JP5593266B2 - Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board - Google Patents

Description

  The present invention relates to a photosensitive composition suitable as a solder resist material, a photosensitive film, 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 in which a photosensitive layer is formed by coating 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.

Improving hardness and the like in a photosensitive composition using a polyurethane resin as a binder for the solder resist is one of important issues, and various studies have been made.
For example, Patent Document 1 discloses a polymerizable composition suitable for an image recording layer of a negative type image recording material containing a polyurethane resin as a binder polymer and having excellent printing durability and image forming properties.
Patent Document 2 discloses a resin composition suitable as a solder resist for a printed wiring board or the like using a polyurethane resin as a binder.

  By the way, with the enhancement of functionality of products using permanent patterns formed from a photosensitive composition, including printed wiring boards and printing plate materials, the photosensitive composition is required to have further fine pattern formability. ing. However, all of the techniques described in the above prior art documents are difficult to form a fine pattern, and are sufficiently satisfactory in terms of various properties such as development residue removability, heat resistance, toughness, resolution, and insulation. The present situation is that further improvement and development are desired.

JP-A-2005-250438 JP 2006-243563 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is a photosensitive composition that has high development residue removability, can form a fine pattern, and is excellent in heat resistance, toughness, resolution, and insulation, and a photosensitive composition using the photosensitive composition. It aims at providing a conductive film, a photosensitive laminated body, a permanent pattern formation method, and a printed circuit board.

  As a result of intensive studies by the present inventors in order to solve the above problems, a photosensitive composition containing an alkali-developable resin, a polymerizable compound, a photopolymerization initiator, and a thermal cross-linking agent is used as the alkali-developable resin. By using a polyurethane resin linked by a urethane group and having at least one carboxyl group at the end of the main chain of the polyurethane resin and having an ethylenically unsaturated group in the side chain, Has been found to improve, and can impart good developability.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A photosensitive composition containing an alkali-developable resin, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent,
The alkali-developable resin is a polyurethane resin linked by a urethane group, has at least one carboxyl group at the end of the main chain of the polyurethane resin, and has an ethylenically unsaturated group in the side chain. It is the photosensitive composition characterized.
<2> The photosensitive composition according to <1>, wherein the main chain of the polyurethane resin has 2 or more and 5 or less carboxyl groups.
<3> The photosensitive composition according to any one of <1> to <2>, having a structure represented by the following general formula (I) at a terminal of a main chain of the polyurethane resin.
-L ¹ - _(COOH) n ··· general formula (I)
In the general formula (I), L ¹ represents an (n + 1) -valent organic connecting chain, and n represents an integer of 1 or more.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the alkali-developable resin has an alkali-developable unit having a carboxyl group in a side chain of the polyurethane resin.
<5> The photosensitive composition according to <4>, wherein the alkali developable unit is represented by the following general formula (II).
However, in the general formula (II), R ¹ represents a hydrogen atom or an alkyl group, and R ² and R ³ each independently have a single bond, an ether group, an ester group, an amide group, or a carbonate group. It represents either an alkylene group that may be present or an arylene group that may have a carbonate group.
<6> The photosensitive composition according to any one of <1> to <5>, wherein the alkali-developable resin has a structural unit represented by the following general formula (VI).
However, in the general formula (VI), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. Y represents —NH—, —NHCO—, —NHCOO—, —CONH—, or —OCONH—. R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ may be the same as or different from each other, and are each a hydrogen atom, a monovalent organic group, a halogen atom, —OR ¹⁵ , —N (R ^{16) (R 17),} or an ^{-SR 18, R 15, R 16} , R 17, and ^{R 18} represents a hydrogen atom, or a monovalent organic group.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the functional group having an ethylenically unsaturated group is a (meth) acryloyl group.
<8> The photosensitive composition according to any one of <1> to <7>, wherein the alkali-developable resin is obtained by introducing a carboxylic acid compound having at least one carboxyl group at the terminal of the main chain of the polyurethane resin. It is a thing.
<9> The photosensitive composition according to any one of <1> to <8>, wherein the alkali-developable resin is obtained by polymerizing a diisocyanate compound, a diol compound, and a carboxylic acid compound having at least one carboxyl group. It is.
<10> The photosensitive composition according to any one of <8> to <9>, wherein the carboxylic acid compound is a dicarboxylic acid compound.
<11> The photosensitive composition according to <10>, wherein the diisocyanate compound is an aromatic diisocyanate compound.
<12> The photosensitive composition according to any one of <1> to <11>, wherein the alkali-developable resin has a weight average molecular weight of 5,000 to 60,000.
<13> A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <12> on a support.
<14> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <12> on a substrate.
<15> 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 <12>.
<16> A printed board comprising a permanent pattern formed by the method for forming a permanent pattern according to <15>.

