WO2012132580A1 - Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern formation method, and printed substrate - Google Patents

Abstract

A photosensitive composition comprising: a polyurethane resin containing an acid-modified ethylenically unsaturated group, which has a structural unit represented by general formula (G); a specific organic phosphoric acid metal salt having an average particle diameter of 1.0 μm or less; and a polymerizable compound. In general formula (G), R¹ - R³ independently represent a hydrogen atom or a univalent organic group; A represents a bivalent organic group; X represents an oxygen atom, a sulfur atom or -N(R⁴)-; and R⁴ represents a hydrogen atom or a univalent organic group.

Description

Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board

The present invention relates to a photosensitive composition suitable as a solder resist material for a flexible substrate, a photosensitive film using the photosensitive composition, a photosensitive laminate, a method for forming a permanent pattern, and a printed board.

Conventionally, when forming a permanent pattern such as a solder resist, a photosensitive film having a photosensitive layer formed by applying a photosensitive composition on a support and drying it has been used. As a method for forming a permanent pattern such as a solder resist, for example, a photosensitive film is laminated on a substrate such as a copper-clad laminate on which a permanent pattern is formed to form a laminate, and the photosensitive layer in the laminate is formed. There is known a method of forming a permanent pattern by performing exposure on the substrate, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like.

Improvement of flame retardancy in the photosensitive composition used for the solder resist is one of important issues, and various studies have been made.

For example, a urethane resin (A) having a carboxyl group and an ethylenically unsaturated group and a phosphinic acid salt (B) having a volume average particle diameter in the range of 0.1 μm to 1 μm are added to 100 parts by mass of the urethane resin (A). On the other hand, a photosensitive flame retardant resin composition containing 5 to 50 parts by mass has been proposed (see Patent Document 1).
In this proposed technique, the carboxyl group in the carboxyl group-containing urethane prepolymer (a) is reacted with the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group. A urethane resin obtained by reacting the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) and the acid anhydride group in the polybasic acid anhydride (d) is used.

Photosensitivity containing (A) a novolac acid-modified vinyl group-containing epoxy resin having a biphenyl skeleton, (B) a phosphinic acid salt, (C) a photopolymerizable compound, and (D) a photopolymerization initiator. Resin compositions have been proposed (see Patent Documents 2 and 3).

And (A) a novolac acid-modified vinyl group-containing epoxy resin having a biphenyl skeleton, (B) a polyurethane resin, (C) a phosphinic acid salt, and (D) at least one ethylenically unsaturated group in the molecule. The photosensitive resin composition containing the photopolymerizable compound which has and (E) photoinitiator is proposed (refer patent document 4).
In this proposed technique, a polyurethane resin that is a reaction product of an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group is used.

However, these proposed technologies have the problem that the required flame resistance is obtained, but the folding resistance is not sufficient.

Examples of flame retardants other than phosphinates that can be used in the photosensitive composition include phosphazene compounds, condensed phosphate esters, and cyclic phosphorus compounds.
However, when these flame retardants are used, there is a problem that plating resistance is lowered.

JP 2010-117452 A JP 2010-169810 A Japanese Patent No. 4586922 JP 2009-251585 A

In view of such a situation, an object of the present invention is to achieve the following object. That is, the present invention is a photosensitive composition excellent in flame retardancy, folding resistance, and plating resistance, and a photosensitive film, a photosensitive laminate, a permanent pattern forming method using the photosensitive composition, And to provide a printed circuit board.

Means for solving the problems are as follows.
<1> An acid-modified ethylenically unsaturated group-containing polyurethane resin, a phosphoric acid metal salt represented by the following general formula (1), a polymerizable compound, and a photopolymerization initiator,
The acid-modified ethylenically unsaturated group-containing polyurethane resin has a structural unit represented by the following general formula (G),
The photosensitive composition whose average particle diameter of the phosphoric acid metal salt represented by this General formula (1) is 1.0 micrometer or less.

In general formula (1), A ^P and B ^P are each independently any one of a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, and an aryl group. To express. M represents any of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K. m represents an integer of 1 to 4.

In general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group. A represents a divalent organic group. X represents one of an oxygen atom, a sulfur atom, and —N (R ⁴ ) —. R ⁴ represents a hydrogen atom or a monovalent organic group.
<2> The photosensitive composition according to <1>, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin contains a polymer diol residue as a repeating unit.
<3> The photosensitive composition according to <2>, wherein the polymer diol residue has a mass average molecular weight of 400 to 8,000.
<4> The photosensitive composition according to <2> or <3>, wherein a mass ratio of the polymer diol residue in the acid-modified ethylenically unsaturated group-containing polyurethane resin is 10 to 60%.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has an aromatic group.
<6> The acid-modified ethylenically unsaturated group-containing polyurethane resin has at least one skeleton selected from bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, and anthracene type <1> to The photosensitive composition of any one of <5>.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the maximum particle diameter (d100) of the metal phosphate represented by the general formula (1) is 5 μm or less.
<8> The photosensitive composition according to any one of <1> to <7>, further containing a thermal crosslinking agent.
<9> A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <8> on a support.
<10> A photosensitive laminate having a photosensitive layer containing the photosensitive composition according to any one of <1> to <8> on a substrate.
<11> A method for forming a permanent pattern comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <8>.
<12> A printed board on which a permanent pattern is formed by the method for forming a permanent pattern according to <11>.

According to the present invention, the above object can be achieved, and a photosensitive composition excellent in all of flame retardancy, folding resistance, and plating resistance, and a photosensitive film and a photosensitive laminate using the photosensitive composition. A body, a method for forming a permanent pattern, and a printed circuit board can be provided.

The above and other features and advantages of the present invention will become more apparent from the following description.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least an acid-modified ethylenically unsaturated group-containing polyurethane resin, a metal phosphate, a polymerizable compound, and a photopolymerization initiator, and, if necessary, a crosslinking agent. Contains other ingredients such as.

<Acid-modified ethylenically unsaturated group-containing polyurethane resin>
The acid-modified ethylenically unsaturated group-containing polyurethane resin is a polyurethane resin having an acid group and an ethylenically unsaturated group, and has a structural unit represented by the following general formula (G).
There is no restriction | limiting in particular as said acid group, According to the objective, it can select suitably, For example, a carboxyl group is mentioned.
There is no restriction | limiting in particular as said ethylenically unsaturated group, According to the objective, it can select suitably, For example, a vinyl group is mentioned.
Examples of the functional group having an ethylenically unsaturated group include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinylphenyl group, vinyl ester group, vinyl ether group, allyl ether group, and allyl ester group. .

In general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group. A represents a divalent organic group. X represents one of an oxygen atom, a sulfur atom, and —N (R ⁴ ) —. R ⁴ represents a hydrogen atom or a monovalent organic group. Here, the monovalent organic group in R ¹ to R ³ and R ⁴ includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, Aryloxy group, alkylthio group, arylthio group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamido group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl Groups, acyloxy groups, carbamoyl groups, sulfamoyl groups, hydroxyl groups, mercapto groups, cyano groups, nitro groups, carboxyl groups, sulfo groups, ureido groups, urethane groups, etc., and these groups are further substituted with these substituents. Has been May be. In addition, the same group is mentioned for the monovalent organic group and substituent in each of the following general formulas.
Although the photosensitive composition containing a metal phosphate is usually not sufficiently folding-resistant, the acid-modified ethylenically unsaturated group-containing polyurethane resin has a structural unit represented by the general formula (G). The present inventors have found that folding resistance is unexpectedly excellent by having it.

