JP2005258092A - Photosensitive resin composition and photosensitive transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a tent film which is less liable to tear, even if thinned from a photosensitive resin composition. <P>SOLUTION: In the photosensitive resin composition containing a binder, a polymerizable compound and a photopolymerization initiator, a compound having a linking group, comprising a tri- to hexavalent aliphatic group or aromatic group or a combination of these and 3-6 polymerizable end groups is used as the polymerizable compound. Each of the polymerizable end groups has two urethane bonds and two polyalkylene oxide is bonded to both sides thereof, wherein a (meth)acryloyl group is bonded to one polyalkylene oxide bond and a tri- to hexavalent linking group bonds to the other polyalkylene oxide bond. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a printed wiring board, a lead frame, a semiconductor package, a display member (for example, a color filter, a pillar material, a rib member, a spacer, a partition wall), a three-dimensional stereolithography, and an image forming material (for example, a printing plate, a proof). The present invention relates to a photosensitive resin composition and a photosensitive transfer sheet used in the field of pattern forming materials, and particularly relates to a photosensitive resin composition and a photosensitive transfer sheet useful for producing a printed wiring board. The present invention also relates to a method for producing a printed wiring board using the photosensitive transfer sheet.
More specifically, for high-density printed wiring boards that have excellent developability with a weak alkaline aqueous solution and excellent releasability with a strong alkaline aqueous solution, can achieve high resolution by thinning, and have excellent tent strength on through-holes even with thin films. The present invention relates to a photosensitive resin composition and a photosensitive transfer sheet.

  In the printed wiring board manufacturing field, a wiring pattern is formed by a photolithography technique using a photosensitive transfer sheet comprising a support (for example, polyethylene terephthalate) and a photosensitive layer formed on the support. Has been done. For example, in the case of a printed wiring board having a through hole, a through hole is formed in a printed wiring board forming substrate (for example, a copper-clad laminate), a metal layer is formed on the inner side wall of the through hole, and then the surface of the substrate is exposed to light. The photosensitive layer of the photosensitive transfer sheet is superposed and closely adhered, and light is applied to the area including the wiring pattern formation area and the through hole opening in a predetermined pattern to cure the photosensitive layer. Next, the support of the photosensitive transfer sheet is peeled off, and the uncured photosensitive layer region other than the cured layer on the wiring pattern formation region and the cured layer (called a tent film) on the through-hole opening region is dissolved and removed. Then, the exposed metal layer portion is etched, and then the hardened layer is removed to form a wiring pattern on the substrate surface. A method of protecting the metal plating of the through hole using this tent film is generally called a tenting method. In multilayer printed wiring boards, interlayer connection holes called via holes may be provided. In this case as well, it is necessary to protect the via hole portion with a tent film when forming a wiring pattern.

  In recent years, the demand for higher density of printed wiring boards has increased, and a photoresist capable of higher resolution has been demanded. In order to increase the resolution of the photoresist, it is effective to reduce the thickness of the photosensitive layer. However, as described in the background art, the photosensitive layer also has a role of protecting through holes or via holes formed in the printed wiring board. If the thickness of the photosensitive layer is simply reduced, the photosensitive resin composition is not yet formed. There is a problem that the tent film is broken in the step of dissolving and removing the cured photosensitive layer region and the step of etching the exposed metal layer portion.

  Research and development of a photosensitive resin composition and a photosensitive transfer sheet that can form a tent film that is difficult to break with high resolution have been actively conducted, and the results are disclosed as follows.

  Patent Document 1 discloses a photosensitive resin comprising a binder component (preferably containing a styrene-acrylic polymer), a monomer component containing an ethylenically unsaturated compound having a specific urethane bond, and a photopolymerization initiator. A photosensitive transfer sheet having a composition layer is disclosed.

  Patent Document 2 discloses a photosensitive transfer sheet having a photosensitive resin composition layer comprising a binder component having a carboxyl group, a monomer component containing a specific vinylurethane compound and a specific acrylate compound, and a photopolymerization initiator. Has been.

Patent Document 3 discloses that at least one of α, β-unsaturated carboxyl group-containing monomers having 3 to 15 carbon atoms is 15 to 35% by mass, butyl acrylate is 5 to 30% by mass, and the number of carbon atoms is 1. A binder component composed of 35 to 80% by mass of a methacrylic acid ester having 8 to 8 alkyl groups and having a mass average molecular weight in the range of 20,000 to 200,000, and ethylenic unsaturation of two or more monomers in one molecule A photosensitive transfer sheet having a photosensitive resin composition layer comprising a monomer component having a group and a photopolymerization initiator is disclosed.
These photosensitive transfer sheets have certainly improved the strength of the tent film, but the film thickness of the photosensitive layer is about 35 to 50 μm, and sufficient resolution has not been achieved.

Patent Document 4 or Patent Document 5 discloses a photosensitive resin composition comprising a binder component having a carboxyl group, a monomer component containing a specific urethane bond and an isocyanuric ester having an ethylenically unsaturated group, and a photopolymerization initiator. A photosensitive transfer sheet having a layer is disclosed.
Although these photosensitive transfer sheets have certainly improved the strength of the tent film, the film thickness of the photosensitive layer is 50 μm, and sufficient resolution has not been achieved.
Moreover, the monomer component which has an isocyanurate ring used by these patent documents uses the multimer of polyfunctional isocyanate as a raw material. However, since a multimer of polyfunctional isocyanate is usually obtained as a mixture, the monomer component having an isocyanurate ring is a mixture of monomers having various structures. For this reason, the sensitivity of the photosensitive transfer sheet may be unstable, the resolution may be insufficient, or the performance may not be sufficiently exhibited. Furthermore, since the polyfunctional isocyanate multimer is expensive, the monomer having an isocyanurate ring is also expensive, and it is difficult to say that it is industrially advantageous.

  In Patent Document 6, a first photosensitive layer that is alkali-soluble and has low fluidity by heating and is sensitive to active energy rays is provided on a support, and further, it is alkali-soluble and has fluidity by heating. A photosensitive transfer sheet having a two-layer photosensitive layer provided with a second photosensitive layer sensitive to active energy rays is disclosed. This patent document describes that the metal layer of the through hole can be protected by embedding the second photosensitive layer of the photosensitive transfer sheet in the through hole. However, since the cured resin (cured product of the second photosensitive layer) embedded in the through hole in the final process of manufacturing the printed wiring board has to be removed, there is a problem that the manufacturing process of the printed wiring board becomes complicated. is there. Also, the resolution was insufficient.

JP 2001-290266 A Japanese Patent Laid-Open No. 10-142789 JP-A-7-271032 Japanese Patent Laid-Open No. 10-10723 Japanese Patent No. 3199600 JP-A-8-54732

  An object of the present invention is to develop with a weak alkaline aqueous solution and to have excellent releasability with a strong alkaline aqueous solution, to enable high resolution by thinning, and to have a high resolution and a thinner thickness than the conventional one. It is another object of the present invention to provide a photosensitive resin composition and a photosensitive transfer sheet that can form a tent film that is difficult to tear. Another object of the present invention is to provide a method for industrially advantageously producing a printed wiring board having a through hole or a via hole using the photosensitive transfer sheet.

The present invention provides a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator, wherein the polymerizable compound is represented by the following formula (I): To:
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. A divalent linking group consisting of a combination, or a divalent linking group in which an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group or a sulfonyl is interposed between the combinations. P and q are each independently an integer from 1 to 10; l and m are each independently an integer from 1 to 50; n is an integer from 3 to 6; and L ² Is an n-valent aliphatic group or an n-valent aromatic group, or an alkylene group, a substituted alkylene group, an alkenylene group or a substituted alkenylene group It is an n-valent linking group consisting of an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. ].

In formula (I), l is preferably an integer of 1 to 14, and m is preferably an integer of 1 to 30.
In the formula (I), it is preferable that p and q are each independently 2 or 3.
In formula (I), L ¹ is preferably a divalent linking group comprising an alkylene group, an arylene group, a substituted arylene group, or a combination thereof.
In the formula (I), L ² is preferably an n-valent aliphatic group.
The binder is preferably a polymer having a carboxyl group. The binder is a copolymer having a repeating unit having a carboxyl group and a repeating unit having no carboxyl group, and the proportion of the repeating unit having a carboxyl group in the copolymer is more preferably 5 to 50 mol%.
The photopolymerization initiator is preferably selected from the group consisting of a heterocyclic compound having a halogen-substituted alkyl group, oxime, hexaarylbiimidazole and ketone.
The photosensitive resin composition preferably contains 10 to 90% by mass of the binder, 5 to 60% by mass of the polymerizable compound, and 0.1 to 30% by mass of the photopolymerization initiator.
It is preferable that the photosensitive resin composition further contains a sensitizer.
It is preferable that the photosensitive resin composition is for printed wiring board manufacture.

The present invention also provides a photosensitive transfer sheet having a support and a photosensitive resin layer containing a binder, a polymerizable compound, and a photopolymerization initiator, wherein the polymerizable compound is represented by the formula (I). A photosensitive transfer sheet is also provided.
The thickness of the photosensitive resin layer is preferably 5 μm or more and less than 35 μm.
A protective film layer can be provided on the photosensitive resin layer.

Furthermore, the present invention performs the following steps (1) to (6) in this order to produce a printed wiring board having a through hole or via hole whose inner wall surface is covered with a metal layer. Provide manufacturing method:
(1) A support, a binder, a polymerizable compound represented by the above formula (I), and photopolymerization are formed on the surface of a printed wiring board forming substrate having a through hole or a via hole and the surface is covered with a metal layer. A photosensitive transfer sheet having an initiator-containing photosensitive resin layer is pressure-bonded so that the photosensitive resin layer is in contact with the metal layer, and the printed wiring board forming substrate, the photosensitive resin layer, and the support are A laminating step for obtaining a laminated body laminated in order;
(2) Irradiate light in a pattern from the support side of the laminate to cure the photosensitive resin layer, and a curable resin composition region for wiring pattern formation and a cured resin for metal protection of through holes or via holes An exposure step of forming a cured resin composition pattern comprising a composition region;
(3) a support peeling process for peeling the support from the laminate;
(4) A development step of dissolving and removing the uncured region of the photosensitive resin layer on the printed wiring board forming substrate to expose the metal layer of the uncured region on the substrate surface;
(5) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(6) A cured layer removing step of removing the cured layer from the printed wiring board forming substrate.
In the step (3), laser light can be used as light.

Furthermore, in the present invention, a photosensitive resin layer containing a binder, a polymerizable compound and a photopolymerization initiator is laminated on a printed wiring board forming substrate having a through hole or a via hole whose inner wall surface is covered with a metal layer. There is also provided a laminate, wherein the polymerizable compound is represented by the formula (I).
A support can be laminated on the photosensitive resin layer.

 The present invention provides a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on a support, and a relative relative to the photosensitivity of the first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator. The second photosensitive layer having high photosensitivity is laminated in this order, and the polymerizable compound contained in at least one of the first photosensitive layer and the second photosensitive layer is represented by the formula (I). A featured photosensitive transfer sheet is also provided.