  According to the present invention, various conventional problems can be solved, development residue removal property is high, a fine pattern can be formed, and a photosensitive composition excellent in heat resistance, toughness, resolution, and insulation, and the photosensitive composition. A photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed board using the photosensitive composition can be provided.

FIG. 1 is a diagram showing a permanent pattern shape.

(Photosensitive composition)
The photosensitive composition of the present invention contains an alkali-developable resin, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, and further contains other components as necessary.

<Alkali developable resin>
The alkali-developable resin is a polyurethane resin linked by a urethane group, has at least one carboxyl group at the end of the main chain of the polyurethane resin, and has an ethylenically unsaturated group in the side chain.

-Carboxyl group at the end of main chain-
The polyurethane resin has at least one carboxyl group at the end of the main chain and preferably has 2 or more and 5 or less carboxyl groups, and having two carboxyl groups is excellent in developability and forms a fine pattern. It is particularly preferable in terms of sex.
The polyurethane resin has two main chain ends, but preferably has at least one carboxyl group at one end, and may have at least one carboxyl group at both ends.
It is preferable that the terminal of the main chain of the polyurethane resin has a structure represented by the following general formula (I): -L ^1- (COOH) _n ... General formula (I)
In the general formula (I), ^{L 1} is, (n + 1) -valent organic linking chain, n represents an integer of 1 or more, 1 to 5 preferably 2 is particularly preferred.
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 L ² and the terminal COOH in the general formula (III) described later, and there are a plurality of linking paths. In some cases, it refers to an atom or atomic group that constitutes the path with the least number of atoms used.

  The method for introducing at least one carboxyl group at the end of the main chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a raw material for producing a polyurethane resin, at least one Examples include a method using a carboxylic acid compound having a carboxyl group.

-Carboxylic acid compound-
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.
However, in said general formula (III), L < ¹ > and n represent the same meaning as the said general formula (I).

L ² in the general formula (III) represents a single bond or an alkylene group which may have a substituent. As said alkylene group, a C1-C20 alkylene group is preferable and a C2-C10 alkylene group 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.
Examples of the reaction product of the diol compound and the acid anhydride include compounds represented by the following structural formulas.

-Ethylenically unsaturated group-
The polyurethane resin as the alkali-developable resin has an ethylenically unsaturated group in the side chain.
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 etc. are 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. . Among these, a methacryloyl group and an acryloyl group are particularly preferable from the viewpoint of forming a crosslinked cured film.

  The method for introducing an ethylenically unsaturated group into the side chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose. For example, as a raw material for producing a polyurethane resin, an ethylenically unsaturated group is introduced into the side chain. Examples thereof include a method using a diol compound having a saturated group.

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 easily produced by the reaction with
There is no restriction | limiting in particular as a diol compound which has an ethylenically unsaturated group in the said side chain, According to the objective, it can select suitably, For example, Paragraph [0057]-[0060] of Unexamined-Japanese-Patent No. 2005-250438. And the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the following general formula (G). Among these, the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the following general formula (G) are preferable.
However, in said general formula (G), R < ¹ > -R < ³ > represents a hydrogen atom or a monovalent organic group each independently, A represents a bivalent organic residue, X is an oxygen atom and a sulfur atom. Or -N (R ¹² )-, wherein R ¹² represents a hydrogen atom or a monovalent organic group.

The monovalent organic group R ¹ in the general formula (G), not particularly limited and may be appropriately selected depending on the intended purpose, for example, like an alkyl group which may have a substituent It is done.
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 not particularly limited and may be appropriately selected depending on the intended purpose. For example, the alkyl which may have a substituent Group and the like.
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, it may have a substituent 2 And a valent alkylene group. Specific examples of the divalent organic residue 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 R ¹² in the general formula (G), not particularly limited and may be appropriately selected depending on the intended purpose, for example, like an alkyl group which may have a substituent It is done. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable.