The monovalent organic group for R ^{1 in} the general formula (G) is preferably an alkyl group that may have a substituent. R ¹ in the general formula (G) is preferably a hydrogen atom or a methyl group.
The monovalent organic group of R ² and R ^{3 in} the general formula (G) is preferably an alkyl group that may have a substituent.
As R < ² > and R < ³ > in the said general formula (G), a hydrogen atom is preferable.
A in the general formula (G) is not particularly limited as long as it is a divalent organic residue, and can be appropriately selected according to the purpose. For example, an alkylene group which may have a substituent In the alkylene chain of the alkylene group, —O—, —S—, —N (R ^A1 ) —, —OCONH—, —OCONH—Z ^A1 —NHCOO—, —O—Z ^A1 —O—, —OCO—Z ^And groups having ^A1 Z—COO— and —SZ ^A1 —S—. Here, R ^A1 represents a hydrogen atom or a monovalent organic group, and Z ^A1 represents an alkylene group, a cycloalkylene group, an arylene group or a divalent heterocyclic group. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, a methylene group is preferable.
X in the general formula (G) is preferably an oxygen atom.
The monovalent organic group represented by R ^{4 in} the general formula (G) is preferably an alkyl group that may have a substituent, and more preferably a methyl group, an ethyl group, or an isopropyl group.

The method for introducing the structural unit represented by the general formula (G) into the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose. And a method of reacting a diisocyanate compound with a compound represented by the following general formula (G-1).

In the general formula ^{(G-1), R 1} ~ R 3, A, and X, ^R 1 ^{~ R} 3 in the general formula (G), A, and is the same as X.

Specific examples of the compound represented by the general formula (G-1) are shown below.

The acid-modified ethylenically unsaturated group-containing polyurethane resin preferably has an aromatic group. Further, it preferably has at least one skeleton selected from bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, and anthracene type.
Here, the term “aromatic” refers to a conventional concept of aromatics as defined in the literature, particularly Jerry MARCH, MARCH'S Advanced Organic Chemistry, 5th edition, John Wiley and Sons, 2001, page 37 and below. means.

Examples of the skeleton having the aromatic group in the acid-modified ethylenically unsaturated group-containing polyurethane resin include groups represented by the following general formula (I).

In formula (I), X ¹ represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same as or different from each other, and each represents a hydrogen atom, a monovalent organic group, a halogen atom, —OR ⁹ , —N ( R ¹⁰ ) (R ¹¹ ), or —SR ¹² , and R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² represent a hydrogen atom or a monovalent organic group.
X ¹ is preferably —CH ₂ — or —O—, particularly preferably —CH ₂ —, from the viewpoint of developability.
The monovalent organic group in R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is not particularly limited and may be appropriately selected depending on the purpose. , An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, —OR ¹³ (wherein R ¹³ represents a monovalent organic group), an aryl group, an aryloxy group, an arylamino group, a diarylamino Groups and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and the like.
R ⁵ , R ⁶ , R ⁷ , and R ⁸ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or —OR ¹³ from the viewpoint of resolution, and particularly preferably a hydrogen atom.

The acid-modified ethylenically unsaturated group-containing polyurethane resin is a structural unit represented by a reaction product of a compound having an alcohol group, which may be monofunctional or polyfunctional, and 4,4′-diphenylmethane diisocyanate (MDI). It is preferable that it is a polyurethane resin containing.
The mass composition ratio of the MDI in the acid-modified ethylenically unsaturated group-containing polyurethane resin is preferably 30% by mass or more, more preferably 30% by mass to 70% by mass, still more preferably 33% by mass to 70% by mass, 35% by mass to 70% by mass is particularly preferable.
If the mass composition ratio of the MDI is less than 30% by mass, the hardness may decrease.

The acid-modified ethylenically unsaturated group-containing polyurethane resin comprises at least one diisocyanate compound represented by the following general formula (i) and at least one diol compound represented by the following general formula (ii). It is preferable that the polyurethane resin has a structure represented by the general formula (G) while the structural unit represented by the reaction product is a basic skeleton.

OCN-X ⁰ -NCO General formula (i)
HO—Y ⁰ —OH... General formula (ii)

In general formulas (i) and (ii), X ⁰ and Y ⁰ each independently represent a divalent organic group.

-Diisocyanate compound represented by formula (i)-
There is no restriction | limiting in particular as a diisocyanate compound represented by the said general formula (i), According to the objective, it can select suitably.
In the general formula (i), X ⁰ may have another functional group that does not react with an isocyanate group, such as an ester, urethane, amide, or ureido group.
Examples of the diisocyanate compound represented by the general formula (i) include 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and p-xylylene diisocyanate. , Aromatic diisocyanate compounds such as m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate; Aliphatic diisocyanate compounds such as methylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl Cycloaliphatic-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane and other alicyclic diisocyanate compounds; adducts of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate, etc. And a diisocyanate compound which is a reaction product of a diol and a diisocyanate. Among these, 4,4′-diphenylmethane diisocyanate (MDI) is particularly preferable from the viewpoint of hardness.

Moreover, as a diisocyanate compound represented by the said general formula (i), for example, it is obtained by addition-reacting a triisocyanate compound and 1 equivalent of monofunctional alcohol or monofunctional amine compound which has an ethylenically unsaturated group. Products to be obtained.
The triisocyanate compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0034] to [0035] of JP-A-2005-250438. .
The monofunctional alcohol having an ethylenically unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs of JP 2005-250438 A [ And the compounds described in [0037] to [0040].
These diisocyanate compounds may be used individually by 1 type, and may use 2 or more types together.

-Diol compound represented by general formula (ii)-
There is no restriction | limiting in particular as a diol compound represented by the said general formula (ii), According to the objective, it can select suitably, For example, it has a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, and a carboxyl group Examples thereof include diol compounds and diol compounds containing an ethylenically unsaturated group in the side chain.
These may be used individually by 1 type and may use 2 or more types together.

The polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0068] to [0076] of JP-A-2005-250438. It is done.
The polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paragraphs [0077] to [0079] and paragraphs [0083] to [0085] of JP-A-2005-250438. No. 1-No. 8 and no. 13-No. 18 and the like.

The polycarbonate diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the paragraphs [0080] to [0081] and paragraph [0084] of JP-A-2005-250438, No. 9-No. 12 and the like.

Examples of the diol compound having a carboxyl group include those represented by the following formulas (X) to (Z).

In the formulas (X) to (Z), R ¹⁵ represents a hydrogen atom, a substituent {for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc., —CONH ₂ , — COOR ¹⁶ , —OR ¹⁶ , —NHCONHR ¹⁶ , —NHCOOR ¹⁶ , —NHCOR ¹⁶ , —OCONHR ¹⁶ (wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms). Each group is included. }, An alkyl group that may have a substituent, an aralkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, As long as it represents an aryloxy group which may have the above-mentioned substituent, there is no particular limitation, and it can be appropriately selected according to the purpose, but a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, An aryl group having 6 to 15 carbon atoms is preferred. In the above formulas (X) to (Z), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group). As long as it represents a divalent aliphatic or aromatic hydrocarbon group that may have an alkyl group, and an alkoxy group and a halogen atom are not particularly limited, and can be appropriately selected depending on the purpose. However, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. If necessary, the L ⁹ to L ¹¹ may have other functional groups that do not react with isocyanate groups, such as carbonyl, ester, urethane, amide, ureido, ether, and other groups and bonds. In addition, you may form a ring by two or three of said R < ¹⁵ >, L < ⁹ >, L < ¹⁰ >, L < ¹¹ >.
In the formula (Y), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose. However, an aromatic group having 6 to 15 carbon atoms is preferred.

The diol compound having a carboxyl group represented by the formulas (X) to (Z) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3,5-dihydroxybenzoic acid, 2, 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxy Phenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-Carboxy-propionamide and the like. These may be used individually by 1 type and may use 2 or more types together.

The diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the purpose. For example, a commercially available product such as trimethylolpropane monoallyl ether may be used. Or compounds such as halogenated diol compounds, triol compounds, aminodiol compounds, and compounds containing ethylenically unsaturated groups, such as carboxylic acids, acid chlorides, isocyanates, alcohols, amines, thiols, alkyl halide compounds, etc. It may be a compound produced by the reaction.
In addition, compounds described in paragraphs [0057] to [0060] of JP-A-2005-250438, compounds represented by the general formula (G-1), and the like can be given. Among these, the compound represented by the general formula (G-1) can easily introduce the structural unit represented by the general formula (G) into the acid-modified ethylenically unsaturated group-containing polyurethane resin. Is preferable.

When obtaining the acid-modified ethylenically unsaturated group-containing polyurethane resin, in addition to the diol compound described above, a diol compound having a substituent that does not react with an isocyanate group may be used in combination.
The diol compound having a substituent that does not react with the isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs [0087] to [0088] of JP-A-2005-250438 And the compounds described.

In addition to the diol compound described above, a compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound can be used in combination for the synthesis of the acid-modified ethylenically unsaturated group-containing polyurethane resin.
The compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraph [0095] to JP 2005-250438 A And the compounds described in [0101].

The acid-modified ethylenically unsaturated group-containing polyurethane resin used in the present invention is, for example, from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. A diol compound other than a diol compound containing an ethylenically unsaturated group or a diol compound containing a carboxyl group can be copolymerized, and in the present invention, it is particularly preferable to copolymerize such a diol compound.
Such a diol compound is not particularly limited and can be appropriately selected according to the purpose. For example, a low-molecular diol compound or a polymer diol compound such as a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, Mention may be made of polycarbonate compounds of m-dihydroxybenzene.

Such a diol compound is represented by the following general formula (U) and, when incorporated as a polyurethane resin, is represented by a partial structure represented by the following general formula (U1).

In the general formulas (U) and (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group.

L ^U1 includes, for example, an alkylene group, an arylene group, and a divalent heterocyclic group, and the alkylene group includes —O—, —OCOO—, a phenylene group, and a carbon-carbon double bond in the chain of the alkylene group. And a carbon-carbon triple bond, —OCO—Z ^L1 —COO— (Z ^L1 represents an alkylene group, an alkenylene group or an arylene group).

Of the diol compounds represented by the general formula (U), the low molecular weight diol compound preferably has a mass average molecular weight of less than 400, and is described, for example, in paragraph [0048] of JP-A-2007-2030. And the like.
In the present invention, a polymer diol compound is preferable and will be described in detail below.

-Polymer diol compound-
The polymer diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block copolymer or random copolymer Polyether diols such as coalesced polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol; polyhydric alcohol or polyether diol and maleic anhydride, maleic acid, fumaric acid, Polyester diols that are condensates of polybasic acids such as itaconic anhydride, itaconic acid, adipic acid, terephthalic acid, isophthalic acid; reaction of glycol or bisphenol with carbonate Alternatively, polycarbonate diols obtained by reacting phosgene with glycol or bisphenol in the presence of an alkali; caprolactone-modified polymer diols such as caprolactone-modified polytetramethylene diol, polybutadiene-based polymers such as polyolefin-based polymer diols and hydrogenated polybutadiene diols Examples thereof include polymer diols and silicone polymer diols. These may be used individually by 1 type and may use 2 or more types together.

In the present invention, preferred compounds and partial structures are such that L ^U1 in the general formulas (U) and (U1) is — (CH ₂ CH ₂ O) n ^U1 CH ₂ CH ₂ —, — [CH ₂ CH (CH ₃ ) O] n ^U1 —CH ₂ CH (CH ₃ ) —, — (CH ₂ CH ₂ CH ₂ O) n ^U1 —CH ₂ CH ₂ CH ₂ —, a structure represented by the following general formula (LL1), It is a polybutadienediol residue represented by the structure represented by the formula (LL2) or the following general formula (LL3).

Here, R ^LL1 and R ^LL2 each independently represent a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group. n ^U1 to n ^U4 each independently represents a number of 1 or more. n ^U1 to n ^U4 are usually 1000 or less, preferably 500 or less, more preferably 100 or less.

As the divalent chain hydrocarbon group, an alkylene group, an alkenylene group or an alkynylene group is preferable. These may have a branched or substituted group. More preferable carbon number is 2 to 8, ethylene group, trimethylene group, propylene group, tetramethylene group, 2-methyl-tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, 2-butenylene group, A 2-butynylene group is a preferred example.
The divalent cyclic hydrocarbon group is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. . A single ring or a condensed ring may be used, and a single ring is preferable. Either an aromatic ring or an aliphatic ring may be used. Among these, preferred examples of the aromatic ring include a benzene ring and a naphthalene ring, and preferred examples of the aliphatic ring include a cyclohexane ring and a bicyclo [2.2.2] octane ring.

The polymer diol compound preferably has a mass average molecular weight of 400 to 8,000, more preferably 500 to 5,000, still more preferably 600 to 3,000, and 800 to 2,000. It is particularly preferred that If the mass average molecular weight is less than 400, sufficient folding resistance may not be obtained, and if it exceeds 8,000, the glass transition temperature (Tg) of the resulting polyurethane resin is too low. Reliability may be reduced.
Here, the mass average molecular weight is determined using, for example, a high-speed GPC apparatus (manufactured by Toyo Soda Co., Ltd., HLC-802A), a 0.5 mass% THF solution as a sample solution, and a column of one TSKgel HZM-M. 200 μL of sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm).

The mass ratio of the polymer diol residue in the acid-modified ethylenically unsaturated group-containing polyurethane resin is preferably 10 to 60%, more preferably 20 to 60%, and more preferably 25 to 55%. More preferably, the content is 30 to 50%. When the mass ratio is less than 10%, it may be difficult to suppress warping after curing, and when it exceeds 60%, the sensitivity of photocuring may be excessively lowered and resolution may be deteriorated.

-Carboxyl group at the end of the main chain-
In addition, as the acid-modified ethylenically unsaturated group-containing polyurethane resin, those having at least one carboxyl group at the end of the polymer main chain are also preferable in terms of excellent developability of non-image areas with an alkaline developer. Used. It has at least one carboxyl group at the terminal of the polymer main chain and preferably has 2 or more and 5 or less carboxyl groups, and having two carboxyl groups is excellent in developability and has a fine pattern forming property. Is particularly preferable.
The acid-modified ethylenically unsaturated group-containing polyurethane resin has two main chain ends, but preferably has at least one carboxyl group at one end, and has at least one carboxyl group at both ends. You may do it.

It is preferable that a terminal chain of the acid-modified ethylenically unsaturated group-containing polyurethane resin has a structure represented by the following general formula (II).

-L ^1- (COOH) _n ... General formula (II)

In general formula (II), L ¹ represents an (n + 1) -valent organic linking chain, n represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 2.
The organic linking group represented by L ¹ includes one or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Specifically, the organic linking group is represented by L ^1. The number of atoms constituting the main skeleton of the organic linking group is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 1 to 10.
The “main skeleton of the organic linking group” means an atom or an atomic group used only for linking the main chain of the polyurethane resin and the terminal COOH, and when there are a plurality of linking paths, The atom or atomic group which comprises the path | route with the fewest number of atoms used is pointed out.

The method for introducing at least one carboxyl group into the terminal of the main chain of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyurethane Examples of the raw material for resin production include a method using a carboxylic acid compound having at least one carboxyl group.

Examples of the carboxylic acid compound include a monocarboxylic acid compound having one carboxyl group, a dicarboxylic acid compound having two carboxyl groups, a tricarboxylic acid compound having three carboxyl groups, a tetracarboxylic acid compound having four carboxyl groups, and a carboxyl group. Examples thereof include pentacarboxylic acid compounds having five groups. Among these, a dicarboxylic acid compound having two carboxyl groups is particularly preferable in terms of excellent developability and fine pattern formability.