The present invention also provides a method for producing a printed wiring board having a through hole or a via hole comprising the following steps:
(1) The surface of the printed wiring board forming substrate having a through hole or via hole whose inner wall surface is covered with a metal layer, the surface being covered with a metal layer, a support, a binder, a polymerizable compound, and light A first photosensitive layer containing a polymerization initiator, a second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator and having a photosensitivity relatively higher than the photosensitivity of the first photosensitive layer are laminated in this order. The polymerizable compound contained in at least one of the first photosensitive layer and the second photosensitive layer is pressed with the photosensitive transfer sheet represented by the formula (I) so that the second photosensitive layer side is in contact with the metal layer. And a laminating step of obtaining a laminate in which at least the second photosensitive layer, the first photosensitive layer, and the support are laminated on the printed wiring board forming substrate;
(2) The process of peeling a support body as needed;
(3) From the opposite side of the laminate to the printed wiring board forming substrate, the wiring pattern forming region of the printed wiring board forming substrate is irradiated with a predetermined amount of light necessary for curing the second photosensitive layer. To form a hardened layer region of a predetermined pattern, and a region including the opening of the through hole or via hole is supplied with a predetermined amount of light necessary to cure both the first photosensitive layer and the second photosensitive layer. An exposure step of forming a cured layer region that covers the opening region of the through hole or via hole by irradiating the pattern of
(4) A support peeling step of peeling the support from the laminate as necessary;
(5) A developing step of dissolving and removing uncured regions of the first photosensitive layer and the second photosensitive 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 layer removing step of removing the cured layer from the printed wiring board forming substrate.

  Separately, the present invention relates to a second photosensitive layer comprising a binder, a polymerizable compound and a photopolymerization initiator on a substrate, and a relative relative to the photosensitivity of the second photosensitive layer comprising a binder, a polymerizable compound and a photopolymerization initiator. The first photosensitive layer having low photosensitivity is laminated in this order, and the polymerizable compound contained in at least one of the first photosensitive layer and the second photosensitive layer is represented by the formula (I). A photosensitive laminate is also provided.

  Since the photosensitive resin composition of the present invention and the photosensitive transfer sheet using the photosensitive resin composition can form a tent film that is not easily torn even if the thickness of the photosensitive resin composition layer is reduced, the photosensitive resin High resolution can be achieved by thinning the composition layer. Therefore, the photosensitive resin composition of the present invention and the photosensitive transfer sheet using the photosensitive resin composition can be advantageously used for the production of a high-density printed wiring board, particularly a double-sided printed wiring board or multilayer The present invention can be advantageously used for manufacturing a printed wiring board having a metal plated through hole such as a printed wiring board.

[Polymerizable compound]
The polymerizable compound is represented by the following formula (I).
(I)

In the formula (I), R ¹ is a hydrogen atom or a methyl group. The n (3 to 6) groups represented by R ¹ are preferably the same.

In the formula (I), L ¹ is a divalent linking group comprising an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a combination thereof. Or an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl (—CO—), an imino (—NH—), a substituted imino group (—NR—, R) Is a divalent linking group intervening by a substituent) or sulfonyl (—SO ₂ —). L ¹ is particularly preferably a divalent linking group comprising an alkylene group, an arylene group, a substituted arylene group, or a combination thereof. The n (3 to 6) groups represented by L ¹ are preferably the same.

The alkylene group may have a cyclic structure or a branched structure. The number of carbon atoms in the alkylene group is preferably 1 to 18, more preferably 2 to 14, and most preferably 4 to 10.
Examples of alkylene groups are methylene, ethylene, trimethylene, propylene, tetramethylene, 1-methyltrimethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, cyclohexylene, heptamethylene, octamethylene 2-ethylhexamethylene, nonamethylene, decamethylene, dodecamethylene, dicyclohexylmethylene, octadecamethylene. The following cyclic alkylene groups are also included in the examples of the alkylene group.

The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent of the substituted alkylene group include a halogen atom (F, Cl, Br, I), an aryl group, an alkoxy group (eg, methoxy, ethoxy, 2-ethoxyethoxy), an aryloxy group (eg, phenoxy), acyl Groups (eg, acetyl, propionyl), acyloxy groups (eg, acetoxy, butyryloxy), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl) and aryloxycarbonyl groups (eg, phenoxycarbonyl).
Examples of substituted alkylene groups include diphenylmethylene.

The alkenylene group and the alkynylene group may have a cyclic structure or a branched structure. The number of carbon atoms in the alkenylene group and alkynylene group is preferably 2 to 18, more preferably 2 to 14, and most preferably 4 to 10.
The alkenylene part of the substituted alkenylene group is the same as the above alkenylene group. The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent of the substituted alkylene group and the substituted alkynylene group are the same as the examples of the substituent of the substituted alkylene group.

The number of carbon atoms in the arylene group is preferably 6 to 18, and more preferably 6 to 14.
Examples of arylene groups include phenylene, biphenyldiyl and naphthylene.
The arylene part of the substituted arylene group is the same as the above arylene group. Examples of the substituent of the substituted arylene group include an alkyl group in addition to the examples of the substituent of the substituted alkylene group.
Examples of substituted arylene groups include methylphenylene and dimethylphenylene.

  The divalent linking group comprising a combination of an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group or a substituted arylene group preferably has 7 to 25 carbon atoms. 7 to 18 is more preferable, and 7 to 15 is most preferable. An example of a divalent linking group comprising a combination includes xylene-α, α'-diyl.

  A combination of an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group or a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or Groups in which these are combined (—OCO—, —COO—, —CONH—, —NHCO—, etc.) may intervene. Examples of the substituent of the substituted imino group include an alkyl group and an aryl group. The alkyl group preferably has 1 to 18 carbon atoms, and more preferably 1 to 10 carbon atoms. The number of carbon atoms in the aryl group is preferably 6 to 18, and more preferably 6 to 10.

In formula (I), p and q are each independently an integer of 1 to 10. p and q are each independently preferably an integer of 1 to 6, more preferably 2, 3 or 4, and most preferably 2 or 3.
-C p _H 2p _- are good number of carbon atoms which may have a branch means a chain unsubstituted alkylene group is p.
_{(-O-C p H 2p -} ) l plurality of oxyalkylene included in _{(-O-C p H 2p -} ) If different, polyoxyalkylene moiety which is a copolymer, a random, alternating, block Either is acceptable.
-C q _H 2q _- can be carbon atoms which may have a branch means a chain unsubstituted alkylene group is q.
(—C _q H _2q —O—) When a plurality of oxyalkylenes (—C _q H _2q —O—) contained in _m are different, the polyoxyalkylene moiety to be a copolymer is random, alternating, block Either may be sufficient.

In formula (I), l and m are each independently an integer of 1 to 50.
l is preferably an integer of 1 to 14, more preferably an integer of 4 to 14, and most preferably an integer of 4 to 10.
m is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and most preferably an integer of 1 to 10.

_{Below, - (- O-C p} H 2p -) - shows an example of a _l. l1 and l2 are integers from 1 to 49 that satisfy l1 + l2 = 1. _{- (- C q H 2q -O-} ) m - ( except the left and right are reversed) is also an example of the same.
_{L01: - (- O-CH} 2 -CH 2 -) l -
_{L02: - (- O-CH} 2 -CH (CH 3) -) l -
_{L03: - (- O-CH} 2 -CH 2 -CH 2 -) l -
_{L04: - (- O-CH} 2 -CH 2 -CH 2 -CH 2 -) l -
L05: — (— O—CH ₂ —CH ₂ —) <sub>11
- (- O-CH 2 -CH</sub> (CH 3) -) l2 -
L06: — (— O—CH ₂ —CH ₂ —) <sub>11
- (- O-CH 2 -CH</sub> 2 -CH 2 -CH 2 -) l2 -
L07: — (— O—CH ₂ —CH (CH ₃ ) —) <sub>11
- (- O-CH 2 -CH</sub> 2 -CH 2 -CH 2 -) l2 -

  In the formula (I), n is each independently an integer of 3 to 6. n is preferably 3, 4 or 6.

In the formula (I), L ² is an n-valent aliphatic group or an n-valent aromatic group, or an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene. Group, arylene group, substituted arylene group, oxygen atom (—O—), sulfur atom (—S—), carbonyl group (—CO—), imino group (—NH—), substituted imino group (—NR—, R) Is a combination with a substituent) or a sulfonyl group (—SO ₂ —). L ² is particularly preferably an n-valent aliphatic group.

The n-valent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 30, more preferably 1 to 20, and most preferably 3 to 10. The aliphatic group may have a substituent. The example of the substituent of an aliphatic group is the same as the example of the substituent of a substituted alkylene group.
The number of carbon atoms in the n-valent aromatic group is preferably 6 to 100, more preferably 6 to 50, and most preferably 6 to 30. The aromatic group may have a substituent.
The alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group, arylene group, substituted arylene group, and substituted imino group are as described for L ¹ .

Hereinafter, examples of ^{L 2.}

Two or more polymerizable compounds represented by the formula (I) may be used in combination. When the polymerizable compound represented by the formula (I) is synthesized by a general production method (described later), a mixture having different degrees of polymerization of the alkylene oxide units (numerical values of 1 and m) is often obtained. In the present invention, the obtained mixture can be used as it is.
Examples of the polymerizable compound represented by the formula (I) and a mixture thereof are shown below. In the case of a mixture, l (including l1 and l2) and m are average values.

Polymerizable compound represented by formula (I) are, for ^{example, [OCN-L 1 -NH-} CO-O - (- C q H 2q -O-) m -] with a polyisocyanate corresponding to n ^{L 2} CH ₂ ═C (—R ¹ ) —CO — (— O—C _p H _2p —) ₁ —OH can be synthesized by a reaction with a (meth) acrylic acid ester corresponding to —OH.
The polyisocyanate is, for example, a reaction between an alkylene oxide adduct corresponding to HO — (— C _q H _2q —O—) _m —] _n L ² and a diisocyanate corresponding to OCN-L ¹ —NCO. Can be synthesized. The alkylene oxide adduct can be synthesized, for example, by a reaction with a polyvalent (3 to 6 valent) alcohol corresponding to (HO—) _n L ² .

The content of the polymerizable compound (including other polymerizable compounds described later) in the photosensitive resin composition layer is generally 5 to 90% by mass of the total amount (excluding the solvent) of the photosensitive resin composition. However, it is preferably 5 to 60% by mass, more preferably 15 to 60% by mass, and most preferably 20 to 50% by mass. If the amount of the polymerizable compound is small, the strength of the tent film may be reduced. When there are many polymerizable compounds, when used as a photosensitive transfer sheet, edge fusion during storage (bleed out from the roll end) tends to deteriorate.
The proportion of the polymerizable compound represented by the formula (I) in the total polymerizable compound is preferably 20% by mass or more, more preferably 30% by mass or more, and most preferably 50% by mass or more.

[Other polymerizable compounds]
The polymerizable compound represented by the formula (I) may be used in combination with another polymerizable compound.
As such a polymerizable compound, it is preferable to use a monomer (polyfunctional monomer) containing two or more polymerizable groups or an oligomer. It is also preferable to use a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester), epoxy, and the like. Group, oxetane group and the like. Of these, ethylenically unsaturated bonds are preferred, and among the ethylenically unsaturated bonds, vinyl groups such as (meth) acryloyl groups and styryl groups are particularly preferred.

  Examples of such polyfunctional monomers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated Examples include amides of carboxylic acids and polyvalent amine compounds.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include (meth) acrylic acid ester, 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, tetrapropylene glycol di (meth) a Relate, dodecapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanedio Di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-pentanediol (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, dimethylol dicyclopentanedi (meth) acrylate Rate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, di (meth) acrylate of polyethylene glycol / polypropylene glycol copolymer, ethylene oxide Examples include tri (meth) acrylic acid ester polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, and xylenol di (meth) acrylate added to trimethylolpropane.