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

  The amount of the ethylenically unsaturated group introduced into the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. The vinyl group equivalent is 0.05 mmol / g to 3.0 mmol / g. Is preferable, 0.2 mmol / g to 2.7 mmol / g is more preferable, and 0.5 mmol / g to 2.5 mmol / g is particularly preferable.

-Alkali developable unit-
The polyurethane resin as the alkali-developable resin preferably has an alkali-developable unit having a carboxyl group in the side chain.
There is no restriction | limiting in particular as said alkali developable unit, Although it can select suitably according to the objective, The unit represented by the following general formula (II) is preferable.
However, in the general formula (II), R ¹ represents a hydrogen atom or an alkyl group, and R ² and R ³ each independently have a single bond, an ether group, an ester group, an amide group, or a carbonate group. It represents either an alkylene group that may be present or an arylene group that may have a carbonate group.

In the general formula (II), the alkyl group in R ¹ is not particularly limited and may be appropriately selected depending on the purpose, and preferably has 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Etc.
Examples of the substituent that can be introduced into the alkyl group include a halogen atom (—F, —Br, —Cl, —I), a cyano group, a nitro group, and the like.
In the general formula (II), the alkylene group in R ² and R ³ is not particularly limited and may be appropriately selected depending on the purpose, and preferably has 1 to 10 carbon atoms, such as a methylene group, an ethylene group, A propylene group, a butylene group, etc. are mentioned.
The arylene group for R ² and R ^3, are not particularly limited and may be appropriately selected depending on the purpose, 6 to 15 carbon atoms are preferred, such as a phenylene group, and the like.

  The method for introducing the alkali-developable unit into the side chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose. For example, as a raw material for producing a polyurethane resin, a carboxyl group in the side chain The method using a diol compound having

Examples of the diol compound having a carboxyl group in the side chain include compounds represented by the following general formula (IV).
However, in said general formula (IV), Z represents a trivalent or more atom. L ³ and L ⁴ each independently represents an alkylene group which may have a single bond or a substituent, and both L ³ and L ⁴ do not become a single bond. L ⁵ represents a single bond or a linking group. n represents an integer of 1 to 5.

In the general formula (IV), Z represents a trivalent or higher valent atom. Examples of the trivalent or higher atom include 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 Z is trivalent or more means that at least Z has ^three bonds to which the terminal —COOH is bonded through L ³ , L ⁴ and L ^5. , Z may further have a hydrogen atom or a substituent.
Examples of the substituent that can be introduced into Z 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 ³ and L ⁴ in the general formula (IV) each independently represent a single bond or an alkylene group which may have a substituent, and both L ³ and L ⁴ do not become a single bond. . The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms. 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.

In the general formula (IV), L ⁵ represents a single bond or a linking group. Examples of the linking group represented by L ⁵ include a linking group including one or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Specifically, the number of atoms constituting the main skeleton of the linking group represented by L ⁵ is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 1 to 10. In the present invention, the “main skeleton of the linking group” means an atom or an atomic group used only for linking Z and the terminal COOH in the general formula (IV), and there are a plurality of linking paths. In some cases, it refers to an atom or atomic group that constitutes a pathway that uses the least number of atoms.

  The diol compound having a carboxyl group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 3,5-dihydroxybenzoic acid and 2,2-bis (hydroxymethyl) butanoic acid. (DMBA), 2,2-bis (hydroxymethyl) propionic acid (DMPA), 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxy Methyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, 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. Among these, 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 2,2-bis (hydroxymethyl) propionic acid (DMPA) are particularly preferable.

  The content of the alkali-developable unit represented by the general formula (II) in the polyurethane resin is not particularly limited, but when the total structural unit of the polyurethane resin is 100 mol%, the content of the general formula (II) The alkali-developable unit represented is preferably contained in an amount of 80 mol% or less, and more preferably 2 mol% to 70 mol%.