The carboxylic acid compound is not particularly limited as long as it has at least one carboxyl group, and can be appropriately selected according to the purpose. However, a compound represented by the following general formula (III) is preferable.

HO—L ² —YL ¹ — (COOH) Formula (III)

In the general formula (III), L ¹ and n represent the same meaning as in the general formula (I).
Y represents a divalent or higher valent atom. L ² represents a single bond or an alkylene group which may have a substituent.
In the general formula (III), Y represents a divalent or higher valent atom. Examples of the divalent or higher atom include an oxygen atom, a nitrogen atom, a carbon atom, and a silicon atom. Among these, a nitrogen atom and a carbon atom are particularly preferable. Here, the atom represented by Y is divalent or more means that at least Y has ^two bonds in which the terminal —COOH is bonded via L ¹ and L ^2. May further have a hydrogen atom or a substituent.
Examples of the substituent that can be introduced into Y include a substituent including an atom selected from a hydrogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom. Among these, a hydrocarbon group having 1 to 50 carbon atoms is preferable, a hydrocarbon group having 1 to 40 carbon atoms is more preferable, and a hydrocarbon group having 1 to 30 carbon atoms is particularly preferable.

L ² in the general formula (III) represents a single bond or an alkylene group which may have a substituent. As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 2 to 10 carbon atoms is more preferable. Examples of the substituent that can be introduced into the alkylene group include a halogen atom (F, Br, Cl, I), an alkyl group that may have a substituent, and the like.

The carboxylic acid compound represented by the general formula (III) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include lactic acid, malic acid, hydroxyhexanoic acid, citric acid, and a diol compound. Examples include a reaction product of an acid anhydride. These may be used individually by 1 type and may use 2 or more types together. Among these, malic acid is particularly preferable.

-Method for producing acid-modified ethylenically unsaturated group-containing polyurethane resin-
The method for producing the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the diisocyanate compound and the diol compound, and if necessary, the ethylenically unsaturated group may be selected. A method of synthesizing a diol compound having no saturated group or carboxyl group, particularly preferably a polymer diol compound, by adding a known catalyst having an activity corresponding to the reactivity in an aprotic solvent and heating the mixture. Is mentioned. The molar ratio of diisocyanate and diol compound used in the synthesis (M _a : M _b ) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1: 1 to 1.2: 1. By treatment with alcohols or amines, a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.

The amount of the ethylenically unsaturated group in the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. 0.05 mmol / g to 3.0 mmol / g is preferable, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.
Here, the ethylenically unsaturated group equivalent can be determined, for example, by measuring the bromine number. The bromine number can be measured, for example, according to JIS K2605.
Here, the ethylenically unsaturated equivalent is typically a vinyl group equivalent, and the number of grams of bromine (Br ₂ ) added to 100 g of the resin to be measured obtained by the bromine number (gBr ₂ / 100 g) is converted to the number of moles of added bromine (Br ₂ ) per 1 g of resin.

The mass average molecular weight of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably from 3,000 to 50,000, and from the viewpoint of developability. To 3,000 to 30,000 is more preferable.

The acid value (solid acid value) of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 mgKOH / g to 120 mgKOH / g. 30 mg KOH / g to 110 mg KOH / g is more preferable, and 35 mg KOH / g to 100 mg KOH / g is particularly preferable. If the acid value is less than 20 mgKOH / g, the developability may be insufficient, and if it exceeds 120 mgKOH / g, the development speed may be too high, and the development control may be difficult.
In addition, the said acid value can be measured based on JISK0070, for example. However, if the sample does not dissolve, dioxane or tetrahydrofuran is used as the solvent.

The content of the acid-modified ethylenically unsaturated group-containing polyurethane resin in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. % Is preferable, and 30% by mass to 60% by mass is more preferable. When the content is 5% by mass or more, developability and exposure sensitivity are good, and when the content is 80% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

<Metallic phosphates>
The metal phosphate is a metal phosphate represented by the following general formula (1).

However, in the general formula (1), ^AP and ^BP are each independently a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, or an aryl group. Represents either. M represents any of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K. m represents an integer of 1 to 4.
As the ^AP and ^BP , a linear alkyl group having 1 to 6 carbon atoms is preferable, a methyl group, an ethyl group, or an n-propyl group is more preferable, and an ethyl group is particularly preferable.
As said M, Al is preferable.
The m is preferably 3.

Commercially available products can be used as the metal phosphate represented by the general formula (1). Examples of the commercially available products include Exolite OP-935, Exolite OP-930, Exolite OP1230, Exolite OP-1240, and Exolite OP-1312 (all manufactured by Clariant Japan), which are aluminum phosphinates.

The average particle diameter of the metal phosphate represented by the general formula (1) is 1.0 μm or less, preferably 0.5 μm or less, and more preferably 0.1 μm or less. When the average particle diameter exceeds 1.0 μm, folding resistance is lowered and folding resistance becomes insufficient. There is no restriction | limiting in particular as a lower limit of the said average particle diameter, Although it can select suitably according to the objective, 0.01 micrometer or more is preferable.
The maximum particle diameter of the metal phosphate represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm or less, more preferably 3 μm or less, and 2 μm. The following are particularly preferred: There is no restriction | limiting in particular as a lower limit of the said maximum particle diameter, Although it can select suitably according to the objective, 1 micrometer or more is preferable.
The average particle size and the maximum particle size can be measured using, for example, a concentrated particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.). Specifically, the measurement principle is a dynamic light scattering method, and the size distribution analysis method is a cumulant method and / or a histogram method.
The average particle size is defined as a particle size with an integrated value of 50% when expressed as an integrated (cumulative) mass percentage, and is defined as d50 (D50) or the like.
The maximum particle size is defined as a particle size having an integrated value of 100% and is defined as d100 (D100) or the like.

The method for setting the metal phosphate represented by the general formula (1) to the average particle size and the maximum particle size is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a method using a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor.

The content of the metal phosphate of the general formula (1) in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. 40 parts by mass is preferable, and 5 to 25 parts by mass is more preferable. If the content is less than 5 parts by mass, sufficient flame retardancy may not be obtained, and if it exceeds 40 parts by mass, folding resistance may be reduced.

<Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has one or more ethylenically unsaturated groups is preferable. The polymerizable compound is a compound different from the binder resin described above, and is preferably a monomer or oligomer having a molecular weight of 1000 or less, for example.

Examples of the functional group having an ethylenically unsaturated group include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinylphenyl group, vinyl ester group, vinyl ether group, allyl ether group, and allyl ester group. .

The compound having one or more ethylenically unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. However, at least one selected from monomers having a (meth) acryloyl group is preferable.

There is no restriction | limiting in particular as a monomer which has the said (meth) acryloyl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meta) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dicyclopentane dimethylol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate , Trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanate Nurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; a polyfunctional alcohol such as trimethylolpropane, glycerin, bisphenol and (meth) acrylate after addition reaction of ethylene oxide or propylene oxide; Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentane dimethylol di (meth) acrylate, Polyfunctional acrylates and methacrylates such as tricyclodecane dimethanol (meth) acrylate and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid are more preferable.
As the polymerizable compound, polyfunctional acrylates and methacrylates such as those having two or more acryloyloxy groups and methacryloyloxy groups, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid are particularly preferable.

The content of the polymerizable compound in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass to 50% by mass, and preferably 10% by mass to 40 mass% is more preferable. When the content is 5% by mass or more, developability and exposure sensitivity are good, and when the content is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. Those having photosensitivity are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of monomer. May be.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm. The wavelength is more preferably 330 nm to 500 nm.
As said photoinitiator, a neutral photoinitiator is preferable. Moreover, the other photoinitiator may be included as needed.