  Among these (meth) acrylic acid esters, preferred examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol because of their availability. Di (meth) acrylate, polyethylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol triacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (Meth) acrylate, glycerin tri (meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol Examples thereof include di (meth) acrylate, 1,5-pentanediol (meth) acrylate, neoventyl glycol di (meth) acrylate, and tri (meth) acrylic acid ester of trimethylolpropane added with ethylene oxide.

  Examples of esters of itaconic acid and aliphatic polyhydric alcohol compounds (itaconic acid esters) include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, and 1,4-butanediol. 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.

Examples of amides of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis (meth). Examples include acrylamide, diethylenetriamine tris (meth) acrylamide, diethylenetriamine bis (meth) acrylamide, and xylylene bis (meth) acrylamide.
Further, 2,2-bis [p- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane having a bisphenol skeleton, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4 -((Meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypenta) Decaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl Nyl) propane, 2,2-bis [4-((meth) acryloyloxypropoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyl) Oxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane And polyethylene oxide in the same molecule as the polyether moiety of these compounds And compounds containing both of case and polypropylene oxide backbone can be cited. These compounds can be obtained, for example, as BPE-200, BPE-500, BPE-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Furthermore, compounds having an isocyanate group and a polymer group (2-isocyanatoethyl (meth) acrylate, α, α-dimethyl) with respect to a compound having a hydroxyl group at the terminal obtained as an adduct or polyaddition product such as bisphenol and ethylene oxide or propylene oxide A polymerizable compound having a bisphenol skeleton and a urethane group can also be used, such as an adduct of vinylbenzyl isocyanate.
Also novolak type epoxy resin, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl A compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, or glycerin triglycidyl ether can also be used.

  In addition, a compound containing a polymerizable group and a urethane group other than those represented by formula (I) can also be used. Examples of such compounds are described in JP-B-48-41708, JP-A-51-37193, JP-B-5-50737, JP-B-7-7208, JP-A-2001-154346, JP-A-2001-356476, and the like. For example, a polyisocyanate compound having two or more isocyanate groups per molecule (for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenyl diisocyanate, burettes and isocyanurates of these diisocyanates Any trimer) and vinyl monomers containing hydroxyl groups in the molecule (eg 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (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 mono (meth) acrylate, trimethylolpropane di ( Vinylurea containing two or more polymerizable vinyl groups in one molecule obtained by adding (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.) Down compounds, and the like. In addition, compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid can also be used.

  Further, polyester acrylates and polyester (meth) acrylate oligomers, epoxy compounds (novolak type epoxy resins, etc.) described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490 are disclosed. Butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether Ethers, glycerin triglycidyl ether, etc.) and (meth) acrylic acid reacted with epoxy acrylates It is possible to increase the capacity of the acrylate or methacrylate. Moreover, the esterified substance etc. which are obtained from a vinyl monomer which contains a hydroxyl group in the said molecule | numerator with a phthalic acid, trimellitic acid, etc. are mentioned. Furthermore, what is introduce | transduced as a photocurable monomer and an oligomer by the Japan Adhesive Association magazine vol.20, No.7, 300-308 pages (1984) can also be used.

  Further, allyl esters (for example, diallyl phthalate, diallyl adipate, diallyl malonate, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, triallyl isocyanurate); and diallylamide can also be used.

Moreover, cationically polymerizable divinyl ethers (for example, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, Trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, bisphenol A divinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (novolac type epoxy resin, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether) , Diethylene glycol diglycidyl ether Dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, glycerin triglycidyl ether, etc.), oxetanes (for example, 1,4-bis [( 3-ethyl-3-oxetanylmethoxy) methyl] benzene etc.) can also be used.
Examples of vinyl esters that can be used include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinyl benzene-1,3-disulfonate, divinyl butane-1,4-disulfonate, and the like.
Examples of the styrene compound include divinylbenzene, p-allyl styrene, p-isopropene styrene, and the like.

  Further, as compounds other than the above-mentioned compounds, different ethylenically unsaturated diesters such as N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, and allyl methacrylate are used. A compound having two or more heavy bonds can also be mentioned as a compound suitably used in the present invention.

  Examples of monofunctional monomers include compounds exemplified as a raw material for the binder described later, and dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) disclosed in JP-A-6-236031. And monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate and the like.

  These polyfunctional monomers, oligomers, and monofunctional monomers can be used alone or in combination of two or more.

[binder]
The binder used in the photosensitive resin composition is preferably soluble in an alkaline aqueous solution, or preferably has at least swellability. Examples of such binders include those having an acidic group (carboxyl group, sulfonic acid group, phosphoric acid group, etc.). Particularly, binders having a carboxyl group are typical, for example, a carboxyl group-containing vinyl copolymer. Polymers, carboxyl group-containing polyurethane resins, polyamic acid resins, modified epoxy resins, etc. are mentioned, but carboxyls are used because of their solubility in coating solvents, solubility in alkaline developers, suitability for synthesis, and ease of adjustment of film properties. A group-containing vinyl copolymer is preferred.

The carboxyl group-containing vinyl copolymer is obtained by copolymerization of at least (1) a carboxyl group-containing vinyl monomer, and (2) a monomer copolymerizable therewith.
Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxypolycaprolactone mono (Meth) acrylate and the like can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride and itaconic anhydride, as a precursor of a carboxyl group. Of these, from the viewpoints of copolymerizability, cost, solubility and the like, monomers having a hydroxyl group such as (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate, maleic anhydride, phthalic anhydride, cyclohexane An addition reaction product with a cyclic anhydride such as dicarboxylic acid anhydride is more preferable, and (meth) acrylic acid is particularly preferable.

The other copolymerizable monomer that can be used for the synthesis of the copolymer preferably has no reactivity with a carboxyl group. Examples of such monomers include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers. , Styrenes, (meth) acrylonitrile and the like.
Examples of such a compound include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate Rate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol Monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol (meta ) Acrylate, dicyclopentanyl (meth) acrelane Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) ) Acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate. Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn butylacryl (meth) amide, N-tert. Butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (Meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, etc. are mentioned.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples include styrene, methyl vinylbenzoate, and α-methylstyrene. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  In addition, (meth) acrylonitrile, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone, and the like can also be used. Further, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl acryloyl phosphate, 2-hydroxypropyl acryloyl phosphate and the like can be used.

In addition to these, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used.
As such a monomer, a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Specific examples of the isocyanate group-containing monomer include the following compounds (R ¹ represents a hydrogen atom or a methyl group).

Specific examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, and phenyl isocyanate.
Specific examples of the hydroxyl group-containing monomer include the following compounds (R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more).

  Examples of the compound containing one hydroxyl group include alcohols (methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (phenol, cresol, naphthyl alcohol, etc.), and further containing a substituent such as fluoroethanol, Examples include trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the primary or secondary amino group-containing monomer include, for example, vinylbenzylamine.

  Specific examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), arylamine ( Aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and further amines containing substituents (trifluoroethylamine, hexafluoroiso) Ropiruamin, methoxyaniline, and methoxy propylamine, etc.) and the like.

  These compounds may be used alone or in combination of two or more.

Other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, methylstyrene, hydroxystyrene, methoxystyrene, chlorostyrene, bromostyrene, (meth) acrylonitrile, 2-acrylamide-2- Preferred are methylpropane sulfonic acid, 2-hydroxyethyl acryloyl phosphate, 2-hydroxypropyl acryloyl phosphate, methyl (meth) acrylate, ethyl (Meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, styrene, methylstyrene, hydroxystyrene, chlorostyrene , Bromostyrene, (meth) acrylonitrile and the like are more preferable, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, styrene, hydroxy Styrene, chlorostyrene, bromostyrene and the like are particularly preferable.
Such a vinyl copolymer can be obtained by copolymerizing corresponding monomers according to a conventional method in accordance with a conventional method. For example, it can be obtained by using a method (solution polymerization method) in which these monomers are dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Further, polymerization may be carried out by so-called emulsion polymerization or the like in a state where the above monomer is dispersed in an aqueous medium.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene can be mentioned. These solvents may be used as a mixture of two or more. Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

  The content of the repeating unit derived from the polymerizable monomer having a carboxyl group in the vinyl copolymer obtained from these monomers is preferably from 5 to 50 mol%, more preferably from 10% of all repeating units of the copolymer. It is -40 mol%, and 15-35 mol% is especially preferable. If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

Moreover, although the molecular weight of the binder which has a carboxyl group can be adjusted arbitrarily, 2000-300,000 are preferable as a mass mean molecular weight, and 4000-150,000 are especially preferable. When the mass average molecular weight is less than 2000, the strength of the film is insufficient, and stable production tends to be difficult. On the other hand, if the molecular weight exceeds 300,000, the developability tends to decrease. Furthermore, although the glass transition temperature (Tg) of the binder which has a carboxyl group can be adjusted arbitrarily, 40 to 200 degreeC is preferable, 55 to 165 degreeC is more preferable, and 70 to 150 degreeC is especially preferable. If the Tg is less than 40 ° C., stickiness may occur when used as a photosensitive transfer sheet, or edge fusion during storage (exudation failure from the end of the roll) tends to occur. On the other hand, if Tg exceeds 200 ° C., the viscosity of the photosensitive resin composition is high, making it difficult to handle, and the laminate properties when used as a photosensitive transfer sheet tend to be lowered.
These binders having a carboxyl group may be used alone or in combination of two or more binders.

  The content of the binder having a carboxyl group in the photosensitive resin composition is 10 to 90% by mass, preferably 20 to 80% by mass, particularly 20 to 80% by mass of the total amount of the photosensitive resin composition (excluding the solvent). Preferably it is 40-80 mass%. If the content of the binder having a carboxyl group (and a polymer binder used in combination as needed) is small, the alkali developability tends to decrease. Conversely, if the content is too large, The strength of the cured film (tent film) tends to decrease.

[Photopolymerization initiator]
As the photopolymerization initiator, any compound having the ability to initiate the polymerization of the above-mentioned monomer components can be used, and any compound having photosensitivity to visible light from the ultraviolet region can be preferably 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 causes some action with the photoexcited sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer. Good.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thio compounds, ketone compounds, aromatic oniums. Examples thereof include salts and ketoxime ethers. Of these, the use of a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, hexaarylbiimidazole, and a ketone compound is particularly sensitive to the sensitivity and storability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate. From the viewpoint of the above.

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- (4 -Chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-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, for example, 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6-bis (trichloro) Methyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-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- (4-methoxystyryl) ) Phenyl) -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-thiophen-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-vinylenef Nyl) -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- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenylethynyl) phenyl ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1, , 5-triazine.

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

  2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1,3,5-triazine described in JP-A-5-34920, Trihalomethyl-s-triazine compounds described in U.S. Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -4,6-bis (Tribromomethyl) -s-triazine and the like.

  In addition, compounds having an oxadiazole skeleton described in US Pat. No. 4,221,976 can be used. Examples of the compound having an oxadiazole skeleton include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadi Azole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2- Tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxy) Styryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) ) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4-oxadiazole, and the like.

  Examples of the oxime derivative that can be suitably used in the present invention include compounds represented by the following general formula.

  Examples of the hexaarylbiimidazole that can be used in the present invention include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2 -Fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (3-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4- Methoxypheni ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole Examples include imidazole, 2,2′-bis (2-trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and compounds described in WO 00/52529.

  The above biimidazoles can be easily synthesized by, for example, the methods disclosed in Bull. Chem. Soc. Japan, 33,565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). it can.

  Examples of ketone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxy. Carbonyl benzolphenone, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexylamino) Benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether) Ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - chloro acridone and the like.