  The polyurethane resin having at least one carboxyl group at the end of the main chain as the alkali developable resin and having an ethylenically unsaturated group in the side chain is, for example, a diol compound, a diisocyanate compound, and at least one carboxyl group. It is obtained by polymerizing a carboxylic acid compound having

-Diol compound-
The diol compound is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, a diol compound having a carboxyl group, and an ethylenic group on the side chain. Examples thereof include a diol compound having a saturated group. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said polyether diol compound, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph [0068]-[0076] of Unexamined-Japanese-Patent No. 2005-250438 etc. are mentioned. It is done. Specifically, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, tetra -1,2-propylene glycol, hexa-1,2-propylene glycol, di-1,3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol, di-1,3- Butylene glycol, tri-1,3-butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol having a weight average molecular weight of 1000, polyethylene glycol having a weight average molecular weight of 1500, polyethylene having a weight average molecular weight of 2000 Ethylene glycol, polyethylene glycol having a weight average molecular weight of 3000, polyethylene glycol having a weight average molecular weight of 7500, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, polypropylene glycol having a weight average molecular weight of 1000, polypropylene glycol having a weight average molecular weight of 2000 And polypropylene glycol having a weight average molecular weight of 3000 and polypropylene glycol having a weight average molecular weight of 4000.

  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.

  There is no restriction | limiting in particular as said polycarbonate diol compound, According to the objective, it can select suitably, For example, Unexamined-Japanese-Patent No. 2005-250438 Paragraph [0080]-[0081] and Paragraph [0084] No. 9-No. 12 and the like.

Examples of the diol compound having an ethylenically unsaturated group in the side chain include those similar to the diol compound having an ethylenically unsaturated group in the side chain described above for the ethylenically unsaturated group.
Examples of the diol compound having a carboxyl group include those represented by the general formula (IV).

When obtaining the said polyurethane resin, the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above can also be used together.
There is no restriction | limiting in particular as a diol compound which has a substituent which does not react with the said isocyanate group, According to the objective, it can select suitably, For example, Paragraph [0087]-[0088] of Unexamined-Japanese-Patent No. 2005-250438 And the compounds described.

Moreover, in the synthesis | combination of the said polyurethane resin, the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
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, JP-A-2005-250438, paragraph [0095] to And the compounds described in [0101].

-Diisocyanate compound-
There is no restriction | limiting in particular as said diisocyanate compound, Although it can select suitably according to the objective, For example, the diisocyanate compound etc. which are represented with the following general formula (V) are preferable.
<General formula (V)>
OCN-L ⁶ -NCO
In the general formula (V), L ⁶ represents a also may divalent substituted aliphatic or aromatic hydrocarbon group. L ⁶ may have another functional group that does not react with an isocyanate group, for example, an ester group, a urethane group, an amide group, or a ureido group, if necessary.

There is no restriction | limiting in particular as a diisocyanate compound represented by the said general formula (V), Although it can select suitably according to the objective, The following general formula (VI) is used for the polyurethane resin as said alkali developable resin. It is preferable that the group represented by the following general formula (VI) is included at the point which can contain the group represented.
However, in the general formula (VI), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. Y represents —NH—, —NHCO—, —NHCOO—, —CONH—, or —OCONH—. R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ may be the same as or different from each other, and are each a hydrogen atom, a monovalent organic group, a halogen atom, —OR ¹⁵ , —N (R ^{16) (R 17),} or an ^{-SR 18, R 15, R 16} , R 17, and ^{R 18} represents a hydrogen atom, or a monovalent organic group.

X is preferably —CH ₂ — or —O—, particularly preferably —CH ₂ —, from the viewpoint of developability.
The monovalent organic group in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ is not particularly limited and may be appropriately selected depending on the purpose. For example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, —OR ¹⁹ (where R ¹⁹ represents a monovalent organic group), aryl group, aryloxy group, arylamino group, diarylamino Group and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and the like.
Wherein ^{R 11, R 12, R 13} , and as ^{R 14,} from the viewpoint of resolution, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably ^{-OR 19,} hydrogen atom is particularly preferred.

  There is no restriction | limiting in particular as mass composition ratio of the aromatic group represented by the said general formula (VI), Although it can select suitably according to the objective, 20 mass% or more is preferable and 20 mass%-70 mass. % Is more preferable. In addition, when the mass composition ratio of the said aromatic group contains the structural unit represented by the said general formula (VI), X represents the ratio calculated by including in an aromatic.

