is malachite green oxalate.

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

[Adhesion promoter]
In the dry film photoresist of the present invention, a known so-called adhesion promoter can be added to the photosensitive resin composition layer in order to improve adhesion to the printed wiring board manufacturing substrate. As the adhesion promoter, those described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638 can be preferably used. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxanol, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3- Examples thereof include morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthiothiadiazole. Among these, 3-morpholinomethyl-1-phenyltriazole-2-thione is particularly preferable.

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

[Production of dry film photoresist]
The dry film photoresist of the present invention is prepared by, for example, preparing a photosensitive resin composition solution by dissolving the above-described various constituents in a solvent, which is a known method on a support (flexible transparent film). It can manufacture by apply | coating by and drying. The coating method of the photosensitive resin composition solution is not particularly limited. For example, spray method, roll coating method, spin coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, wire bar coating method. And various methods such as a knife coating method can be employed. The conditions for drying the photosensitive resin composition solution vary depending on the components, the types of solvents, the blending ratio thereof, and the like, but are usually about 30 seconds to 15 minutes at a temperature of 60 to 110 ° C.

  Examples of the solvent for the photosensitive resin composition solution include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclogexanone, And ketones such as diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; toluene, xylene, benzene, And aromatic hydrocarbons such as ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene; tetrahydride Furan, diethyl ether, ethylene glycol monomethyl ether, ethers such as ethylene glycol monoethyl ether, and 1-methoxy-2-propanol; may be mentioned dimethylformamide, and dimethyl sulfoxide and the like.

[Support and protective film]
The support is required to be flexible, capable of peeling the photosensitive resin composition layer, and having good light transmittance. Moreover, it is desirable that the surface smoothness is good. 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, Examples include various plastic films such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene. it can. Furthermore, a composite material composed of two or more of these can also be used. Among these, a 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.

  In the dry film resist of the present invention, a protective film can be further provided on the photosensitive resin composition layer on the support. Examples of the protective film include those used for the support, and paper or paper laminated with a plastic film such as a polyethylene film or a polypropylene film. In particular, a polyethylene film and a polypropylene film are preferable. The thickness of the protective film is generally in the range of 5 to 100 μm, and preferably in the range of 10 to 50 μm.

  The support and the protective film are preferably in a relationship (A> B) in which the adhesive force A between the photosensitive resin composition layer and the support is stronger than the adhesive force B between the photosensitive resin composition layer and the protective film. . Examples of the support / protective film combination include polyethylene terephthalate film / polypropylene film, polyethylene terephthalate film / polyethylene film, polyvinyl chloride film / cellophane film, and polyimide film / polypropylene film. As described above, in addition to the method of selecting the support and the protective film from different types, it is possible to satisfy the relationship of the adhesive force as described above by surface-treating at least one of the support and the protective film. . The surface treatment of the support is generally performed in order to increase the adhesive force with the photosensitive resin composition layer, for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, Examples thereof include high-frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

  In addition, for example, when a long dry film photoresist is manufactured and stored and transported in a roll, the coefficient of static friction between the support and the protective film is also important. The static friction coefficient is preferably in the range of 0.3 to 1.4, and particularly preferably in the range of 0.5 to 1.2. If it is less than 0.3, it slips too much, so that it may cause a winding deviation when it is rolled. Moreover, when it exceeds 1.4, it may become difficult to wind in a roll shape.

  Furthermore, you may surface-treat a protective film. The surface treatment is performed to reduce the adhesion between the protective film and the photosensitive resin composition layer. For example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and polyvinyl alcohol is provided on the surface of the protective film. The undercoat layer is generally formed by applying the polymer coating solution onto the surface of the protective film and then drying it at a temperature of 30 to 150 ° C. (particularly 50 to 120 ° C.) for 1 to 30 minutes.

  Furthermore, a layer having various functions such as an undercoat layer, an adhesive layer, a release layer, and a protective layer may be provided, or two or more types of photosensitive resin composition layers having different film properties and sensitivity may be provided.

[Manufacture of printed wiring boards]
The dry film photoresist of this invention can be used suitably for manufacture of the printed wiring board which has a through hole or a via hole.
A method for producing a printed wiring board having a through hole using the dry film photoresist of the present invention will be described with reference to FIG. 2 of the accompanying drawings.