The neutral photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a compound having at least an aromatic group, such as (bis) acylphosphine oxide or an ester thereof. More preferred are acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds. Two or more neutral photopolymerization initiators may be used in combination.

Examples of the photopolymerization initiator include (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime derivatives, organic peroxides, thiols, and the like. Compound etc. are mentioned. Among these, from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, oxime derivatives, (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone Of these compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are preferred.

Examples of the (bis) acylphosphine oxide, the acetophenone compound, the benzophenone compound, the benzoin ether compound, the ketal derivative compound, and the thioxanthone compound include, for example, paragraph [0042] of JP-A-2010-256399. Examples thereof include (bis) acylphosphine oxides, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds.

Examples of the oxime derivative include oxime derivatives described in paragraphs [0043] to [0059] of JP 2010-256399 A.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
The content of the photopolymerization initiator in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 30% by mass, More preferably, the content is 5% by mass to 20% by mass, and particularly preferably 0.5% by mass to 15% by mass.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose.In order to improve the film strength after curing of the photosensitive layer, in a range that does not adversely affect developability, for example, Epoxy compounds (for example, epoxy compounds having at least two oxirane groups in one molecule), oxetane compounds having at least two oxetanyl groups in one molecule can be used, and are described in JP-A-2007-47729. A compound obtained by reacting a blocking agent with an isocyanate group of an epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate or a derivative thereof ( Blocked polyisocyanate compound), oxazoline derivative And the like.

Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

Examples of the epoxy compound include epoxy compounds described in paragraphs [0071] to [0073] of JP2010-256399A.

Examples of the oxetane compound include oxetane compounds described in paragraph [0074] of JP2010-256399A.

Examples of the polyisocyanate compound include the polyisocyanate compounds described in paragraph [0075] of JP2010-256399A.

Examples of the blocked polyisocyanate compound include compounds described in paragraph [0076] of JP-A No. 2010-256399.

Examples of the oxazoline derivative include 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, and 2,2′-bis. (2-oxazoline) and the like.

Examples of the melamine derivative include the melamine derivatives described in paragraph [0077] of JP 2010-256399 A.

The content of the thermal crosslinking agent in the solid content of the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 50% by mass, and preferably 3% by mass to 30 mass% is more preferable. When the content is 1% by mass or more, the film strength of the cured film is improved, and when the content is 50% by mass or less, developability and exposure sensitivity are improved.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a filler, a thermosetting accelerator, a thermal-polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye) etc. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tensions) You may use together a regulator, a chain transfer agent, etc.).
By appropriately containing these components, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.
Examples of the filler include paragraphs [0098] to [00099] of JP-A-2008-250074.
However, in the present invention, it is preferable not to contain inorganic fine particles which are inorganic fillers in the photosensitive composition. Even if it is contained, the solid content ratio of the photosensitive composition is less than 10% by mass, more preferably 1% by mass. Is less than.
Examples of the thermal polymerization inhibitor include paragraphs [0101] to [0102] of JP-A-2008-250074.
Examples of the thermosetting accelerator include paragraph [0093] of JP-A-2008-250074.
Examples of the plasticizer include paragraphs [0103] to [0104] of JP-A-2008-250074.
Examples of the colorant include paragraphs [0105] to [0106] of JP-A-2008-250074.
Examples of the adhesion promoter include paragraphs [0107] to [0109] of JP-A-2008-250074.

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer containing the photosensitive composition of the present invention on the support, and further has other layers as necessary.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the support described in paragraphs [0115] to [0117] of JP-A-2008-250074.

<Photosensitive layer>
If the said photosensitive layer is a layer containing the said photosensitive composition of this invention, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
Further, the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.

As the method for forming the photosensitive layer, for example, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support. The method of laminating | stacking by apply | coating directly and drying is mentioned.

The solvent used for the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating etc. are mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually 60 ° C. to 110 ° C. for about 30 seconds to 15 minutes.

The thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and particularly preferably 4 μm to 30 μm.

<Other layers>
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a protective film, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorption layer, a surface protective layer, etc. Layer. The said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.

-Protective film-
The photosensitive film may form a protective film on the photosensitive layer.
There is no restriction | limiting in particular as said protective film, According to the objective, it can select suitably, For example, the protective film as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.
The combination of the protective film and the support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the combination described in paragraph [0118] of JP-A-2008-250074. It is done.

The static friction coefficient between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2.
If the static friction coefficient is 0.3 or more, it is possible to prevent the occurrence of winding misalignment when it is made into a roll shape due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. .

The length and storage method of the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. For example, the length and storage described in paragraph [0120] of JP-A-2008-250074 are disclosed. The method etc. are mentioned.

The protective film may be surface-treated to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 ° C. to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 ° C to 120 ° C.

(Photosensitive laminate)
The photosensitive laminate of the present invention comprises at least a substrate and a photosensitive layer on the substrate, and further laminates other layers as necessary.
The photosensitive layer is a layer containing the photosensitive composition of the present invention.
The photosensitive layer is, for example, transferred from the photosensitive film produced by the above-described manufacturing method, and has the same configuration as described above.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and is appropriately selected depending on the purpose. For example, a material having a high surface smoothness to a material having an uneven surface can be arbitrarily selected, but a plate-like substrate, that is, a so-called substrate is preferable. Specific examples include a known printed wiring board production substrate (printed substrate), a glass plate (soda glass plate, etc.), a synthetic resin film, paper, a metal plate, etc. In the present invention, a polyimide film is used. Particularly preferred.

<Method for producing photosensitive laminate>
The method for producing the photosensitive laminate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one of heating and pressing at least the photosensitive layer in the photosensitive film of the present invention is performed. For example, a method of transferring and stacking can be used.

An example of the manufacturing method of the said photosensitive laminated body is the method of laminating | stacking the photosensitive film of this invention on the surface of the said base | substrate, performing at least any one of a heating and pressurization. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
The heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 15 ° C. to 180 ° C. is preferable, and 60 ° C. to 140 ° C. is more preferable.
The pressurizing pressure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.1 MPa to 1.0 MPa is preferable, and 0.2 MPa to 0.8 MPa is more preferable.

The apparatus for performing at least one of the heating is not particularly limited and may be appropriately selected depending on the purpose. For example, a laminator (for example, Taisei Laminator, VP-II, Nichigo Morton, VP130) is preferable.

The photosensitive film and the photosensitive laminate of the present invention can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be particularly suitably used for forming a permanent pattern on a printed circuit board.

(Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps as necessary.

<Exposure process>
The exposure step is not particularly limited as long as it is a step of exposing the photosensitive layer formed of the photosensitive composition of the present invention, and can be appropriately selected according to the purpose. The process etc. which expose with respect to the photosensitive layer in the said photosensitive laminated body are mentioned.

The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose, but while performing at least one of heating and pressurizing the photosensitive film on the substrate. It is preferable to be performed on a laminated body formed by laminating.

The exposure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include digital exposure and analog exposure.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a development process, a hardening process process, a post exposure process etc. are mentioned.

-Development process-
The developing step is a step of removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as a removal method of the said exposed part, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

The developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the developers described in paragraphs [0171] to [0173] of JP-A-2008-250074.

-Curing process-
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

The method for the whole surface exposure treatment and the whole surface heat treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, in paragraphs [0176] to [0177] of JP-A-2008-250074 The method of description is mentioned.

When the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern is formed on a printed circuit board by the permanent pattern forming method. Then, soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

(Printed board)
The printed circuit board of the present invention includes at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further includes other members appropriately selected as necessary.
There is no restriction | limiting in particular as another member, According to the objective, it can select suitably, For example, the buildup board | substrate etc. in which the insulating layer was further provided between the base material and the said permanent pattern are mentioned. In the present invention, it is particularly preferable to use it for a flexible wiring board.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “part” represents “part by mass”.