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said general formula (V), According to the objective, it can select suitably, For example, the dimer of 2, 4- tolylene diisocyanate and 2, 4- tolylene diisocyanate 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4 Aromatic diisocyanate compounds such as 4,4'-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4 ' Alicyclic diisocyanate compounds such as methylene bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate 2 A diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate; These may be used individually by 1 type and may use 2 or more types together. Among these, an aromatic diisocyanate compound is preferable in terms of hardness, and 2,4-tolylene diisocyanate, m-xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI) are particularly preferable.

The diisocyanate compound represented by the general formula (V) is obtained by, for example, subjecting a triisocyanate compound and one equivalent of a monofunctional alcohol or monofunctional amine compound having an ethylenically unsaturated group to an addition reaction. 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 the 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 [ 0037] to [0040] and the like.

-Method for producing a polyurethane resin having at least one carboxyl group at the end of the main chain and having an ethylenically unsaturated group in the side chain-
There is no restriction | limiting in particular as a manufacturing method of the said polyurethane resin, According to the objective, it can select suitably, For example, the said diisocyanate compound, the said diol compound, the said carboxylic acid compound, and other copolymerization components as needed And a method in which a known catalyst having an activity corresponding to each reactivity is added in an aprotic solvent and heated. The molar ratio of the diisocyanate used in the synthesis and the diol _compound: As the _(M a M _b), is not particularly limited and may be appropriately selected depending on the intended purpose, 1: 1 to 1.2: 1, preferably 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.

There is no restriction | limiting in particular as a weight average molecular weight of the polyurethane resin as said alkali developable resin, Although it can select suitably according to the objective, 5,000-60,000 are preferable and 5,000-50,000 are preferable. Is more preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 5,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 60,000, coating suitability and developability may deteriorate. is there.
Here, the weight average molecular weight is, for example, a high-speed GPC apparatus (HLC-802A, manufactured by Toyo Soda Co., Ltd.), a 0.5% by mass tetrahydrofuran (THF) solution is used as a sample solution, and the column is TSKgel HZM. -Using one M, inject 200 μL of sample, elute with the THF solution, and measure at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm). Next, the weight average molecular weight can be determined from the molecular weight distribution curve calibrated with standard polystyrene.

The acid value of the alkali-developable 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, more preferably 30 mgKOH / g to 110 mgKOH / g, / G to 100 mg KOH / g is particularly preferred. 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.
The acid value can be measured, for example, according to JIS K0070. However, when the sample does not dissolve, dioxane or tetrahydrofuran is used as a solvent.

  5 mass%-80 mass% are preferable, and, as for content in the said photosensitive composition solid content of the said alkali developable resin, 30 mass%-60 mass% are 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.

<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.

  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 bonds is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from monomers having a (meth) acryl group is Preferably mentioned.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) 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, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate , Tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; polyfunctional alcohols such as trimethylolpropane, glycerin, bisphenol, and (meth) acrylate after addition reaction of ethylene oxide and propylene oxide; epoxy Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of 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 Particularly preferred.

  5 mass%-50 mass% are preferable, and, as for content in the said photosensitive composition solid content of the said polymeric compound, 10 mass%-40 mass% are 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 2010-256399 A 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 JP2010-256399A.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said photoinitiator, Although it can select suitably according to the objective, 0.1 mass%-30 mass% are preferable, 0 0.5 mass% to 20 mass% is more preferable, and 0.5 mass% to 15 mass% is particularly preferable.

<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, An epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), an oxetane compound having at least two oxetanyl groups in one molecule can be used, and is 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 an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule.