  In addition to these, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and other polyhalogen compounds (for example, carbon tetrabromide, phenyltribromo, etc.) Methylsulfone, phenyltrichloromethyl ketone, etc.), coumarins (eg, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7 -Diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxy) Coumarin), 3,3′-carbonylbis (7-diethylaminocoumarin) ), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridyl) Carbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and the like, and in addition, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206. No., JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethyl N-butyl aminobenzoate, phenethyl 4-dimethylaminobenzoate, 4-dimethyla Minobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl and pentamethylene ester of 3-dimethylaminobenzoic acid, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, aminophen Luolans (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (eg, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H -Pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP 53-133428, JP 57-1819, 57-6096, and Such as the compounds disclosed in U.S. Patent No. 3,615,455 may also be mentioned.

  Furthermore, the vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, the acyloin ether compound described in US Pat. No. 2,448,828, the α-form described in US Pat. No. 2,722,512 Aromatic acyloin compounds substituted with hydrocarbons, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, organoboron compounds described in JP-A-2002-229194, and other exemplified radicals Generators, phosphonium salt compounds (effective as a cationic polymerization initiator) such as triarylsulfonium salts (salts with hexafluoroantimony or hexafluorophosphate), (phenylthiophenyl) diphenylsulfonium salts, WO01 / 71428 Onium in the publication And compounds can also be used.

Two or more photopolymerization initiators can be used in combination. Examples of combinations of photopolymerization initiators include a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl- Combinations of s-triazine compounds, combinations of aromatic ketone compounds such as thioxanthone and hydrogen donors (for example, dialkylamino-containing compounds and phenol compounds), combinations of hexaarylbiimidazole and titanocene, coumarins, titanocene and phenyl Combinations with glycines can also be used.
The amount of the photopolymerization initiator used is generally in the range of 0.1 to 30% by mass, preferably in the range of 0.5 to 20% by mass, based on the total amount of the photosensitive resin composition (excluding the solvent). Especially preferably, it is the range of 0.5-15 mass%.

  When using as a photosensitive transfer sheet having two photosensitive resin composition layers, and adjusting the sensitivity difference between the first photosensitive layer and the second photosensitive layer by the content of the photopolymerization initiator, The photopolymerization initiator content of the layer is preferably 1.5 to 100 times, particularly 2 to 20 times the content of the photopolymerization initiator of the first photosensitive layer. preferable.

[Sensitizer]
In the photosensitive resin composition of the present invention, a so-called sensitizer is used for the purpose of adjusting the sensitivity in exposure of the photosensitive resin composition, or when using visible light or ultraviolet laser as light (active energy ray). Can be added.
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), anthraquinones (eg, anthraquinone) , Squaraines (eg, squalium), acridones (eg, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butylchloroacridone, etc.), coumarins (eg 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.) Domo available.
Moreover, as a combination of these initiators and sensitizers, for example, an electron transfer-type initiator system described in JP-A-2001-305734 ((1) an electron-donating initiator and a sensitizing dye, (2) an electron-accepting initiator, and Examples include sensitizing dyes, (3) electron donating initiators, sensitizing dyes and electron accepting initiators (ternary initiator systems)).

  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, particularly preferably, based on the total amount of the photosensitive resin composition (excluding the solvent). It is the range of 0.2-10 mass%. When the addition amount of the sensitizer is large, it is precipitated from the photosensitive resin composition at the time of storage, and when it is too small, the sensitivity to the active energy ray is lowered, the exposure process takes time, and the productivity may be lowered.

[Other ingredients]
The photosensitive resin composition of the present invention comprises, if necessary, a thermal polymerization inhibitor, a plasticizer, a color change agent, a colorant, an adhesion promoter for a substrate surface when used as a photosensitive transfer sheet, and other auxiliary agents. (For example, pigments, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) may be used in combination. Properties such as stability, photographic properties, print-out properties, and film properties of the intended photosensitive resin composition can be adjusted.

[Thermal polymerization inhibitor]
The thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the polymerizable compound of the photosensitive resin composition. 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, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, p -Toluidine, methylene blue, organic copper, methyl salicylate, phenothiazine and the like.

  The addition amount of the thermal polymerization inhibitor is preferably in the range of 0.001 to 5% by mass, more preferably in the range of 0.005 to 2% by mass with respect to the polymerizable monomer of the photosensitive resin composition. Especially preferably, it is the range of 0.01-1 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 decrease.

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

  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 the total amount of the photosensitive resin composition (excluding the solvent). Is in the range of 1-30% by weight.

[Discoloring agent]
When used as a photosensitive transfer sheet, 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, tris (p-dipropyl) Aminotriarylmethanes such as aminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (o-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethylamino) ) -9- (o-ethoxycarbonylphenyl) thioxanthene, 3,6-bis (dimethylamino) thioxanthene and other aminothioxanthenes; 3,6-bis (diethylamino) -9,10-dihydro-9-phenyl Acridine, amino-9,10-dihydroacridines such as 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine; aminophenoxazines such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (p-dimethylaminophenyl); ) Aminophenylmethanes such as anilinomethane; 4-amino-4'-di Aminohydrocinnamic acids such as methylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Amino-2,3-dihydroanthraquinones of ethylamino) -2,3-dihydroanthraquinones; Phenethylanilines such as N, N-diethyl-p-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound that does not have oxidizable hydrogen such as tris (4-diethylamino-o-tolyl) ethoxycarbonylmentane, but can be oxidized to a coloring compound; Id dyes; U.S. Pat. Nos. 3,042,515 and 3,042,5 Organic amines that can be oxidized to a colored form as described in No. 7 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole). Particularly preferred is leuco crystal violet.

  Furthermore, it is known to combine with a halogen compound for the purpose of coloring these leuco bodies. Examples of halogen compounds are halogenated hydrocarbons (eg carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, diphenyl bromide). Methyl, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo -4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, etc. Halogenated alcohol compounds (for example, 2,2,2-trichloroethanol, tribromoethane) 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-tert-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) , Di (2-bromoethyl) ether, 1,2-dic Halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β- Halogenated amide compounds (eg chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2-trichloropropionamide) N-chlorosuccinimide, N-bromosuccinimide, etc.);

  Compounds having sulfur or phosphorus (for example, tribromomethylphenylsulfone, p-nitrophenyltribromomethylsulfone, p-chlorophenyltribromomethylsulfone, tris (2,3-dibromopropyl) phosphate), 2,4-bis (Trichloromethyl) 6-phenyltriazole and the like. Of the organic halogen compounds, a halide having two or more halogen atoms bonded to the same carbon atom is preferable, and a halide having three halogen atoms in one carbon atom is particularly preferable. The organic halogen compounds may be used alone or in combination of two or more. Of these, particularly preferred organic halogen compounds are tribromomethylphenylsulfone and 2,4-bis (trichloromethyl) 6-phenyltriazole.

  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, particularly preferably the total amount (excluding the solvent) of the photosensitive resin composition. Is in the range of 0.1 to 5% by mass. The amount of the halogen compound is generally in the range of 0.001 to 5 mass%, preferably 0.005 to 1 mass% of the total amount of the photosensitive resin composition (excluding the solvent).

[dye]
In the present invention, a dye can be used in the photosensitive resin composition for the purpose of coloring the composition for improving handleability or imparting storage stability. Examples of suitable dyes include brilliant green (eg sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymol. Phthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl-Yellow, Thymolsulfophthalein, 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 (eg, its oxalate salt), parafuchsin, o Ruburu # 603 (manufactured by Orient Chemical Industries, Ltd.), Rhodamine B, and Rotamin 6G, and the like Victoria Pure Blue BOH. A particularly preferred dye is malachite green oxalate.

  The preferable addition amount of the dye is in the range of 0.001 to 10% by mass of the total amount (excluding the solvent) of the photosensitive resin composition. More preferably, it is the range of 0.01-5 mass%, Most preferably, it is the range of 0.1-2 mass%.

[Adhesion promoter]
In the photosensitive resin composition of the present invention, a known so-called adhesion promoter is added to the photosensitive resin composition in order to improve adhesion to a printed wiring board manufacturing substrate when used as a photosensitive transfer sheet. Can do. As the adhesion promoter, adhesion promoters 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 include morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, and the like. .

  A preferable addition amount of the adhesion promoter is in the range of 0.001% by mass to 20% by mass of the total amount of the photosensitive resin composition (excluding the solvent). More preferably, it is the range of 0.01-10 mass%, Most preferably, it is the range of 0.1 mass%-5 mass%.

  In addition, the photosensitive resin composition of the present invention is disclosed in, for example, J. Org. It contains organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, photocyclic dyes, and organic halogen compounds as described in Chapter 5 of “Light Sensitive Systems” by Korser. Also good. Examples of organic sulfur compounds include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. be able to. Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide. The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides. Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as p-aminodiphenylamine. Examples of the photoreductive dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

  In the photosensitive resin composition of the present invention, a known surfactant may be added in order to improve surface unevenness and the like generated when a photosensitive transfer sheet is produced. As an example of the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a fluorine-containing surfactant are appropriately selected from the viewpoint of adhesion. The addition amount is preferably 0.001 to 10% by mass of the total amount of the photosensitive resin composition (excluding the solvent), and if it is less than 0.001% by mass, the effect of improving the surface condition cannot be obtained, and if it exceeds 10% by mass There is a problem that the adhesion deteriorates. Fluoroaliphatic group having fluorine chain with hydrogen atoms bonded to at least 3 carbon atoms counted from the non-bonding end as a fluorosurfactant containing 40 mass% or more of carbon atoms with 3 to 20 carbon chains A polymeric surfactant having an acrylate or methacrylate having a copolymerization component is preferred.

  In the photosensitive resin composition of the present invention, each of the above components is dissolved in a solvent that dissolves these components, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methoxypropyl acetate, etc. Esters; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halogens such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Hydrocarbons; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol; by dissolving and mixing in dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. A uniform solution can be obtained.

[Basic structure of photosensitive transfer sheet and photosensitive laminate]
As an example of the photosensitive transfer sheet of the present invention, FIG. 1 shows a cross-sectional view in the case of having one photosensitive resin composition layer. The photosensitive transfer sheet 10 is formed by laminating a support 11, a photosensitive resin composition layer 12, and a protective film 15 in this order. The photosensitive resin composition layer 12 consists of a composition containing a binder, a polymerizable compound represented by the formula (I), and a photopolymerization initiator. The thickness of the photosensitive resin composition layer 12 is preferably 5 μm or more and less than 35 μm, more preferably in the range of 10 to 30 μm, and still more preferably in the range of 10 to 25 μm.
Furthermore, the photosensitive transfer sheet of the present invention is not limited to these layer configurations, and may have layers other than those shown here. For example, a thermoplastic resin layer (cushion layer) is provided between the support 21 and the photosensitive resin composition layer 12, or a barrier is provided between the photosensitive resin composition layer 12 and the thermoplastic resin layer (cushion layer). A layer may be provided.

  Moreover, sectional drawing in case the photosensitive resin composition layer has two layers as an example of the photosensitive transfer sheet of this invention is shown to FIGS.

In FIG. 2, the photosensitive transfer sheet 20 has a support 21, a first photosensitive layer 22, and a second photosensitive layer 24 laminated in this order. The first photosensitive layer 22 and the second photosensitive layer 24 are each composed of a photosensitive resin composition containing a polymer, a polymerizable monomer, and a photopolymerization initiator, and are cured by light irradiation. In the photosensitive transfer sheet of the present invention, the second photosensitive layer 24 has a relatively higher sensitivity than the first photosensitive layer 22, and at least one of the first photosensitive layer 22 or the second photosensitive layer 24 is polymerized. The main characteristic is that the photosensitive monomer component comprises a photosensitive resin composition containing the compound represented by the general formula (I). Here, high sensitivity means that the curing of the second photosensitive layer 24 starts with a light irradiation amount smaller than that of the first photosensitive layer 22.
FIG. 3 shows a photosensitive transfer sheet having a barrier layer 23 between the first photosensitive layer 22 and the second photosensitive layer 24. 4 and 5 are photosensitive transfer sheets having a protective film 25 in addition to the photosensitive transfer sheets of FIGS. 2 and 3, respectively.