In addition, the acid value and mass average molecular weight in the preparation examples were measured by the following methods.
<Acid value>
The acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
<Mass average molecular weight>
The mass average molecular weight was measured using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.). That is, a 0.5 mass% THF (tetrahydrofuran) solution was used as a sample solution, a column using one TSKgel HZM-M, a 200 μL sample was injected, eluted with the THF solution, and a refractive index at 25 ° C. Measured with a detector. Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
<Equivalent ethylenically unsaturated group>
The ethylenically unsaturated group equivalent was determined by measuring the bromine number according to JIS K2605.

(Preparation Example 1)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin U2>
To a 1 L three-necked round bottom flask equipped with a condenser and a stirrer was added 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA) and 35.44 g of glycerol monomethacrylate (GLM). (0.221 mol), 78.75 g (0.079 mol) of polypropylene glycol (molecular weight 1000) (PPG1000) and 6.03 g (0.045 mol) of malic acid were dissolved in 300 mL of cyclohexanone. To this, 23.46 g (0.094 mol) of 4,4-diphenylmethane diisocyanate (MDI), 47.30 g (0.281 mol) of hexamethylene diisocyanate (HMDI), 2,6-di-t-butylhydroxytoluene 0 0.6 g and 0.6 g of a trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) were added as a catalyst, and the mixture was heated and stirred at 75 ° C for 5 hours. After cooling to room temperature, the concentration was adjusted with cyclohexanone to obtain an acid-modified ethylenically unsaturated group-containing polyurethane resin (U2) solution having a solid concentration of 40% by mass. The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a mass average molecular weight of 7000, a solid content acid value of 46 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.1 mmol / g.

(Preparation Example 2)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin U1>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) malic acid were combined with 14.45 g (0.098 mol) 2,2-bis (hydroxymethyl) butyric acid (DMBA). Instead of a combination of 44.45 g (0.278 mol) of glycerol monomethacrylate (GLM) and 6.03 g (0.045 mol) of malic acid, 23.46 g (0.094) of 4,4-diphenylmethane diisocyanate (MDI) Mol), 47.30 g of hexamethylene diisocyanate (HMDI) (0. 81 mol) was replaced with a combination of 75.08 g (0.300 mol) of 4,4-diphenylmethane diisocyanate (MDI) and 12.61 g (0.075 mol) of hexamethylene diisocyanate (HMDI), In the same manner as in Preparation Example 1, an acid-modified ethylenically unsaturated group-containing polyurethane resin (U1) solution having a solid content concentration of 40% by mass was synthesized. The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a mass average molecular weight of 8000, a solid content acid value of 69 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.82 mmol / g.

(Preparation Example 3)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin U3>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) of malic acid were combined into 15.00 g (0.101 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA). , 31.83 g (0.199 mol) of glycerol monomethacrylate (GLM), 75 g (0.075 mol) of polytetramethylene glycol (molecular weight 1000) (PTMG1000) and 6.03 g (0.045 mol) of malic acid The solid content concentration is 40 quality in the same manner as in Preparation Example 1 except that % Acid modified ethylene unsaturated group-containing polyurethane resin (U3) solution was synthesized. The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a mass average molecular weight of 8,600, a solid content acid value of 54 mgKOH / g, and an ethylenically unsaturated group equivalent of 1 mmol / g.

(Preparation Example 4)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin U4>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) of malic acid were combined into 15.00 g (0.101 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA). Glycerol monomethacrylate (GLM) 31.83 g (0.199 mol), ETERNACOL UH-100 (manufactured by Ube Industries, molecular weight 1000) 75 g (0.075 mol) and malic acid 6.03 g (0.045 mol) The solid content concentration was 40% by mass in the same manner as in Preparation Example 1 except that the combination was changed. An acid-modified ethylenically unsaturated group-containing polyurethane resin (U4) solution was synthesized. The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a mass average molecular weight of 8,800, a solid content acid value of 54 mgKOH / g, and an ethylenically unsaturated group equivalent of 1 mmol / g.

(Preparation Example 5)
<Synthesis of Resin U5>
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, an inlet pipe, and a thermometer, polytetramethylene glycol (PTG1000SN: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1,020) 156 parts by mass, 129 parts by mass of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts by mass of cyclohexanone as a solvent were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream and dissolved uniformly. Subsequently, 215 parts by mass of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. A small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer solution having a polystyrene-equivalent mass average molecular weight of 13,000 and an actually measured polymer non-volatile acid value of 98 mgKOH / g.

Next, the nitrogen from the nitrogen inlet tube of this flask was stopped, switched to introduction of dry air, 111 parts by mass of glycidyl methacrylate, 6 parts by mass of dimethylbenzylamine with stirring, and 0.3 parts by mass of hydroquinone as a polymerization inhibitor Was allowed to react at 90 ° C. for 8 hours.

Next, 63 parts by mass of succinic anhydride was added to the flask, and the mixture was further reacted for 6 hours at 90 ° C. in a dry air atmosphere. After confirming the disappearance of the acid anhydride group absorption by FT-IR measurement, the mixture was cooled to room temperature. Subsequently, cyclohexanone was added to this solution, and it adjusted so that solid content might be 40 mass%.

(Preparation Example 6)
<Preparation of resin U6>
ZCR-1569H (manufactured by Nippon Kayaku Co., Ltd., novolac acid-modified ethylenically unsaturated group-containing epoxy resin having a biphenyl skeleton) was diluted with cyclohexanone to adjust the solid content concentration to 40% by mass, and used as resin U6.

(Preparation Example 7)
<Preparation of resin U7>
ZCR-1569H (manufactured by Nippon Kayaku Co., Ltd.) and UXE-3024 (manufactured by Nippon Kayaku Co., Ltd., polyurethane resin having a structure represented by the following general formula) were mixed at a solid content ratio of ZCR-1569H: UXE-3024 = 20: 45. Was mixed with cyclohexanone to adjust the solid concentration to 40% by mass, and used as the resin U7.

Here, in the general formula, R ¹¹ represents an epoxy acrylate residue, R ¹² represents a diisocyanate residue, R ¹³ represents an alkyl group having 1 to 5 carbon atoms, and R ¹⁴ represents a hydrogen atom or a methyl group. In addition, a residue means the structure of the part remove | excluding the functional group used for the coupling | bonding from the raw material component.

(Preparation Example 8)
<Preparation of resin U8>
Acrylic resin (a copolymer of methacrylic acid, methyl methacrylate, and butyl acrylate; methacrylic acid: methyl methacrylate: butyl acrylate = 17% by mass: 62% by mass: 21% by mass and a mass average molecular weight of 10,000,000 acids 110 mg KOH / g) and UXE-3024 (manufactured by Nippon Kayaku Co., Ltd.) in a solid content ratio of acrylic resin: UXE-3024 = 30: 40, diluted with cyclohexanone to a solid content concentration of 40% by mass It adjusted and used as resin U8.

(Preparation Example 9)
<Preparation of flame retardant dispersions (a-1 to a-5 and A-1 to A-7)>
3.64 parts by mass of metal phosphate (trade name: OP-935, manufactured by Clariant Japan), 19.97 parts by mass of each resin solution (solid content concentration 40% by mass), 0.18 parts by mass of dispersant ( (Product name: BYK-W903, manufactured by Big Chemie Japan) and 3.26 parts by mass of cyclohexanone were weighed, and a motor mill M-50 (manufactured by Eiger) dispersed with zirconia beads having a diameter of 0.65 mm was used. To obtain flame retardant dispersions a-1 to 5 and A-1 to 7.
Table 1 shows the relationship between the dispersion time and the particle size of the flame retardant dispersion.