  Examples of the epoxy compound having at least two oxirane groups per molecule include, for example, bisphenol F type epoxy resin (Epototo YDF-170, manufactured by Tohto Kasei Co., Ltd.), bixylenol type or biphenol type epoxy resin (“YX4000, Japan Epoxy resin "etc.) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton, etc. (" TEPIC, Nissan Chemical Industries, Ltd. "," Araldite PT810, Ciba Specialty Chemicals "), Bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin Resin, halogenated epoxy resin (for example, low brominated epoxy resin, highly halogenated epoxy resin, brominated phenol novolac type epoxy resin, etc.), bisphenol condensation type epoxy resin ("VG-3101; manufactured by Printec Co., Ltd."), Allyl group-containing bisphenol A type epoxy resin, trisphenolmethane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; Dainippon Ink and Chemicals, Inc.) ”, Etc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (diglycidyl phthalate) Ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, cycloaliphatic epoxy resin (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexane) Carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries, Ltd.”, etc.), imide type alicyclic epoxy resin , Trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group included Epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-” 4750, EXA-4700; manufactured by Dainippon Ink and Chemicals, Inc.), a reaction product of a polyphenol compound obtained by addition reaction of a phenol compound with a diolefin compound such as divinylbenzene or dicyclopentadiene, and epichlorohydrin, 4 -Ring-opening polymer of vinylcyclohexene-1-oxide epoxidized with peracetic acid or the like, epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methylstilbene type liquid crystal epoxy resin, Dibenzoyloxybenzene Liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; NOF Corporation) And the like, and a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, and the like. These may be used individually by 1 type and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred is a compound containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

  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 the compounds described in paragraph [0076] of JP2010-256399A.

  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 melamine derivatives described in paragraph [0077] of JP 2010-256399 A.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said thermal crosslinking agent, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, and 3 mass%- 30 mass% is more preferable. If the said content is 1 mass% or more, the film | membrane intensity | strength of a cured film will be improved, and if it is 50 mass% or less, developability and exposure sensitivity will become favorable.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a diluent, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, a coloring agent (a coloring pigment or dye) Furthermore, adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances) , Surface tension adjusting agents, chain transfer agents, etc.) may be used in combination.
By appropriately containing these components, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

-Diluent (solvent)-
The diluent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols such as methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, and normal-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, acetic acid-normal amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Halogenated hydrocarbons; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. . These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.
0.5 mass%-60 mass% are preferable, and, as for content in the said photosensitive composition of the said diluent, 5 mass%-50 mass% are more preferable.

The filler is described in detail, for example, in paragraphs [0098] to [0099] of JP-A-2008-250074.
The thermal polymerization inhibitor is described in detail, for example, in paragraphs [0101] to [0102] of JP-A-2008-250074.
The thermosetting accelerator is described in detail in paragraph [0093] of JP-A-2008-250074, for example.
The plasticizer is described in detail, for example, in paragraphs [0103] to [0104] of JP-A-2008-250074.
The colorant is described in detail, for example, in paragraphs [0105] to [0106] of JP-A-2008-250074.
The adhesion promoter is described in detail in, for example, paragraphs [0107] to [0109] of JP-A-2008-250074.

(Photosensitive film)
The photosensitive film of the present invention comprises at least a support and a photosensitive layer comprising the photosensitive composition of the present invention on the support, and further comprises 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 preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned. These may be used alone or in combination of two or more. Among these, polyethylene terephthalate is particularly preferable.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2 micrometers-150 micrometers are preferable, 5 micrometers-100 micrometers are more preferable, 8 micrometers-50 micrometers are especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

-Photosensitive layer-
If the said photosensitive layer is a layer which consists of photosensitive compositions, 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 a method for forming the photosensitive layer, 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, and the solution is directly applied. The method of laminating | stacking by apply | coating and drying is mentioned.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, the thing similar to the said diluent can be used.

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 is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1 micrometer-100 micrometers are preferable, 2 micrometers-50 micrometers are more preferable, and 4 micrometers-30 micrometers are especially preferable.

<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 absorbing 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.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
There is no restriction | limiting in particular in the thickness of the said protective film, Although it can select suitably according to the objective, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially preferable.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
If the static friction coefficient is 0.3 or more, it is possible to prevent the occurrence of winding misalignment when the roll is formed due to overslip, and if it is 1.4 or less, it can be wound into a good roll. .

  For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is preferable.

  The protective film may be surface-treated in order 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 it at 30 to 150 ° C. for 1 to 30 minutes. As for the temperature in the case of the said drying, 50 to 120 degreeC is especially preferable.

(Photosensitive laminate)
The photosensitive laminate has at least a substrate and a photosensitive layer provided on the substrate, and is formed by laminating other layers appropriately selected according to the purpose.
The photosensitive layer is transferred from the photosensitive film produced by the manufacturing method described above, 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 member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

<Method for producing photosensitive laminate>
Examples of the method for producing the photosensitive laminate include a method in which at least the photosensitive layer in the photosensitive film of the present invention is transferred and laminated while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate, the photosensitive film of the present invention is laminated on the surface of the substrate while at least one of heating and pressing. 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.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable and 0.2 MPa-0.8 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator Co., Ltd. make, VP-II, Nichigo Morton Co., Ltd. make, VP130) is preferable.