  Furthermore, the photosensitive transfer sheet of the present invention is not limited to these layer configurations, and may have layers other than those shown here. For example, a layer or a barrier layer for adjusting the peelability or adhesion to the base or substrate is provided between the support 21 and the first photosensitive layer 22 or between the protective film 15 and the second photosensitive layer 24, or the first photosensitive layer. 22. Prevents the transfer of the layers and the layers between the second photosensitive layer 24 and between the first photosensitive layer 22 and the barrier layer 23, and between the second photosensitive layer 24 and the barrier layer 23. A layer or the like may be provided.

  Next, the relationship between the light irradiation amount and the photosensitive layer curing amount in the case where the photosensitive transfer sheet of the present invention has two photosensitive resin composition layers will be described with reference to FIG. FIG. 6 shows an example where the photosensitive transfer sheet shown in FIG. 2 or the photosensitive transfer sheet from which the protective film has been peeled off is transferred onto the substrate. With respect to the laminate obtained by laminating the photosensitive transfer sheet of the present invention on a substrate, from the side opposite to the substrate, that is, through a support when having a support, or a support as necessary. It is a graph (sensitivity curve) which shows the relationship between the irradiation amount of light when peeling and irradiating light to a photosensitive layer, and the thickness of the hardening layer obtained by this exposure and image development processing. In FIG. 6, the horizontal axis represents the amount of light irradiation, and the vertical axis represents the thickness of the cured photosensitive layer after being cured by light irradiation and developed. D on the vertical axis represents the thickness of the second photosensitive layer, and E represents the thickness of the entire photosensitive layer obtained by adding the thickness of the first photosensitive layer and the thickness of the second photosensitive layer.

  The barrier layer preferably contains a resin, and preferably contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. The affinity means that the solvent has emulsification, dispersion, swelling, partial dissolution, and wettability. Moreover, it is preferable that a barrier layer contains resin soluble as a main component with respect to water or a C1-C4 lower alcohol.

  In the production of the barrier layer, a binder similar to that for the photosensitive layer may be used, but a layer made of a different binder is preferable. Examples of such a polymer include various alcohol-soluble, water-soluble polymers, alcohol-dispersible, water-dispersible, emulsifiable or alkali-soluble polymers, such as polyvinyl alcohol (including modified polyvinyl alcohols), polyvinyl pyrrolidone, Examples thereof include water-soluble polyamide, gelatin, cellulose, and derivatives thereof. These polymers may be used alone or in combination of two or more. Furthermore, various polymers such as an acrylic polymer, an amide polymer, and an ester polymer may be added as long as water solubility and alkali water solubility are not impaired. For the barrier layer, the thermoplastic resin described in Japanese Patent No. 2794242 and compounds used in the intermediate layer can also be used.

As shown in FIG. 6, in the photosensitive transfer sheet of the present invention, the light irradiated from the support side, in the case of having the support, proceeds in the order of the support, the first photosensitive layer, and the second photosensitive layer. The curing of the second photosensitive layer starts with a small amount of light before the first photosensitive layer.
When the amount of light is increased after the entire second photosensitive layer is cured, the curing of the first photosensitive layer starts, and when the amount of light is further increased, the entire first photosensitive layer is cured.
The amount of light C required until curing of the first photosensitive layer may be the same as the amount of light A required to cure the second photosensitive layer, but is preferably larger than the amount of light A.

  Further, even in the case where a barrier layer is further provided between the first photosensitive layer and the second photosensitive layer as in the photosensitive transfer sheet shown in FIG. 3 or FIG. A thickness relationship is obtained. However, the film thickness E in this case represents the thickness of the entire photosensitive layer obtained by adding the thickness of the barrier layer to the thickness of the first photosensitive layer and the thickness of the second photosensitive layer.

Thus, when the photosensitive transfer sheet of the present invention has two photosensitive resin composition layers, it is possible to change the thickness of the cured layer obtained by exposure and development processing according to the exposure amount. Yes, by changing the exposure pattern as necessary, it is possible to create a range from the part that cures only the photosensitive layer closest to the substrate to the part that cures the photosensitive layer by changing the thickness in sequence. . For this reason, a single transfer sheet can be used to create three-dimensional modeling with different thicknesses inside the image, an image with characteristics such as increasing the strength of the film only in the desired portion, and increasing the image density only in the desired portion. Can be formed.
For this purpose, for example, when used in the manufacture of printed wiring boards, especially printed wiring boards having through holes and via holes, a relatively thin and high resolution hardened layer is formed in the wiring pattern formation region. A relatively thick and high-strength hardened layer can be formed in the hole or via hole. Therefore, if the photosensitive transfer sheet of the present invention is used, a pattern having sufficient tent film strength that can be used as a tenting method and sufficient resolution can be obtained at a portion where high resolution is required.

  In the photosensitive transfer sheet having the sensitivity curve as described above, the sensitivity of each photosensitive resin composition layer is relatively increased in order from the first photosensitive layer close to the support to the second photosensitive layer separated from the support. This can be achieved by increasing the height. As a method for relatively increasing the sensitivity, all known high-sensitivity techniques can be used. For example, in addition to using a high-sensitivity initiator, a sensitizer is added to the second photosensitive layer. By increasing the content of the photopolymerization initiator and / or the sensitizer in the first photosensitive layer, or increasing the content of the polymerizable monomer in the second photosensitive layer from that of the first photosensitive layer. Can also be obtained.

In addition, the photosensitive transfer sheet of the present invention has two photosensitive layers in particular, and compared with the sensitivity of the photosensitive resin composition layer (first photosensitive layer) on the side close to the support, the sensitivity on the side away from the support. In the case where a printed wiring board is produced using a photosensitive transfer sheet characterized in that the sensitivity of the photosensitive resin composition layer (second photosensitive layer) is relatively high, the light quantity S at which the curing of the second photosensitive layer begins. is preferably in the range of 0.05~10mJ / cm ² (in particular in the range of 0.1~5mJ / cm ^2). Further, the amount of light A required for curing the second photosensitive layer is preferably 20 mJ / cm ² or less (particularly in the range of ^{2 to} 15 mJ / cm ² ). The ratio A / B between the light amount A required to cure the second photosensitive layer and the light amount B required to cure the first photosensitive layer is 0.01 to 0.5 (particularly 0.02 to 0.00. It is preferable that it exists in the range of 3). Further, the ratio C / A between the light amount A necessary for curing the second photosensitive layer and the light amount C necessary until the first photosensitive layer is cured is in the range of 1 to 10 (particularly in the range of 2 to 8). It is preferable that The light quantity C is preferably 200 mJ / cm ² or less (particularly in the range of ^{2 to} 100 mJ / cm ² ).

[Production of photosensitive transfer sheet]
In the photosensitive transfer sheet of the present invention, for example, when the photosensitive resin composition layer is a single layer, a solution of the photosensitive resin composition is prepared, applied onto a support by a known method, and dried. Can be manufactured. The coating method of the photosensitive resin composition solution is not particularly limited, and 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. As drying conditions, although it changes also with each component, the kind of solvent, a usage rate, etc., it is about 30 seconds-15 minutes at the temperature of 60-110 degreeC normally.

For example, when the photosensitive resin composition layer has two layers, it can be produced, for example, as follows.
First, the above various materials are dissolved or dispersed in a solvent to prepare a first photosensitive resin composition solution for forming a first photosensitive layer and a second photosensitive resin composition solution for forming a second photosensitive layer, respectively. To do. In the case of having a barrier layer, a solution for forming the barrier layer is prepared.
As the solvent of the polymer solution for forming the barrier layer, the same coating solvent as that of the photosensitive resin composition layer may be used, but unlike these, water or a mixed solvent of water and an organic solvent can be used. . As the organic solvent, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and n-hexanol can be used.

Next, a 1st photosensitive resin composition solution is apply | coated on a support body, and a 1st photosensitive layer is formed by drying. When it has a barrier layer, a coating solution for forming a barrier layer is applied onto the first photosensitive layer and dried. A second photosensitive resin composition solution is applied thereon and dried to form a second photosensitive layer. The coating method of the photosensitive resin composition solution is not particularly limited, and 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. As drying conditions, although it changes also with each component, the kind of solvent, a usage rate, etc., it is about 30 seconds-15 minutes at the temperature of 60-110 degreeC normally.
Even when there are more photosensitive layers than two layers, it can be produced by repeating the same operation.

[Support and protective film]
It is desirable that the support is capable of peeling the photosensitive resin composition layer, has good light transmittance, and has good surface smoothness. 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, Various plastics such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulosic film, nylon film, etc. A film can be mentioned. Furthermore, a composite material composed of two or more of these can also be used. Of these, polyethylene terephthalate is particularly preferred. As for the thickness of a support body, 5-150 micrometers is common, and 10-100 micrometers is preferable.

In the photosensitive transfer sheet of the present invention, a protective film layer can be further provided on the photosensitive resin composition layer on the support. Examples of the protective film include a plastic film used for the support and a paper or a paper laminated with a plastic film such as a polyethylene film or a polypropylene film. In particular, polyethylene film and 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. At that time, it is preferable that the adhesive force A between the photosensitive resin composition layer and the support and the adhesive force B between the photosensitive resin composition layer and the protective film satisfy the relationship of A> B. Examples of the support / protective film combination include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, and the like. In addition to the method of selecting the support and the protective film from different types as described above, the above-described adhesive force relationship can be satisfied 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 strength with the photosensitive resin composition layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment , High frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment, and the like. In addition, for example, when a long drip 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 favorable roll shape.
Further, as described above, the photosensitive transfer sheet is wound and stored on, for example, a cylindrical core. In this case, it is preferable that the support is wound up so that it is on the outermost side. Also, from the viewpoint of protecting the end face during storage and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof) on the end face, and it is also preferable to use a material with low moisture permeability for packaging.

Further, the protective film may be surface-treated. The surface treatment is performed to adjust 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 at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.
In addition to the photosensitive resin composition layer, the support, and the protective film, it may have layers such as a cushion layer, a release layer, an adhesive layer, a light absorption layer, a gas barrier layer, and a surface protective layer. Two or more types of photosensitive resin layers having different film properties and sensitivities may be provided.

[Method of manufacturing printed wiring board]
An example of a method for producing a printed wiring board using the photosensitive transfer sheet of the present invention (when the photosensitive resin composition layer is one layer) is taken as an example of the production of a printed wiring board having metal plated through holes. This will be described with reference to FIG.

  A printed wiring board forming substrate 31 having a through hole 32 as shown in FIG. 7A and having a surface plated with metal 33 is prepared. A known material such as a copper clad laminate or glass epoxy is used for the printed wiring board forming substrate 31.

Next, as shown in FIG. 7B, the photosensitive resin composition layer 12 of the photosensitive transfer sheet 10 of the present invention is pressure-bonded to the surface of the printed wiring board forming substrate 31 using a pressure roller 41. Then, a laminate in which the printed wiring board forming substrate 31, the photosensitive resin composition layer 12, and the support 11 are laminated in this order is obtained (laminating step). As the pressure roller 41, 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 31 and the pressure roller 41 respectively. The heating temperature of the printed wiring board forming substrate 31 is preferably 50 to 100 ° C. The heating temperature of the pressure roller 41 is preferably 60 to 120 ° C. The roll pressure of the pressure-bonding roll is preferably in the range of ^{2 to} 5 kg / cm ² . The crimping speed is preferably 1 to 3 m / min. Further, the printed wiring board forming substrate 31 may be preheated.