  As shown in FIG. 2A, a printed wiring board manufacturing substrate 21 having a through hole 22 and having a surface covered with a metal layer 23 is prepared. As a printed wiring board manufacturing substrate 21, a copper-clad laminate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer. A substrate (laminated substrate) can be used.

Next, as shown in FIG. 2B, the photosensitive resin composition layer 13 of the dry film photoresist 11 of the present invention is pressure-bonded to the surface of the printed wiring board forming substrate 21 using a pressure roller 31. Then, a laminate in which the printed wiring board forming substrate 21, the photosensitive resin composition layer 13, and the support 12 are laminated in this order is obtained (laminating step). As the pressure roller 31, a known roller such as a metal roller or a rubber roller can be used. During the pressure bonding, it is preferable to heat the printed wiring board forming substrate 21 and the pressure roller 31 respectively. The heating temperature of the printed wiring board forming substrate 21 is preferably 50 to 100 ° C. The heating temperature of the pressure roller 31 is preferably 60 to 120 ° C. The roller pressure of the pressure roller is preferably in the range of ^{2 to} 5 kg / cm ² . The crimping speed is preferably 1 to 3 m / min.

  Next, as shown in FIG. 2 (C), light (active energy) is irradiated in a pattern form from the surface on the support 12 side of the laminate to cure the photosensitive resin composition layer 13 to form a wiring pattern. A cured product pattern 17 composed of a region of the cured resin composition 15 for forming and a region of the cured resin composition 16 for protecting the metal layer of the through hole is formed (exposure process). As a method of irradiating light in a pattern, a method of irradiating the entire surface with ultraviolet light through a photomask or a method of irradiating according to a pattern signal with a laser scanning exposure apparatus having a wavelength in the ultraviolet to visible light region is used. It is preferable. In particular, the latter method using a laser scanning exposure apparatus can form a pattern without using an expensive photomask, which eliminates the process problems caused by the photomask and is suitable for manufacturing a small variety of products. ing.

  Next, as shown in FIG. 2D, the support 12 is peeled from the laminate (support peeling process).

  Next, as shown in FIG. 2 (E), a weak alkaline aqueous solution (pH: 9 to 11) is brought into contact with the resin composition layer 13 so that the uncured region of the resin composition layer on the printed wiring board forming substrate. Is dissolved and removed to expose the metal layer 23 on the substrate surface (development process). A sodium carbonate aqueous solution can be used as the weak alkaline aqueous solution.

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

  Finally, as shown in FIG. 2 (G), the cured resin pattern is brought into contact with a strong alkaline aqueous solution (pH: 13 to 14), and the cured product pattern is finely crushed into a release piece 18 for forming a printed wiring board. It removes from the board | substrate 21 (hardened | cured material removal process). As the strong alkaline aqueous solution, an aqueous sodium hydroxide solution can be used.

  The dry film photoresist of the present invention may be used not only in the above etching process but also in a plating process. Examples of plating methods include copper plating such as copper sulfate plating and copper pyrophosphate plating, high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate plating, hard gold plating, and soft gold plating. There is gold plating such as plating.

[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 dilaurate was further added. The mixture was heated and stirred at a temperature of 90 ° C. for 7 hours. Thereafter, 13.7 parts by mass of 1-methoxy-2-propanol was added to obtain a polyurethane solution 1 (solid content 35% by mass) having a carboxyl group and having no ethylenically unsaturated bond. When the molecular weight of the polymer was measured by gel permeation chromatography (GPC), it was 45,000 in terms of mass average molecular weight (polystyrene conversion).

[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. A mixed solution of 12.1 parts by mass of 2,2-bis (hydroxymethyl) propionic acid, 10 parts by mass of both terminal diols of polypropylene glycol (average molecular weight 1000) and 50.8 parts by mass of N, N-dimethylacetamide was added thereto. In addition, 0.1 parts by mass of dibutyltin dilaurate was further added, and the mixture was heated and stirred at a temperature of 90 ° C. for 7 hours. Thereafter, 15.6 parts by mass of 1-methoxy-2-propanol was added to obtain a polyurethane solution 2 having a carboxyl group and no ethylenically unsaturated bond (solid content: 35% by mass). When the molecular weight of the polymer was measured by gel permeation chromatography (GPC), it was 52,000 in terms of mass average molecular weight (polystyrene conversion).