  Since the photosensitive film of the present invention and the photosensitive laminate have a uniform film thickness and an extremely low occurrence rate of surface defects such as pinholes and repellencies, they have excellent insulating properties and high-definition permanent patterns (protective films) , Interlayer insulating film, solder resist pattern, etc.) can be formed efficiently. Therefore, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be suitably used particularly 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 such as a development step appropriately selected as necessary.

<Exposure process>
The said exposure process is a process of exposing with respect to the photosensitive layer in the photosensitive laminated body of this invention. The photosensitive laminate of the present invention is as described above.

  The exposure target is not particularly limited as long as it is a photosensitive layer in the photosensitive laminate, and can be appropriately selected according to the purpose. For example, as described above, a photosensitive film is formed on a substrate. It is preferably performed on a laminate formed by laminating while performing at least one of heating and pressurization.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned.

<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 development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably 8-12, more preferably 9-11. As said weak alkaline aqueous solution, 0.1 mass%-5 mass% sodium carbonate aqueous solution or potassium carbonate aqueous solution etc. are mentioned, for example.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

<< Curing treatment 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.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
The heating temperature in the entire surface heating is preferably 120 ° C to 250 ° C, more preferably 120 ° C to 200 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the resin in the photosensitive composition is decomposed to prevent the film quality from being weak and brittle.
The heating time in the entire surface heating is preferably 10 minutes to 120 minutes, more preferably 15 minutes to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are 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 the printed wiring board by the permanent pattern forming method. Further, 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 wiring 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. And a semiconductor, components, etc. are mounted in the part which soldered. At this time, the permanent pattern by the hardened layer functions 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.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In addition, the acid value and weight average molecular weight in the following synthesis 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.

<Weight average molecular weight>
The said weight average molecular weight was measured using the high-speed GPC apparatus (The Toyo Soda Co., Ltd. make, HLC-802A). That is, 0.5% by mass of THF (tetrahydrofuran) solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 μL of sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. did. Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.

(Synthesis Example 1)
-Synthesis of polyurethane resin U-1-
In a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer, 1.62 g (0.018 mol) of lactic acid and 8.00 g (0.000 g) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) were added. 054 mol) and 15.38 g (0.096 mol) of glycerol monomethacrylate were dissolved in 73 g of cyclohexanone. To this, 30.03 g (0.12 mol) of 4,4′-diphenylmethane diisocyanate (MDI), 4.80 g (0.03 mol) of 1,4-phenylene diisocyanate (PDI), 2,6-di-t- 0.1 g of butylhydroxytoluene and 0.2 g of a trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) were added as a catalyst, and the mixture was heated and stirred at 75 ° C. for 5 hours. Then, it diluted with 9.61 mL of methyl alcohol, and stirred for 30 minutes, The polyurethane resin U-1 solution (solid content 45 mass%) represented by a following formula of 165g was obtained.
The obtained polyurethane resin U-1 solution had a solid content acid value of 68 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 8,500.

<Polyurethane resin U-1>
However, in said formula, a1, b1, c1, d1, and e1 represent a composition ratio (mass%).

(Synthesis Example 2)
-Synthesis of polyurethane resin U-2-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) was added 2.41 g (0.018 mol) of malic acid, 5.23 g (0.039 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 17.78 g (0.111 of glycerol monomethacrylate). Mol)
Change cyclohexanone 73g to 74g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). Polyurethane resin U-2 represented by the following formula in the same manner as in Synthesis Example 1 except that 30.03 g (0.12 mol) and hexamethylene diisocyanate (HMDI) were changed to 5.05 g (0.03 mol). A solution (solid content: 45% by mass) was synthesized.
The obtained polyurethane resin U-2 solution had a solid content acid value of 64 mgKOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 6,500.

<Polyurethane resin U-2>
However, in the said formula, a2, b2, c2, d2, and e2 represent a composition ratio (mass%).