  Next, as shown in FIG. 7C, when the support of the laminate is light transmissive, light (active energy) is irradiated in a pattern form from the surface on the support 11 side to form a photosensitive resin composition. The physical layer 12 is cured to form a cured product pattern 17 composed of a cured resin composition region 16 for forming a wiring pattern and a cured resin composition region 17 for protecting metal plating of a through hole (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 is suitable for the production of a small variety of products because the pattern can be formed without using an expensive mask, and the process problems caused by the mask are eliminated. . Moreover, the method of irradiating light after peeling this support body as needed (for example, when the light transmittance of a support body is inadequate etc.) can also be utilized.

  Next, when the support is not peeled off, the support 11 is peeled off from the laminate as shown in FIG. 7D (support peeling step).

Next, as shown in FIG. 7E, an appropriate developer is brought into contact with the resin composition layer 12 to dissolve and remove the uncured regions of the resin composition layer on the printed wiring board forming substrate. An etching resist is formed so that the metal plating layer 33 on the surface is exposed (development process) so as to cover the part where the wiring pattern of the panel is formed and the through hole part (tent shape). A weak alkaline aqueous solution is preferred as the developer. Base components of this weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate , Sodium pyrophosphate, potassium pyrophosphate and the like. The pH of the weak alkaline aqueous solution used for development is preferably about 8 to 12, particularly about 9 to 11. Specifically, 0.1-5 mass% sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. can be used. Moreover, although the temperature of a developing solution can be adjusted according to the developability of the photosensitive resin layer, generally about 25 to 40 degreeC is preferable. In addition, a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, etc.) or a small amount of an organic solvent for promoting development may be used in combination with the developer.
Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing and post-exposure processing as needed after image development.

  Next, as shown in FIG. 7F, the exposed metal plating layer 33 is dissolved with an etching solution (etching step). Since the opening of the through hole 32 is covered with the cured resin composition (tent film) 17, the metal plating of the through hole is performed without the etching solution entering the through hole and corroding the metal plating in the through hole. It will remain in a predetermined shape. By this etching, a wiring pattern 34 of the printed wiring board is formed. When the metal plating layer 33 is formed of copper, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used as an etching solution. Among these, a ferric chloride solution is particularly preferable from the viewpoint of etching factor.

  Finally, as shown in FIG. 7 (G), a strong alkaline aqueous solution is brought into contact with the cured resin pattern, and the cured product pattern is finely crushed into strips 18 and removed from the printed wiring board forming substrate 31 (cured). Object removal step). Examples of the basic component of the strong alkaline aqueous solution include sodium hydroxide and potassium hydroxide. The pH of the strong alkaline aqueous solution used is preferably about 12 to 14, particularly about 13 to 14. Specifically, 1-10 mass% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. can be used.

The printed wiring board may be a multilayer printed wiring board. Further, the photosensitive transfer sheet of the present invention may be used not only in the above etching process but also in a plating process.

  Next, an example of a method of manufacturing a printed wiring board using the photosensitive transfer sheet of the present invention (when the photosensitive resin composition layer is two layers) is taken as an example of manufacturing a printed wiring board having metal plated through holes. This will be described with reference to FIG. 8 of the accompanying drawings. 8 shows the case where the photosensitive transfer sheet shown in FIG. 3 or the photosensitive transfer sheet shown in FIG. 5 is used, but even when the photosensitive transfer sheet shown in FIG. 2 or 4 is used, It is similar except that the barrier layer 23 is not included.

  As shown in FIG. 8A, a printed wiring board forming substrate 31 having a through hole 32 and having a surface covered with a metal plating layer 33 is prepared. As the printed wiring board forming substrate 31, a copper-clad laminated substrate 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. 8B, the second photosensitive layer 24 of the photosensitive transfer sheet 20 of the present invention is formed on the printed wiring board by peeling off the protective film if it has a protective film. The pressure roller 41 is used for pressure bonding so as to be in contact with the surface of the substrate 31 (lamination process). Thereby, a laminate in which the printed wiring board forming substrate 31, the second photosensitive layer 24, the barrier layer 23, the first photosensitive layer 22, and the support 21 are laminated in this order is obtained. Lamination of the photosensitive transfer sheet can be performed at room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.). In particular, the heating is preferably performed at 60 to 140 ° C. The roll pressure of the pressure-bonding roll is preferably in the range of ^{2 to} 5 kg / cm ² . The crimping speed is preferably 1 to 3 m / min. Further, the printed wiring board forming substrate 31 may be preheated.
Instead of using the photosensitive transfer sheet, the second photosensitive resin composition solution, the barrier layer solution, and the first photosensitive resin composition solution for manufacturing the photosensitive transfer sheet are sequentially added to the printed wiring board forming substrate in this order. By directly coating on the surface and drying, it is also possible to obtain a laminate in which the printed wiring board forming substrate, the second photosensitive layer, the barrier layer, and the first photosensitive layer are laminated in this order.

  Next, as shown in FIG. 8C, the photosensitive layer is cured by irradiating light from the surface on the support 21 side of the laminate. At this time, light irradiation may be performed after peeling the support as necessary (for example, when the light transmittance of the support is insufficient). The wiring pattern forming region of the printed wiring board forming substrate 31 is irradiated with a predetermined amount of light necessary for curing the second photosensitive layer 24 to form a region of the hardened layer 26 for forming the wiring pattern. (Wiring part exposure step). The opening portion of the through hole 32 of the printed wiring board forming substrate and the periphery thereof are irradiated with light of a light amount necessary for curing the first photosensitive layer 22 and the second photosensitive layer 24, respectively. A region of the hardened layer 27 for protecting the metal layer is formed (hole part exposure step). The wiring portion exposure step and the hole portion exposure step may be performed independently, but are preferably performed in parallel. The exposure is performed by irradiating light through a photomask, or by irradiating laser light using a laser exposure apparatus. In particular, the latter method using a laser scanning exposure apparatus is suitable for the production of a small variety of products because the pattern can be formed without using an expensive mask, and the process problems caused by the mask are eliminated. .

In the case of irradiating light through a photomask, a light amount for curing only the second photosensitive layer is irradiated through a photomask for forming a region of the hardened layer 26 for forming a wiring pattern, thereby protecting the metal layer of the through hole It is also possible to use a method in which exposure is performed twice so as to irradiate a light amount for curing both the second photosensitive layer and the first photosensitive layer through a photomask for forming the region of the cured layer 27 for use. Alternatively, the light transmittance corresponding to the region portion of the hardened layer 26 for forming the wiring pattern is low and the light transmittance corresponding to the region portion of the hardened layer 27 for protecting the metal layer of the through hole is high. Batch exposure can also be performed using a mask. On the other hand, when irradiating laser light using a laser exposure apparatus, it is preferable to perform scanning exposure while changing the light irradiation amount in each necessary region.
As a light source used for exposure, when light irradiation is performed through a support, the electromagnetic wave is transmitted through the support 21 and is active with respect to the photopolymerization initiator used. The wavelength is 310 to 700 nm (preferably A light source that generates visible light from ultraviolet rays in the range of 350 to 500 nm) is used. For example, a known light source such as an (ultra) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a copying fluorescent tube, or a semiconductor laser can be used. In addition, an electron beam or an X-ray may be used. The same light source can be used even when light irradiation is performed after the support is peeled off.

Next, when the support is not peeled off, the support 21 is peeled off from the laminate as shown in FIG. 8D (support peeling step).
Next, as shown in FIG. 8 (E), the uncured regions of the first photosensitive layer 22, the barrier layer 23, and the second photosensitive layer 24 on the printed wiring board forming substrate 31 are dissolved with an appropriate developer. The pattern of the hardened layer 26 for wiring pattern formation and the hardened layer 27 for protecting the metal layer of the through hole is formed by removing, and the metal plating layer 33 on the substrate surface is exposed (development process). The developer is preferably a weak alkaline aqueous solution. Base components of this weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate , Sodium pyrophosphate, potassium pyrophosphate and the like. The pH of the weak alkaline aqueous solution used for development is preferably about 8 to 12, particularly about 9 to 11. Specifically, 0.1-5 mass% sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. can be used. Moreover, although the temperature of a developing solution can be adjusted according to the developability of the photosensitive resin layer, generally about 25 to 40 degreeC is preferable. In addition, a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, etc.) or a small amount of an organic solvent for promoting development may be used in combination with the developer.

Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing and post-exposure processing as needed after image development.
Next, as shown in FIG. 8F, the exposed metal plating layer 33 on the substrate surface is dissolved and removed with an etching solution (etching step). Since the opening of the through hole 32 is covered with the cured resin composition (tent film) 27, the metal plating of the through hole is performed without the etching solution entering the through hole and corroding the metal plating in the through hole. It will remain in a predetermined shape. Thereby, the wiring pattern 34 is formed on the printed wiring board forming substrate 31. When the metal plating layer 33 is formed of copper, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used as an etching solution. Among these, a ferric chloride solution is particularly preferable from the viewpoint of etching factor.

Next, as shown in FIG. 8G, the hardened layers 26 and 27 are removed from the printed wiring board forming substrate as a release piece 28 with a strong alkaline aqueous solution or the like (hardened product removing step). Examples of the basic component of the strong alkaline aqueous solution include sodium hydroxide and potassium hydroxide. The pH of the strong alkaline aqueous solution used is preferably about 12 to 14, particularly about 13 to 14. Specifically, 1-10 mass% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. can be used.
The printed wiring board may be a multilayer printed wiring board. Further, the photosensitive transfer sheet 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, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, There are gold plating such as soft gold plating.

[Example 1]
(Formation of photosensitive resin layer)
A photosensitive resin composition solution having the following composition was prepared, applied to a 20 μm thick polyethylene terephthalate film so as to have a dry film thickness of 20 μm, and dried to form a photosensitive resin layer.

────────────────────────────────────────
Photopolymer composition solution --------------------------------
A 35% by mass solution of methacrylic acid / methyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate copolymer (binder) (copolymerization composition: 29/55/12/4 mol%, weight average molecular weight: 100,000) 18.2 masses Part polymerizable compound (1) 10.9 parts by mass 4,4′-bis (diethylamino) benzophenone 0.06 parts by mass 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole 1.4 parts by mass Phenyltribromomethylsulfone 0.02 parts by mass Leucocrystal violet 0.02 parts by mass Malachite green oxalate 0.02 parts by mass p-toluenesulfonamide 0.63 parts by mass Methyl ethyl ketone 31.8 Parts by mass 1-methoxy-2-propanol 17.1 parts by mass ------- ─────────────────────────────────

  Next, a 12 μm-thick polypropylene film was laminated on the photosensitive resin composition layer. The photosensitive transfer sheet thus obtained was evaluated for (1) shortest development time, (2) sensitivity, (3) resolution, (4) adhesion, (5) number of tent film tears, and (6) peeling time. The results are shown in Table 2. The shortest development time, resolution, adhesion, number of tent film breaks, and peeling time were measured by the following methods. The results are shown in Table 1.