[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. To this, 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 The solution was added, and further 0.1 part by weight of dibutyltin dilaurate was added, and the mixture was heated and stirred at a temperature of 90 ° C. for 7 hours. Thereafter, 15.6 parts by mass of 1-methoxy-2-propanol was added to obtain a polyurethane solution 3 having a carboxyl group and no ethylenically unsaturated bond (solid content: 35% by mass). When the molecular weight of the polymer was measured by gel permeation chromatography (GPC), it was 50,000 in terms of mass average molecular weight (polystyrene conversion).

Synthesis Example 4 (Polyurethane solution having a carboxyl group and no ethylenically unsaturated bond: polyurethane solution 4)]
2,0.0 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. A mixed solution of 12.1 parts by mass of 2,2-bis (hydroxymethyl) propionic acid, 10 parts by mass of both terminal diols of polypropylene glycol (average molecular weight 1000) and 48.4 parts by mass of N, N-dimethylacetamide was added thereto. In addition, 0.1 parts by mass of dibutyltin dilaurate was further added, and the mixture was heated and stirred at a temperature of 90 ° C. for 7 hours. Thereafter, 16.3 parts by mass of 1-methoxy-2-propanol was added to obtain a polyurethane solution 4 having a carboxyl group and no ethylenically unsaturated bond (solid content: 35% by mass). When the molecular weight of the polymer was measured by gel permeation chromatography (GPC), it was 44,000 in terms of mass average molecular weight (polystyrene conversion).

[Synthesis Example 5 (polyurethane solution having a carboxyl group and no ethylenically unsaturated bond: polyurethane solution 5)]
2,2.5 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. A mixed solution of 12.1 parts by mass of 2,2-bis (hydroxymethyl) propionic acid, 10 parts by mass of both terminal diols of polypropylene glycol (average molecular weight 1000) and 50.4 parts by mass of N, N-dimethylacetamide was added thereto. In addition, 0.1 parts by mass of dibutyltin dilaurate was further added, and the mixture was heated and stirred at a temperature of 90 ° C. for 7 hours. Thereafter, 16.7 parts by mass of 1-methoxy-2-propanol was added to obtain a polyurethane solution 5 (solid content: 35% by mass) of a polyurethane having a carboxyl group and having no ethylenically unsaturated bond. When the molecular weight of the polymer was measured by gel permeation chromatography (GPC), it was 51000 in terms of mass average molecular weight (polystyrene conversion).

Synthesis Example 6 (Polyurethane solution having carboxyl group and ethylenically unsaturated bond: polyurethane solution 6)]
200 parts by mass of the 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 triethylbenzylammonium 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 (solid content mass%) having a carboxyl group and an ethylenically unsaturated bond. When the molecular weight of the polymer was measured, it was 51000 in terms of mass average molecular weight (polystyrene conversion).

[Example 1]
A photosensitive resin composition solution having the following composition was applied to a polyethylene terephthalate film having a thickness of 25 μm and dried to form a photosensitive resin composition layer having a thickness of 15 μm. Next, a 12 μm-thick polypropylene film was laminated on the photosensitive resin composition layer to produce a dry film photoresist.

[Composition of photosensitive resin composition solution]
────────────────────────────────────────
Polyurethane solution 1 shown in Synthesis Example 1 (solid content concentration 35% by 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, leuco Crystal violet 0.02 parts by mass, malachite 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 evaluation of (1) the shortest development time, (2) resolution, (3) adhesion, and (4) tent film strength (number of tent film breaks) of the dry film photoresist thus produced. . The shortest development time, resolution, adhesion, and tent film strength were measured by the following methods.

(1) Measuring method of shortest development time The surface of the surface is dried and the photosensitive resin composition layer is laminated on the surface of a dry copper-clad laminate (without through holes) while peeling the dry film photoresist polypropylene film. (MODEL8B-720-PH, Taisei Laminator Co., Ltd.) is used for pressure bonding to produce a laminate composed of a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The pressure bonding conditions are a laminated plate temperature of 70 ° C., a pressure roller temperature of 105 ° C., a pressure roller pressure of 3 kg / cm ² , and a pressure bonding speed of 1.2 m / min. The polyethylene terephthalate film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.1 MPa over the entire surface of the photosensitive resin composition layer on the copper clad laminate. The time required from the start of spraying the aqueous sodium carbonate solution until the photosensitive resin composition layer on the copper clad laminate is dissolved and removed is measured, and this is defined as the shortest development time.