The average particle size and the maximum particle size were measured by the following methods.
A solution obtained by diluting the flame retardant dispersion by a factor of 50 was measured using a dense particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.). The measurement principle was a dynamic light scattering method, and the size distribution analysis method was measured as a cumulant method and / or a histogram method.
The average particle size is defined as a particle size of an integrated value of 50% when expressed as an integrated (cumulative) mass percentage, and is defined as d50 (D50), and the maximum particle size is an integrated value of 100%. And is defined as d100 (D100) or the like.

(Preparation Example 10)
<Preparation of flame retardant dispersions b, c, d>
A flame retardant was prepared in the same manner as the preparation of flame retardant dispersion a-1 in Preparation Example 9 (ie, dispersion time 0 minutes) except that the flame retardant in Preparation Example 9 was replaced with the flame retardant listed in Table 2. Dispersions b, c and d were prepared.

The flame retardants in Table 2 are as follows.
Phosphazene compound: SPS-100, manufactured by Otsuka Chemical Co., Ltd. Condensed phosphate ester: CR-741, manufactured by Daihachi Chemical Co., Ltd. Cyclic phosphorus compound: SANKO-BCA, manufactured by Sanko Co., Ltd.

(Preparation Example 11)
<Preparation of pigment dispersion>
0.018 parts by mass of a blue pigment (manufactured by BASF, HELIOGEN BLUE D7086), 0.005 parts by mass of yellow pigment (manufactured by BASF, Pariotol Yellow D0960), and melamine (melamine, manufactured by Wako Pure Chemical Industries, Ltd.) 0 548 parts by mass and 69.29 parts by mass of cyclohexanone were weighed and dispersed for 90 minutes using a motor mill M-50 (Eiger) disperser filled with zirconia beads having a diameter of 0.65 mm. Got.

Example 1
-Production of photosensitive film-
A photosensitive composition solution having the following composition was applied on a polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) having a thickness of 16 μm as a support, and dried to form a photosensitive layer having a thickness of 38 μm on the support. did. On the photosensitive layer, a 20 μm-thick polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated as a protective layer to produce a photosensitive film.

-Composition of photosensitive composition solution-
-Flame retardant dispersion a-3 of Preparation Example 9 ... 27.06 parts by mass-Pigment dispersion of Preparation Example 11 ... 4 .26 parts by mass-Acid-modified ethylenically unsaturated group-containing polyurethane resin U1 solution of Preparation Example 1 (adjusted to a solid concentration of 40%) ... 6.66 parts by mass -Photopolymerization initiator (IRGACURE 907, manufactured by Ciba Japan)
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.50 parts by mass ・ Photoinitiator (DETX-S, Nippon Kayaku Co., Ltd.) ・ ・ 0.0047 parts by mass ・ Photoinitiator (EAB-) F, manufactured by Hodogaya Chemical Co., Ltd.) 0.0167 parts by mass Polymerizable compound (Lipoxy VR-60, manufactured by Showa Denko) 4.57 parts by mass Surfactant (B1176 (3% dilution), DIC) 1.94 parts by mass Crosslinking agent (Epototo YDF-170, manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin) ... 4.98 Mass part ・ Solvent (Cyclohexanone) ... 2.80 parts by mass

-Lamination on substrate-
A substrate was prepared by subjecting the surface of a copper-clad laminate (no through-holes, copper thickness 18 μm) to an acid cleaning treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were as follows: a vacuuming time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure time of 10 seconds.
About the obtained photosensitive laminated body, the resist pattern was formed with the evaluation method shown below.

-Exposure process-
A predetermined pattern can be obtained from the polyethylene terephthalate film (support) side with respect to the photosensitive layer in the prepared photosensitive laminate using a blue-violet laser exposure pattern having a predetermined pattern by an ultrahigh pressure mercury lamp. In this way, an energy amount of 200 mJ / cm ² was irradiated and exposed to cure a part of the photosensitive layer.

-Development process-
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1% by mass sodium carbonate aqueous solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Was spray-developed at 30 ° C. for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the permanent pattern is subjected to heat treatment at 160 ° C. for 1 hour, and then the surface of the permanent pattern is cured by irradiating with an energy amount of 1,000 mJ / cm ² to increase the film strength. A test plate was prepared.

Supplied for the following evaluation. The results are shown in Table 3.

<Flame retardance>
Etching a substrate for flexible printed wiring boards (made by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX” M series), which is made by laminating a copper foil (copper foil thickness 12 μm) on a polyimide substrate (polyimide thickness 12.5 μm), and removing the copper foil As a result, a polyimide substrate having a thickness of 12.5 μm was obtained.
The photosensitive layer (thickness 38 μm) of the produced photosensitive film was adhered to both surfaces of this polyimide substrate by lamination. After standing at room temperature for 10 minutes, an exposure was performed by irradiating with an ultra high pressure mercury lamp with an energy amount of 150 mJ / cm ² , the photosensitive layer was cured, and after heat treatment at 160 ° C. for 1 hour, an energy amount of 1, The photosensitive layer was cured by irradiating with 000 mJ / cm ² to increase the film strength.
A composite sample was obtained by cutting the polyimide base material on which the cured photosensitive layer obtained above was formed into a size of 20 cm × 5 cm. The obtained composite sample was wound around a cylindrical rod having a diameter of 1 cm × 20 cm, and the position of 12.5 cm from the end of the composite sample was fixed with heat-resistant tape, and then the rod was removed to obtain a length of 20 cm and a diameter of 1 cm. A flame retardant test sample was obtained.
The obtained flame retardant test sample was hung with a clamp, and a flame test was conducted by indirect flame with a 3 cm flame for 3 seconds.
〔Evaluation criteria〕
○: Meets UL94 VTM-0 ×: Meets UL94 VTM-0

<Folding resistance>
A dry film resist is laminated on a substrate for flexible printed wiring boards (trade name “Espanex” M series, manufactured by Nippon Steel Chemical Co., Ltd.), which is made by laminating a copper foil (copper foil thickness 18 μm) on a polyimide base material (polyimide thickness 25 μm), and 18 mJ After exposure at / cm ² , development was performed under the condition of 0.15 MPa / 40 s to produce a line pattern of L / S = 100/100 μm. After etching the flexible printed wiring board substrate having the dry film resist line pattern, the dry film resist is peeled off by 3% by mass sodium hydroxide aqueous solution / 0.1 MPa / 120 s, so that L / S = 100 A copper foil line pattern of / 100 μm was created.
Then, the obtained photosensitive film photosensitive layer was laminated on the copper foil line pattern side to the obtained copper foil line pattern polyimide, and allowed to stand at room temperature for 10 minutes, and then with an ultra-high pressure mercury lamp, the energy amount was 150 mJ / cm. ² is exposed to light, the photosensitive layer is cured, and after heat treatment at 160 ° C. for 1 hour, the photosensitive layer is cured by irradiating with an energy amount of 1,000 mJ / cm ² to expose the film. A laminate for evaluation was obtained by increasing the strength.
The obtained laminate for evaluation was cut into a 5 mm × 10 cm square, bent 180 ° in the long side direction with the line pattern side outside, and a predetermined weight was placed on the bent portion for 3 seconds, and the folding resistance was evaluated according to the following criteria. did.
〔Evaluation criteria〕
◎: No crack at 400 g ○: No crack at 200 g Δ: No crack at 10 g less than 10% of the length of the bent side ×: 200 g of crack length is the length of the bent side More than 10%

<Bleed out>
The surface layer (permanent pattern) of the test plate on which the permanent pattern was formed was left at 40 ° C. for one week, was observed with a microscope (magnification: 200 times), and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◯: The surface is not whitened, tackiness is not observed, and no crystallized precipitates or liquid material exudation are observed.
X: Any of whitening of the surface, tackiness, precipitation of crystalline substances, and exudation of a liquid substance is observed.