(1) Measuring method of the shortest development time The surface of the surface is dried and the photosensitive resin composition layer is laminated to the laminator while peeling the polypropylene film of the photosensitive transfer sheet on the surface of the dried copper clad laminate (no through-hole). (MODEL8B-720-PH, Taisei Laminator Co., Ltd.) is used for pressure bonding to produce a laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The pressure bonding conditions are a laminate temperature of 70 ° C., a pressure roll temperature of 105 ° C., a pressure roll 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) Sensitivity measurement method Under the same conditions as the shortest development time evaluation method in (1) above, a laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared, and the 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, manufactured by Oak Co., Ltd.) on the surface of the laminated polyethylene terephthalate film via a step tablet (manufactured by Fuji Photo Film, 15-step step tablet) ) Is used to irradiate light of 40 mJ / cm ² to expose the photosensitive resin composition layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. 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 was sprayed for 80 seconds at a spray pressure of 0.05 MPa, and the cured resin pattern was washed with water and dried. Read the maximum number of steps of the step tablet where the film remains completely, and use it as a sensitivity test. (The step tablet has a lower light transmittance as the number of steps increases. Therefore, the higher the sensitivity, the higher the determination step number.) Also, from this sensitivity, the film remains completely up to the third step with the step tablet. A proper exposure amount is calculated. The following tests were conducted using this exposure amount as the evaluation exposure amount.

(3) Resolution measurement method Under the same conditions as the evaluation method for the shortest development time in (1) above, a laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared, and room temperature was measured. Let stand at (23 ° C., 55% RH) for 10 minutes. Ultra high pressure mercury lamp (3kW ultra high pressure mercury lamp double-sided simultaneous exposure device HMW-) via photomask (line / space = 1/1, line width 10 μm to 100 μm with various resolutions) on the surface of laminated polyethylene terephthalate film 6-N type, manufactured by Oak Co., Ltd.) and exposed at the exposure amount calculated in (2), and allowed to stand at room temperature for 10 minutes, and then the polyethylene terephthalate film is peeled off from the laminate. 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.

(4) Adhesion measurement method Except for using a photomask of line / space = 1/3 and a line width of 10 μm to 100 μm, the same operation as the resolution evaluation method in (3) 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.

(5) Method for measuring the number of tent film breaks The shortest development of (1) above, except that a copper clad laminate having 400 copper plated through holes with a diameter of 3 mm is used 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 is prepared under the same conditions as the time evaluation method, and is allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. . The entire surface of the photosensitive resin composition layer is exposed by irradiating light on the surface of the polyethylene terephthalate film of the laminate with the exposure amount determined in (2) above using an ultrahigh pressure mercury lamp. After leaving at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. 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. at a spray pressure of 0.2 MPa for 6 times the shortest development time obtained in (1) above, and cured. The resin part is developed, washed with water and dried. The copper clad laminate was etched by spraying a copper clad laminate with a cured resin obtained in this way with a cupric chloride aqueous solution (etching solution) at 45 ° C. for 60 seconds at a spray pressure of 0.1 MPa. To do. The number of holes whose tent film has been torn is counted up to this point, and this is taken as the number of tents to be broken (small numbers are good).

(6) Measuring method of peeling time Under the same conditions as the evaluation method of the shortest development time in (1) above, a laminate comprising a copper-clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared, Let stand at (23 ° C., 55% RH) for 10 minutes. The entire surface of the photosensitive resin composition layer is exposed by irradiating the surface of the polyethylene terephthalate film of the laminate with the exposure amount obtained in (2) using an ultrahigh pressure mercury lamp. After standing at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. Under the same conditions as the resolution evaluation method of (3) above, an aqueous solution of sodium carbonate is sprayed on the entire surface of the resin composition layer on the copper clad laminate to develop the cured resin pattern, washed with water and dried. The copper-clad laminate with a cured resin pattern thus obtained is immersed in a 3% by mass aqueous sodium hydroxide solution. The time required from the start of immersion of the copper-clad laminate to the complete removal of the cured resin pattern on the copper-clad laminate is measured, and this is taken as the peeling time.

[Example 2]
A dry film photoresist was obtained in the same manner as in Example 1 except that the polymerizable compound (33) was used instead of the polymerizable compound (1). The shortest development time, sensitivity, resolution, adhesion, number of tent film breaks, and peeling time of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
A dry film photoresist was obtained in the same manner as in Example 1 except that the polymerizable compound (65) was used instead of the polymerizable compound (1). The shortest development time, sensitivity, resolution, adhesion, number of tent film breaks, and peeling time of this dry film photoresist were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
Instead of 10.9 parts by mass of the polymerizable compound (1), 8.7 parts by mass of the polymerizable compound (1) and the following polymerizable compound (101) (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2 A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that 2 mass was used. The shortest development time, sensitivity, resolution, adhesion, number of tent film breaks, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane

[Example 5]
Instead of 10.9 parts by mass of polymerizable compound (1), 8.7 parts by mass of polymerizable compound (1), polymerizable compound (102) (Biscoat # 2338, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2.2 parts by mass A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that was used. The shortest development time, sensitivity, resolution, adhesion, number of tent film breaks, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

γ-chloro-β-hydroxypropyl-β′-methacryloyloxy-orthophthalate

[Example 6]
35% by weight of methacrylic acid / methyl methacrylate / styrene copolymer (binder) instead of 51.9 parts by weight of 35% by weight solution of methacrylic acid / methyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate copolymer (binder) Except for using 31.1 parts by mass of a solution (copolymerization composition: 25/50/25 mol%, weight average molecular weight: 100,000, solvent is methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (mass ratio)) A photosensitive transfer sheet was obtained in the same manner as in Example 1. The shortest development time, sensitivity, resolution, adhesion, number of tent film breaks, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 7]
A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that 0.06 parts by mass of N-methylacridone was used instead of 0.06 parts by mass of 4,4′-bis (diethylamino) benzophenone. The shortest development time, sensitivity, resolution, adhesion, number of tent film breaks, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 8]
(Formation of first photosensitive layer)
A photosensitive resin composition solution of Example 1 was prepared and applied to a 20 μm thick polyethylene terephthalate film so that the dry film thickness was 20 μm, thereby forming a 20 μm thick first photosensitive layer.

(Formation of barrier layer)
On the first photosensitive layer, a water-soluble polymer solution having the following composition was applied and dried to form a 1.6 μm thick barrier layer.

────────────────────────────────────────
Water-soluble polymer solution ────────────────────────────────────────
Polyvinyl alcohol 13 parts by weight Polyvinylpyrrolidone 6 parts by weight Water 200 parts by weight Methanol 180 parts by weight ──────────────────────────────── ────────

(Formation of second photosensitive layer)
On the barrier layer, a second photosensitive resin composition solution having the following composition was applied and dried to form a photosensitive layer (second photosensitive layer) having a thickness of 5 μm.

────────────────────────────────────────
Second photosensitive resin composition solution ────────────────────────────────────────
Methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate copolymer (copolymer composition: 29/55/12/4 mol%, mass average molecular weight: 100,000) 15 parts by mass Polypropylene glycol diacrylate 5 parts by mass Tetraethylene glycol dimethacrylate 1.5 parts by mass N-methylacridone 0.16 parts by mass 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 1 .04 parts by weight p-toluenesulfonamide 0.5 parts by weight Malachite green oxalate 0.02 parts by weight 1,2,4-triazole 0.01 parts by weight Leuco Crystal Violet 0.2 parts by weight Tribromomethylphenylsulfone 0 .1 part by weight Methyl ethyl ketone 10 parts by weight 1-methoxy- 2-Propanol 20 parts by mass --------------------------------

(Preparation of photosensitive transfer sheet)
A 12 μm thick polypropylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet.
(1) The shortest development time of this photosensitive transfer sheet was evaluated in the same manner as in Example 1. (2) Sensitivity was measured as follows.

(2) Sensitivity measurement method Under the same conditions as the shortest development time evaluation method in (1) above, a laminate comprising a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film was prepared, and the 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, manufactured by Oak Co., Ltd.) on the surface of the laminated polyethylene terephthalate film via a step tablet (manufactured by Fuji Photo Film, 15-step step tablet) ) Is used to irradiate light of 40 mJ / cm ² to expose the photosensitive resin composition layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. 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 was sprayed for 80 seconds at a spray pressure of 0.05 MPa, and the cured resin pattern was washed with water and dried. The maximum number of steps in which both the first photosensitive layer and the second photosensitive layer of the step tablet are completely left is read and used as a sensitivity test (A). From this sensitivity, the exposure amount such that both the first photosensitive layer and the second photosensitive layer remain completely up to the third stage in the above step tablet is calculated as an evaluation exposure amount (A). 5) Number of tent film tears, (6) Peelability test was performed. Furthermore, the maximum number of steps where only the second photosensitive layer is completely left is read and used as a sensitivity test (b). In addition, from this sensitivity, the exposure amount that only the second photosensitive layer in the above step tablet leaves the film completely up to the third stage is calculated to be the evaluation exposure amount (b). With this exposure amount, (3) resolution (4) An adhesion test was performed.
(3) Resolution, (4) Adhesion, (5) Number of tent film tears, (6) Peelability test was performed in the same manner as in Example 1 except that the exposure dose was changed to the exposure dose calculated in (2). It was. The results are shown in Table 1.

[Comparative Example 1]
Photosensitive transfer sheet in the same manner as in Example 1 except that 8.7 parts by mass of dodecapropylene glycol diacrylate and 2.2 parts by mass of tetraethylene glycol dimethacrylate were used instead of 10.9 parts by mass of the polymerizable compound (1). Got. The shortest development time, resolution, adhesion, number of tent film tears, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that the polymerizable compound (C-1) was used instead of the polymerizable compound (1). The shortest development time, resolution, adhesion, number of tent film tears, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

C-1

[Comparative Example 3]
A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that the polymerizable compound (C-2) was used instead of the polymerizable compound (1). The shortest development time, resolution, adhesion, number of tent film tears, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

C-2

[Comparative Example 4]
A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that the polymerizable compound (C-3) was used instead of the polymerizable compound (1). The shortest development time, resolution, adhesion, number of tent film tears, and peeling time of this photosensitive transfer sheet were evaluated in the same manner as in Example 1. The results are shown in Table 1.

C-3

Table 1 ─────────────────────────────────────────
Photosensitivity Shortest development Evaluation Tent transfer sheet Time Sensitivity Exposure Amount Resolution Adhesion Number of tears Peeling time ──────────────────────────────── ────────
Example 1 15 seconds 3 40 mJ 35 μm 30 μm 2 pieces 22 seconds
Example 2 15 seconds 3 40 mJ 35 μm 30 μm 5 pieces 25 seconds Example 3 15 seconds 3 40 mJ 30 μm 30 μm 8 pieces 26 seconds Example 4 20 seconds 3 40 mJ 25 μm 30 μm 12 pieces 27 seconds Example 5 15 seconds 3 40 mJ 30 μm 28 seconds Example 6 15 seconds 3 40 mJ 30 μm 30 μm 5 pieces 26 seconds Example 7 15 seconds 7 10 mJ 30 μm 30 μm 3 pieces 24 seconds Example 8 25 seconds 3 * 40 mJ * 20 μm 20 μm 3 pieces 30 seconds ────── ─────────────────────────────────
Comparative Example 1 15 seconds 3 40 mJ 40 μm 35 μm 60 pieces 40 seconds Comparative Example 2 11 seconds 3 40 mJ 40 μm 30 μm 30 pieces 25 seconds Comparative Example 3 25 seconds 3 40 mJ 40 μm 35 μm 50 pieces 35 seconds Comparative Example 4 20 seconds 3 40 mJ 40 μm 30 m 35 seconds ─────────────────────────────────────────
(註)
*: Value of the first photosensitive layer (In Example 8, the sensitivity of the second photosensitive layer is 9, and the evaluation exposure amount of the second photosensitive layer is 5 mJ)

[Example 9]
(Formation of cured resin pattern by laser exposure)
The surface is leveled, and the photosensitive resin composition layer of the photosensitive transfer sheet produced in Example 1 is peeled off from the dried copper-clad laminate, and the polypropylene film on the photosensitive resin composition layer is peeled off. The laminate was made of a copper clad laminate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The polyethylene terephthalate film of this laminate is measured by the same method as the sensitivity measurement method using a laser exposure apparatus having a laser light source with a wavelength of 400 to 415 nm. The amount of exposure that remained was calculated to be 105 mJ / cm ² . Photosensitive resin composition by irradiating 105 mJ / cm ² of laser light with a line / space = 1/1 pattern with a line width of 10 μm to 100 μm and a line / space = 1/3 with a line width of 10 μm to 100 μm. The physical layer was exposed. 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 30 μm and peels off 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 15 μm, with the light of the ultra high pressure mercury lamp The resolution and adhesion were improved compared to the case of exposure.