(2) Resolution measurement method Under the same conditions as in the shortest development time evaluation method of (1) above, a laminate comprising a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared, and room temperature ( (23 ° C., 55% RH) for 10 minutes. Ultrahigh pressure mercury lamp (3kW ultra high pressure mercury lamp double-sided simultaneous exposure device HMW-6-N type, oak through a photomask (line / space = 1/1, line width 10 μm to 100 μm) on the surface of the polyethylene terephthalate film of the laminate The photosensitive resin composition layer is exposed by irradiating light of 40 mJ / cm ² using a product manufactured by Co., Ltd. After leaving still at room temperature for 10 minutes, a polyethylene terephthalate film is peeled off from a laminated body. A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the resin composition layer on the copper clad laminate at a spray pressure of 0.1 MPa for 1.5 times the shortest development time obtained in (1) above. Then, the uncured resin composition is dissolved and removed, and the cured resin pattern is developed. Thereafter, 20 ° C. water is sprayed at a spray pressure of 0.05 MPa for 80 seconds, and the cured resin pattern is washed with water and dried. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. To do. A small resolution value is excellent and indicates a high resolution (high resolution).

(3) Adhesion measurement method Except for using a photomask with a line / space of 1/3 and a line width of 10 μm to 100 μm, the same operation as the resolution evaluation method of (2) above was performed, and a cured resin pattern line Measure the minimum line width without any abnormalities such as peeling and twisting, and make this the close contact. The smaller the adhesion value, the better.

(4) Method of measuring tent film strength (number of tent film tears) The above (except for using a copper-clad laminate having 200 copper-plated through-holes with a diameter of 3 mm instead of a copper-clad laminate having no through-holes) A laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared under the same conditions as in 1) for the shortest development time evaluation method, and at room temperature (23 ° C., 55% RH). Let stand for 10 minutes. The surface of the laminated polyethylene terephthalate film is irradiated with light of 50 mJ / cm ² using an ultrahigh pressure mercury lamp to expose the entire surface of the photosensitive resin composition layer. After leaving at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. A sodium carbonate aqueous solution is sprayed on the entire surface of the resin composition layer on the copper clad laminate under the same conditions as in the resolution evaluation method of (2) except that the spray pressure of the sodium carbonate aqueous solution is 0.2 MPa. The cured resin pattern is developed, washed with water and dried. The copper clad laminate with a cured resin pattern thus obtained was sprayed with a 45 ° C. aqueous cupric chloride solution (etching solution) at a spray pressure of 0.1 MPa for 60 seconds to obtain a copper clad laminate. Etch. The total number of holes in which the tent film was torn by the above processing was counted (small numbers indicate good and tent film strength is high).

[Examples 2 to 5]
Instead of the polyurethane solution 1 in Example 1, the same amount of the polyurethane solutions 2 to 5 (35% by mass solution) shown in Synthesis Examples 2 to 5 shown in Table 1 below was used. A film photoresist was prepared. The shortest development 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 following polymerizable compound (M-2) was used instead of the polymerizable compound (M-1) in Example 1. The shortest development 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 to 10]
Instead of the polyurethane solution 1 in Example 6, the same amount of the polyurethane solutions 2 to 5 (35% by mass solution) shown in Synthesis Examples 2 to 5 as shown in Table 1 below was used. To manufacture a dry film photoresist. The shortest development 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 following polymerizable compound (M-3) was used instead of the polymerizable compound (M-1) in Example 2. The shortest development 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]
Dried film photoresists were produced in the same manner as in Examples 1 to 11 except that the thickness of the photosensitive resin composition layers in Examples 1 to 11 was 20 μm. The shortest development 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 polyurethane solution 1 (35% by mass solution) in Example 1, methacrylic acid / methyl methacrylate / 2-isocyanatoethyl methacrylate and n-butyl alcohol reacted with monomer / 2-ethylhexyl methacrylate / benzyl methacrylate copolymer 35% by mass solution of copolymer (copolymerization composition: 29/25/30/12/4 mol%, mass average molecular weight: 80,000) (solvent is methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (mass ratio) ) Was used in the same manner as in Example 1 except that the same amount was used. The shortest development 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 polymerizable compound (M-1) in Comparative Example 1, the same amount of the polymerizable compound (M-2 to M-3) as shown in Table 1 below was used, as in Comparative Example 1. Dried film photoresist was manufactured. The shortest development 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% by mass solution) was used instead of the polyurethane solution 2 in Example 2. The shortest development 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% by mass solution) was used instead of polyurethane solution 2 in Example 7. The shortest development 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% by mass solution) was used instead of polyurethane solution 2 in Example 11. The shortest development 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.