<Resolution>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). Use the pattern forming device to obtain the optimal light energy so that round holes with a diameter of 50 to 200 μm can be formed on the polyethylene terephthalate film (support) of the resulting photosensitive laminate using a round hole pattern. Exposure was carried out in a quantity.
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as a developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove uncured areas. did.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and the minimum round hole pattern width that can form a space without any abnormalities such as curling or peeling of the pattern portion is measured. This was taken as the resolution and evaluated according to the following criteria.
〔Evaluation criteria〕
○: A round hole with a diameter of 100 μm or less can be resolved, and the resolution is good. ×: A round hole with a diameter of 100 μm or less cannot be resolved, and the resolution is inferior. Determined by
The polyethylene terephthalate film (support) is peeled off from the photosensitive layer of the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
The optimum amount of light energy was determined by the following method.
On the surface of the photosensitive layer of the photosensitive laminate, pattern data of L / S (line / space) = 50 μm / 50 μm is set to 0 using INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm). exposed by irradiating light of different light energy from .5MJ / cm ² to 500 mJ / cm ² at ^{2 1/2} times the interval, curing the L / S (line / space) = 50 [mu] m / 50 [mu] m line pattern It was. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed on the entire surface of the photosensitive layer on the copper-clad laminate with a spray pressure of 0.15 MPa. Spray development was performed for 2 to 3 times the shortest development time, and the uncured area was dissolved and removed. The line width of the L = 50 μm pattern obtained in this way was measured using a laser microscope (VK-9500, manufactured by Keyence Corporation, objective lens 50 times), and the amount of light energy at which the line width was 50 μm was determined. This is the optimum amount of light energy.

<Evaluation of plating resistance>
The surface of a substrate for flexible printed wiring boards (manufactured by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX” M series) in which a copper foil (copper foil thickness 18 μm) is laminated on a polyimide base material (polyimide thickness 25 μm) was subjected to an acid cleaning treatment. Except for using one, INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm) was used on the surface of the photosensitive layer of the photosensitive laminate produced in the same manner as the photosensitive laminate. After forming an independent fine line pattern of 30 μm to 1,000 μm with an optimal amount of light energy and allowing to stand at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a copper-clad laminate (flexible print) 2% to 3 times the shortest development time with a 1 mass% sodium carbonate aqueous solution at 30 ° C. at a spray pressure of 0.15 MPa on the entire surface of the photosensitive layer on the wiring substrate). Time (or 40 seconds to 60 seconds) and spray development, to dissolve away the uncured regions. Then, after heat-processing (post-baking) at 160 degreeC for 1 hour, the whole surface exposure was further performed with the ultrahigh pressure mercury lamp at 1,000 mJ / cm < ² >, and the soldering resist pattern (permanent pattern) was formed.
The cured resin pattern (permanent pattern) was immersed in an acidic degreasing solution (Sulcup ACL-007, manufactured by Uemura Kogyo Co., Ltd.) at 50 ° C. for 5 minutes and then washed with water. Next, an activator solution (KAT-450, Uemura at 22 ° C. for 90 seconds in a soft etch solution at 22 ° C. (sodium peroxodisulfate 125 g / L, sulfuric acid 18 g / L), 120 seconds in a 10% sulfuric acid aqueous solution at 22 ° C. (Manufactured by Kogyo Co., Ltd.) for 120 sec. In addition, it washed with water between each process so far. Thereafter, electroless Ni plating (Nimden NDF-2, manufactured by Uemura Kogyo Co., Ltd.) is performed at 85 ° C. for 35 minutes. ~ 13, thick gold plating (0.3 μm) for 4 minutes, after electroless gold plating, immersed in running water for 3 minutes and washed with water, then further immersed in warm water at 60 ° C for 3 minutes. After sufficiently washing with water, it was dried and an electroless gold-plated test substrate was obtained.
The cured resin pattern (permanent pattern) after the plating test was subjected to a peel test with reference to JIS K5600-5-6, and evaluated according to the following criteria.
○: No abnormality after peel test ×: Peeling observed during peel test

(Examples 2 to 3, Comparative Examples 1 to 5)
In Example 1, the photosensitive composition, the photosensitive film, etc. were obtained like Example 1 except having replaced the flame retardant dispersion liquid with the flame retardant dispersion liquid of Table 3.
Evaluation similar to Example 1 was performed. The results are shown in Table 3.

(Examples 4 to 6, Comparative Examples 6 to 9)
In Example 1, the photosensitive composition, the photosensitive film, etc. were obtained like Example 1 except having replaced the flame retardant dispersion liquid and resin with the flame retardant dispersion liquid and resin of Table 4.
Evaluation similar to Example 1 was performed. The results are shown in Table 4.

The photosensitive compositions of Examples 1 to 6 were excellent in flame retardancy, folding resistance, and plating resistance, further free from bleed out, and excellent in resolution. Further, the photosensitive compositions of Examples 3 to 6 were excellent in folding resistance as compared with Examples 1 and 2.
The photosensitive compositions of Comparative Examples 1 and 2 using a metal phosphate having an average particle diameter exceeding 1.0 μm as a flame retardant had insufficient folding resistance. The photosensitive compositions of Comparative Examples 3 to 5 using a flame retardant other than the metal phosphate had insufficient plating resistance. The photosensitive compositions of Comparative Examples 6 to 9 using a resin different from the acid-modified ethylenically unsaturated group-containing polyurethane resin had insufficient folding resistance.

Since the photosensitive composition of the present invention is excellent in all of flame retardancy, folding resistance and plating resistance, it can be suitably used for flexible printed boards and the like.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2011-068626 filed in Japan on March 25, 2011, which is hereby incorporated herein by reference. Capture as part.

Claims (12)

1. An acid-modified ethylenically unsaturated group-containing polyurethane resin, a phosphoric acid metal salt represented by the following general formula (1), a polymerizable compound, and a photopolymerization initiator,
   The acid-modified ethylenically unsaturated group-containing polyurethane resin has a structural unit represented by the following general formula (G),
   The photosensitive composition characterized by the average particle diameter of the metal phosphate represented by the general formula (1) being 1.0 μm or less.
   

   

   In general formula (1), A ^P and B ^P are each independently any one of a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, and an aryl group. To express. M represents any of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K. m represents an integer of 1 to 4.
   

   

   In general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group. A represents a divalent organic group. X represents one of an oxygen atom, a sulfur atom, and —N (R ⁴ ) —. R ⁴ represents a hydrogen atom or a monovalent organic group.
2. The photosensitive composition according to claim 1, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin contains a polymer diol residue as a repeating unit.
3. The photosensitive composition according to claim 2, wherein the polymer diol residue has a mass average molecular weight of 400 to 8,000.
4. 4. The photosensitive composition according to claim 2, wherein a mass ratio of the polymer diol residue in the acid-modified ethylenically unsaturated group-containing polyurethane resin is 10 to 60%.
5. The photosensitive composition according to any one of claims 1 to 4, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has an aromatic group.
6. The acid-modified ethylenically unsaturated group-containing polyurethane resin has at least one skeleton selected from bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, and anthracene type. The photosensitive composition of any one of Claims 1.
7. The photosensitive composition according to any one of claims 1 to 6, wherein the maximum particle diameter (d100) of the metal phosphate represented by the general formula (1) is 5 µm or less.
8. The photosensitive composition according to any one of claims 1 to 7, further comprising a thermal crosslinking agent.
9. A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to any one of claims 1 to 8 on a support.
10. A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of claims 1 to 8 on a substrate.
11. A method for forming a permanent pattern comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of claims 1 to 8.
12. A printed circuit board, wherein a permanent pattern is formed by the method for forming a permanent pattern according to claim 11.