[Example 10]
(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. While peeling off the polypropylene film on the resin composition layer, the film was pressure-bonded 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 processing so far, the number of tent film breaks was 3, which was almost the same as when exposed to light from an ultrahigh pressure mercury lamp.

It is sectional drawing of an example of the photosensitive transfer sheet (one photosensitive resin composition layer) according to this invention. It is sectional drawing of an example of the photosensitive transfer sheet (the photosensitive resin composition layer is two layers) according to this invention. It is a schematic cross section of another example of the photosensitive transfer sheet (the photosensitive resin composition layer is two layers) according to the present invention. It is a schematic cross section of another example of a photosensitive transfer sheet (two photosensitive resin composition layers) according to the present invention. It is a schematic cross section of another example of a photosensitive transfer sheet (two photosensitive resin composition layers) according to the present invention. It is a graph which shows the sensitivity curve showing the relationship between the light irradiation amount and the thickness of a hardened layer when light is irradiated from the support body side to the photosensitive transfer sheet (two photosensitive resin composition layers) according to this invention. . It is the figure which showed schematically the manufacturing process of the printed wiring board which has a metal plating through hole according to this invention. It is a figure which shows the manufacturing process of the printed wiring board which has a through hole according to this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photosensitive transfer sheet 11 Support body 12 Photosensitive resin composition layer 15 Protective film 16 Cured resin composition area | region for wiring pattern formation 17 Cured resin composition area | region for metal plating protection of a through hole 18 Stripping piece 20 Photosensitive transfer Sheet 21 Support 22 First photosensitive layer 23 Barrier layer 24 Second photosensitive layer 25 Protective film 26 Hardened layer for forming wiring pattern 27 Hardened layer for protecting metal layer of through hole 28 Peeling piece 31 Printed wiring board forming substrate 32 Through Hole 33 Metal plating layer 34 Wiring pattern 41 Pressure roller

Claims (21)

A photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator, wherein the polymerizable compound is represented by the following formula (I):
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. It is a divalent linking group consisting of a combination, or an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof is interposed between the combinations. P and q are each independently an integer of 1 to 10; l and m are each independently an integer of 1 to 50; n is an integer of 3 to 6; by and; and, L ² is either a n-valent aliphatic group or an n-valent aromatic group, or they alkylene group, substituted alkylene group, alkenylene It consists of a combination of a len group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. an n-valent linking group].   The photosensitive resin composition according to claim 1, wherein, in formula (I), l is an integer of 1 to 14, and m is an integer of 1 to 30.   The photosensitive resin composition according to claim 1, wherein in formula (I), p and q are each independently 2 or 3. 2. The photosensitive resin composition according to claim 1, wherein in Formula (I), L ¹ is a divalent linking group comprising an alkylene group, an arylene group, a substituted arylene group, or a combination thereof. The photosensitive resin composition according to claim 1, wherein L ² in formula (I) is an n-valent aliphatic group.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the binder is a polymer having a carboxyl group.   The binder is a copolymer having a repeating unit having a carboxyl group and a repeating unit having no carboxyl group, and the ratio of the repeating unit having a carboxyl group in the copolymer is 5 to 50 mol%. Photosensitive resin composition.   The photosensitive resin composition according to any one of claims 1 to 7, wherein the photopolymerization initiator is selected from the group consisting of a heterocyclic compound having a halogen-substituted alkyl group, oxime, hexaarylbiimidazole, and a ketone. .   The photosensitive resin composition according to any one of claims 1 to 8, comprising 10 to 90% by mass of a binder, 5 to 60% by mass of a polymerizable compound, and 0.1 to 30% by mass of a photopolymerization initiator. .   Furthermore, the photosensitive resin composition of any one of Claim 1 to 9 containing a sensitizer.   It is an object for printed wiring board manufacture, The photosensitive resin composition in any one of Claims 1-10. A photosensitive transfer sheet having a support and a photosensitive resin layer containing a binder, a polymerizable compound, and a photopolymerization initiator, wherein the polymerizable compound is represented by the following formula (I): Transfer sheet:
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. It is a divalent linking group consisting of a combination, or an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof is interposed between the combinations. P and q are each independently an integer of 1 to 10; l and m are each independently an integer of 1 to 50; n is an integer of 3 to 6; by and; and, L ² is either a n-valent aliphatic group or an n-valent aromatic group, or they alkylene group, substituted alkylene group, alkenylene It consists of a combination of a len group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. an n-valent linking group].   The photosensitive transfer sheet according to claim 12, wherein the thickness of the photosensitive resin layer is 5 μm or more and less than 35 μm.   The photosensitive transfer sheet according to claim 12 or 13, wherein a protective film layer is provided on the photosensitive resin layer. By performing the following steps (1) to (6) in this order, a printed wiring board manufacturing 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 support, a binder, a polymerizable compound represented by the following formula (I), and photopolymerization are formed on the surface of a printed wiring board forming substrate having a through hole or a via hole and the surface is covered with a metal layer. A photosensitive transfer sheet having an initiator-containing photosensitive resin layer is pressure-bonded so that the photosensitive resin layer is in contact with the metal layer, and the printed wiring board forming substrate, the photosensitive resin layer, and the support are Lamination process to obtain a laminated body laminated in order:
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. It is a divalent linking group consisting of a combination, or an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof is interposed between the combinations. P and q are each independently an integer of 1 to 10; l and m are each independently an integer of 1 to 50; n is an integer of 3 to 6; by and; and, L ² is either a n-valent aliphatic group or an n-valent aromatic group, or they alkylene group, substituted alkylene group, alkenylene It consists of a combination of a len group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. an n-valent linking group];
(2) Irradiate light in a pattern from the support side of the laminate to cure the photosensitive resin layer, and a curable resin composition region for wiring pattern formation and a cured resin for metal protection of through holes or via holes An exposure step of forming a cured resin composition pattern comprising a composition region;
(3) a support peeling process for peeling the support from the laminate;
(4) A development step of dissolving and removing the uncured region of the photosensitive resin layer on the printed wiring board forming substrate to expose the metal layer of the uncured region on the substrate surface;
(5) an etching step of dissolving and removing the metal layer in the exposed region with an etching solution; and
(6) A cured layer removing step of removing the cured layer from the printed wiring board forming substrate.   The method for manufacturing a printed wiring board according to claim 15, wherein laser light is used as light in the step (3). A laminate in which a photosensitive resin layer containing a binder, a polymerizable compound and a photopolymerization initiator is laminated on a printed wiring board forming substrate having a through hole or a via hole whose inner wall surface is covered with a metal layer. A laminate in which the polymerizable compound is represented by the following formula (I):
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. It is a divalent linking group consisting of a combination, or an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof is interposed between the combinations. P and q are each independently an integer of 1 to 10; l and m are each independently an integer of 1 to 50; n is an integer of 3 to 6; by and; and, L ² is either a n-valent aliphatic group or an n-valent aromatic group, or they alkylene group, substituted alkylene group, alkenylene It consists of a combination of a len group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. an n-valent linking group].   The laminate according to claim 17, wherein a support is laminated on the photosensitive resin layer. A first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on the support, and a photosensitivity relatively higher than the photosensitivity of the first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator. The photosensitive transfer, wherein the second photosensitive layer is laminated in this order, and the polymerizable compound contained in at least one of the first photosensitive layer and the second photosensitive layer is represented by the following formula (I): Sheet:
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. It is a divalent linking group consisting of a combination, or an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof is interposed between the combinations. P and q are each independently an integer of 1 to 10; l and m are each independently an integer of 1 to 50; n is an integer of 3 to 6; by and; and, L ² is either a n-valent aliphatic group or an n-valent aromatic group, or they alkylene group, substituted alkylene group, alkenylene It consists of a combination of a len group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. an n-valent linking group]. A manufacturing method comprising the following steps of a printed wiring board having a through hole or a via hole:
(1) The surface of the printed wiring board forming substrate having a through hole or via hole whose inner wall surface is covered with a metal layer, the surface being covered with a metal layer, a support, a binder, a polymerizable compound, and light A first photosensitive layer containing a polymerization initiator, a second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator and having a photosensitivity relatively higher than the photosensitivity of the first photosensitive layer are laminated in this order. A photosensitive transfer sheet in which the polymerizable compound contained in at least one of the first photosensitive layer and the second photosensitive layer is represented by the following formula (I) is pressure-bonded so that the second photosensitive layer side is in contact with the metal layer. And a lamination step of obtaining a laminate in which at least the second photosensitive layer, the first photosensitive layer, and the support are laminated on the printed wiring board forming substrate:
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. It is a divalent linking group consisting of a combination, or an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof is interposed between the combinations. P and q are each independently an integer of 1 to 10; l and m are each independently an integer of 1 to 50; n is an integer of 3 to 6; by and; and, L ² is either a n-valent aliphatic group or an n-valent aromatic group, or they alkylene group, substituted alkylene group, alkenylene It consists of a combination of a len group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. an n-valent linking group];
(2) The process of peeling a support body as needed;
(3) From the opposite side of the laminate to the printed wiring board forming substrate, the wiring pattern forming region of the printed wiring board forming substrate is irradiated with a predetermined amount of light necessary for curing the second photosensitive layer. To form a hardened layer region of a predetermined pattern, and a region including the opening of the through hole or via hole is supplied with a predetermined amount of light necessary to cure both the first photosensitive layer and the second photosensitive layer. An exposure step of forming a cured layer region that covers the opening region of the through hole or via hole by irradiating the pattern of
(4) A support peeling step of peeling the support from the laminate as necessary;
(5) A developing step of dissolving and removing uncured regions of the first photosensitive layer and the second photosensitive 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 layer removing step of removing the cured layer from the printed wiring board forming substrate. A second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on the substrate, and a photosensitivity relatively lower than the photosensitivity of the second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator. The first photosensitive layer is laminated in this order, and the polymerizable compound contained in at least one of the first photosensitive layer and the second photosensitive layer is represented by the following formula (I):
(I)

[Wherein, R ¹ represents a hydrogen atom or a methyl group; L ¹ represents an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a group thereof. It is a divalent linking group consisting of a combination, or an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof is interposed between the combinations. P and q are each independently an integer of 1 to 10; l and m are each independently an integer of 1 to 50; n is an integer of 3 to 6; by and; and, L ² is either a n-valent aliphatic group or an n-valent aromatic group, or they alkylene group, substituted alkylene group, alkenylene It consists of a combination of a len group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, a sulfonyl group, or a combination thereof. an n-valent linking group].

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