Table 1
────────────────────────────────────────
Polyuree Polymerization Photosensitive tree Shortest resolution Resolution Adhesion Tent film strength
Tan solution Compound Fat composition Image time (tent film
Layer thickness Number of tears)
────────────────────────────────────────
Example 1 1 M-1 15 μm 11 seconds 25 μm 30 μm 6 pieces Example 2 2 M-1 15 μm 15 seconds 25 μm 25 μm 4 pieces Example 3 3 M-1 15 μm 20 seconds 25 μm 30 μm 4 pieces Example 4 4 M-1 15 μm 21 seconds 25 μm 30 μm 5 Example 5 5 M-1 15 μm 15 seconds 30 μm 25 μm 5 pieces Example 6 1 M-2 15 μm 11 seconds 30 μm 30 μm 2 pieces Example 7 2 M-2 15 μm 15 seconds 25 μm 25 μm 1 Example 8 3 M-2 15 μm 20 seconds 25 μm 25 μm 2 Examples 9 4 M-2 15 μm 15 seconds 30 μm 25 μm 2 Examples 10 5 M-2 15 μm 15 seconds 25 μm 30 μm 2 Examples 11 2 M-3 15 μm 15 seconds 30 μm 25 μm 7 Example 12 1 M-1 20 μm 15 seconds 30 μm 25 μm 2 Example 13 2 M-1 0 μm 20 seconds 25 μm 20 μm 0 Example 14 3 M-1 20 μm 20 seconds 30 μm 25 μm 0 pieces Example 15 4 M-1 20 μm 25 seconds 30 μm 25 μm 1 piece Example 16 5 M-1 20 μm 20 seconds 35 μm 20 μm 1 Example 17 1 M-2 20 μm 15 seconds 35 μm 25 μm 0 pieces Example 18 2 M-2 20 μm 20 seconds 25 μm 20 μm 0 pieces Example 19 3 M-2 20 μm 20 seconds 30 μm 20 μm 0 pieces Example 20 4 M-2 20 μm 20 Second 35 μm 20 μm 0 Example 21 5 M-2 20 μm 20 Second 30 μm 25 μm 0 Example 22 2 M-3 20 μm 20 Second 35 μm 20 μm 3 ─────────────── ───────────────────────
Comparative Example 1-M-1 15 μm 11 seconds 35 μm 35 μm 44 Comparative Example 2-M-2 15 μm 11 seconds 35 μm 35 μm 39 Comparative Example 3-M-3 15 μm 11 seconds 35 μm 35 μm 65 Comparative Example 4 6 M-1 15 μm 15 seconds 25 μm 25 μm 3 pieces Comparative Example 5 6 M-2 15 μm 15 seconds 25 μm 25 μm 1 piece Comparative Example 6 6 M-3 15 μm 15 seconds 30 μm 25 μm 6 pieces ────────────── ────────────────────────

[Example 23]
In order to forcibly evaluate the maintenance stability of the dry film photoresist produced in the same manner as in Example 2, it was stored in a dark room at 50 ° C. for 72 hours. The shortest development 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 maintenance stability of the dry film photoresist produced in the same manner as in Example 7, it was stored in a dark room at 50 ° C. for 72 hours. The shortest development 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 maintenance stability of the dry film photoresist produced in the same manner as in Example 11, it was stored in a dark room at 50 ° C. for 72 hours. The shortest development 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 maintenance stability of the dry film photoresist produced in the same manner as in Comparative Example 4, it was stored in a dark room at 50 ° C. for 72 hours. The shortest development 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 maintenance stability of the dry film photoresist produced in the same manner as in Comparative Example 5, it was stored in a dark room at 50 ° C. for 72 hours. The shortest development 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 maintenance stability of the dry film photoresist produced in the same manner as in Comparative Example 6, it was stored in a dark room at 50 ° C. for 72 hours. The shortest development 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.

Table 2
────────────────────────────────────────
Polyuree Polymerization Shortest development time Resolution Adhesion Tent film strength
Tan solution Compound ────────────────────────────────────────
Example 23 2 M-1 15 seconds 30 μm 30 μm 5 pieces Example 24 2 M-2 15 seconds 30 μm 25 μm 2 pieces Example 25 2 M-3 15 seconds 30 μm 30 μm 9 pieces ────────── ─────────────────────────────
Comparative Example 7 6 M-1 120 seconds or more (*) (*) 35 (**)
Comparative Example 8 6 M-2 120 seconds or more (*) (*) 22 (**)
Comparative Example 9 6 M-3 120 seconds or more (*) (*) 59 (**)
────────────────────────────────────────
(*) Development was performed for 120 seconds, but the evaluation was not possible because the unexposed portion of the resin composition was cured.
(**) Value evaluated with the shortest development time as 120 seconds.

  From the results of Tables 1 and 2, the dry film photoresists (Comparative Examples 1 to 3) provided with the photosensitive resin composition not containing the polyurethane resin have significantly poor tent strength and are ethylenically unsaturated. Dry film photoresists (Comparative Examples 4 to 9) provided with a photosensitive resin composition containing a polyurethane resin having a bond are excellent in resolution and tent film strength, but have poor storage stability (even though they are unexposed portions). As a result, the shortest development time is greatly extended, resulting in problems such as deterioration in resolution and adhesion (impossibility of evaluation). On the other hand, dry film photoresists (Examples 1 to 22) provided with a photosensitive resin composition containing a polyurethane resin having no ethylenically unsaturated bond show excellent performance in resolution, tent film strength and storage stability. It was.

[Example 26]
(Formation of cured resin pattern by laser exposure)
The surface of the dried copper-clad laminate was prepared and the photosensitive resin composition layer of the dry film photoresist produced in Example 1 was peeled off from the polypropylene film on the photosensitive resin composition layer. The laminate was composed of a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. Using a laser exposure apparatus having a laser light source with a wavelength of 400 to 415 nm on the polyethylene terephthalate film of this laminate, a pattern with line / space = 1/1 and a line width of 10 μm to 100 μm, and line / space = 1/3 The photosensitive resin composition layer was exposed by irradiating a laser beam of 105 mJ / cm ² with a pattern having a line width of 10 μm to 100 μm. After leaving still at room temperature for 10 minutes, the polyethylene terephthalate film was peeled off from the laminated body. The entire surface of the resin composition layer on the copper-clad laminate is sprayed with a 1 mass% sodium carbonate aqueous solution at 30 ° C. for 17 seconds at a pressure of 0.1 MPa to dissolve and remove the uncured resin composition. Developed. Thereafter, water at 20 ° C. was sprayed for 80 seconds at a spray pressure of 0.05 MPa, and the cured resin pattern was washed with water and dried. When the surface of the copper-clad laminate with a cured resin pattern thus obtained was observed with an optical microscope, the line of the cured resin pattern formed with line / space = 1/1 had no abnormality such as tsumari and twist. The line width (resolution) is 25 μm, and it peels off to the line of the cured resin pattern formed with line / space = 1/3, and the minimum line width (adhesion) with no abnormalities such as twist is 10 μm, with the light of the ultra high pressure mercury lamp The resolution and adhesion were improved compared to the case of exposure.

[Example 26]
(Tent film formation by laser exposure)
The photosensitive resin composition layer of the dry film photoresist produced in Example 1 was coated on the surface of a copper-clad laminate having 200 copper-plated through-holes having a diameter of 3 mm and dried. The polypropylene film on the resin composition layer was pressure-bonded while peeling to prepare a laminate composed of a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The entire surface of the polyethylene terephthalate film of the laminate was irradiated with a laser beam of 105 mJ / cm ² using a laser exposure apparatus having a laser light source having a wavelength of 400 to 415 nm to expose the photosensitive resin composition layer. After leaving still at room temperature for 10 minutes, the polyethylene terephthalate film was peeled off from the laminated body. The entire surface of the resin composition layer on the copper clad laminate is sprayed with a 1 mass% sodium carbonate aqueous solution at 30 ° C. for 17 seconds at a pressure of 2 MPa to dissolve and remove the uncured resin composition and develop the cured resin pattern. Washed with water and dried. The copper clad laminate with a cured resin pattern thus obtained was sprayed with a 45 ° C. aqueous cupric chloride solution (etching solution) at a spray pressure of 0.1 MPa for 60 seconds to obtain a copper clad laminate. Etched. When the total number of holes in which the tent film was torn was counted in the above processing, the tent film strength (number of tent film breaks) was 3, which was better than when exposed to light from an ultrahigh pressure mercury lamp.

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

1 is a cross-sectional view of an example of a dry film photoresist according to the present invention. It is the figure which showed roughly the manufacturing method of the printed wiring board which has a metal plating through hole according to this invention.

Explanation of symbols

11 dry film photoresist 12 support (flexible transparent film support)
DESCRIPTION OF SYMBOLS 13 Photosensitive resin composition layer 14 Protective film 15, 16 Cured resin composition 17 Hardened | cured material pattern 18 Peeling piece 21 Printed wiring board formation board 22 Through hole 23 Metal layer 24 Wiring pattern 31 Crimp roller

Claims (12)

  A photosensitive material comprising a support, a polyurethane resin having at least (A) a carboxyl group and having no ethylenically unsaturated bond, (B) a polymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. Film photoresist having a conductive resin composition layer.   The polyurethane resin (A) having no ethylenically unsaturated bond is composed of a reaction product of at least one diisocyanate compound and at least one diol compound including a diol compound having a carboxyl group. Dry film photoresist.   The dry film photoresist according to claim 1 or 2, wherein the polyurethane resin (A) having no ethylenically unsaturated bond has a mass average molecular weight in the range of 5,000 to 300,000.   The dry film photoresist according to any one of claims 1 to 3, wherein the polymerizable compound (B) is a compound containing a urethane bond.   The photosensitive resin composition has a polyurethane resin (A) having no ethylenically unsaturated bond of 10 to 90% by mass, a polymerizable compound (B) of 5 to 60% by mass, and a photopolymerization initiator (C) of 0. The dry film photoresist according to claim 1, which is contained at 1 to 30% by mass.   The dry film photoresist according to any one of claims 1 to 5, wherein the photosensitive layer resin composition layer has a thickness of 5 µm or more and less than 35 µm.   The dry film photoresist according to claim 1, wherein a protective film layer is provided on the photosensitive layer resin composition layer.   The dry film photoresist according to any one of claims 1 to 7, which is used for producing a printed wiring board. A manufacturing method comprising the following steps of a printed wiring board having a through hole or a via hole:
(1) A step of preparing a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer;
(2) The dry film photoresist according to any one of claims 1 to 6 is pressure-bonded to the surface of the printed wiring board forming substrate so that the photosensitive layer resin composition layer is in contact with the metal layer, and printed. A laminating step of obtaining a laminate in which a wiring board forming substrate, a photosensitive layer resin composition layer, and a support are laminated in this order;
(3) Irradiate light from the surface of the laminate on the support side to cure the photosensitive resin composition layer, and protect the metal layer of the cured resin composition region for forming the wiring pattern and the through hole or via hole. An exposure step of forming a cured resin composition pattern comprising a cured resin composition region for use;
(4) a support peeling process for peeling the support from the laminate;
(5) A development step of dissolving and removing the uncured region of the resin composition layer on the printed wiring board forming substrate to expose the metal layer of the uncured region on the substrate surface;
(6) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(7) A cured resin composition removing step of removing the cured resin composition from the printed wiring board forming substrate.   The method for manufacturing a printed wiring board according to claim 9, wherein the light used in the step (3) is laser light.   (A) Polyurethane resin having a carboxyl group and no ethylenically unsaturated bond on a printed wiring board forming substrate having a through hole or a via hole and having a surface covered with a metal layer, (B) ethylenic A laminate in which a polymerizable compound having an unsaturated bond and (C) a photosensitive resin composition layer containing a photopolymerization initiator are laminated.   The laminate according to claim 11, wherein a support is laminated on the photosensitive layer resin composition layer.

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