(Synthesis Example 3)
-Synthesis of polyurethane resin U-3-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) was added 2.68 g (0.020 mol) of malic acid, 3.46 g (0.023 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 22.96 g (0.143 of glycerol monomethacrylate). Mol)
Change the cyclohexanone 73g to 78g,
30.03 g (0.12 mol) of 4,4′-diphenylmethane diisocyanate (MDI) and 4.80 g (0.03 mol) of 1,4-phenylene diisocyanate (PDI) were added to 35.05 g of trimethylhexamethylene diisocyanate (TMHDI). A polyurethane resin U-3 solution (solid content: 45% by mass) represented by the following formula was synthesized in the same manner as in Synthesis Example 1 except that the amount was changed to (0.167 mol).
The obtained polyurethane resin U-3 solution had a solid content acid value of 52 mgKOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 7,000.

<Polyurethane resin U-3>
However, in said formula, b3, c3, d3, and h3 represent a composition ratio (mass%).

(Synthesis Example 4)
-Synthesis of polyurethane resin U-4-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) was added to 3.1 g (0.02 mol) of hydroxyhexanoic acid, 11.2 g (0.08 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 23 g (0.14 of glycerol monomethacrylate). Mol) and 4.7 g (0.01 mol) of polypropylene glycol (PPG1000),
Change the cyclohexanone 73g to 60g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). A polyurethane resin U-4 solution (solid content: 45% by mass) represented by the following formula was synthesized in the same manner as in Synthesis Example 1 except that the amount was changed to 58 g (0.23 mol).
The obtained polyurethane resin U-4 solution had a solid content acid value of 58 mgKOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 9,000.

<Polyurethane resin U-4>
However, in said formula, a4, c4, d4, e4, and h4 represent a composition ratio (mass%).

(Synthesis Example 5)
-Synthesis of polyurethane resin U-5-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) was added to 1.9 g (0.01 mol) of malic acid, 8.4 g (0.06 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 12.7 g (0.08 of glycerol monomethacrylate). Mol), polypropylene glycol (PPG1000) 10.6 g (0.01 mol) and hexamethylene glycol 10.2 g (0.07 mol)
Change the cyclohexanone 73g to 60g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). Polyurethane resin U-5 represented by the following formula in the same manner as in Synthesis Example 1 except that 48.1 g (0.19 mol) and hexamethylene diisocyanate (HMDI) 8.1 g (0.05 mol) were used. A solution (solid content: 45% by mass) was synthesized.
The obtained polyurethane resin U-5 solution had a solid content acid value of 48 mg KOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 11,000.

<Polyurethane resin U-5>
However, in said formula, a5, b5, c5, d5, e5, f5, and h5 represent a composition ratio (mass%).

(Synthesis Example 6)
-Synthesis of polyurethane resin U-6-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) was added to 2.9 g (0.02 mol) of citric acid, 9.4 g (0.07 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 28.9 g (0.18 of glycerol monomethacrylate). Mol)
Change 73g of cyclohexanone to 63g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). Polyurethane resin U- represented by the following formula in the same manner as in Synthesis Example 1 except that 37.7 g (0.15 mol) and trimethylhexamethylene diisocyanate (TMHDI) 21.1 g (0.10 mol) were used. Six solutions (solid content 45 mass%) were synthesized.
The obtained polyurethane resin U-6 solution had a solid content acid value of 63 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 16,000.

<Polyurethane resin U-6>
However, in said formula, a6, b6, c6, d6, and h6 represent a composition ratio (mass%).

(Synthesis Example 7)
<Synthesis of polyurethane resin U-7>
-Synthesis of Carboxylic Acid Compound (A)-
In a 1 L three-necked round bottom flask equipped with a condenser and a stirrer, 73.8 g (0.55 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and hydrogenated trimellitic acid ( 99.1 g (0.5 mol) manufactured by Mitsubishi Gas Chemical Company) was added to 400 mL of tetrahydrofuran (THF), and the mixture was stirred at 60 ° C. for 8 hours. After completion of the reaction, the reaction solution was added dropwise to 2 L of hexane to precipitate crystals. After standing for 1 day, the solid was collected by filtration. Vacuum drying was performed to obtain 158.6 g of a carboxylic acid compound (A) represented by the following formula.
<Carboxylic acid compound (A)>

-Synthesis of polyurethane resin U-7-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) was added to 9.4 g (0.01 mol) of carboxylic acid compound (A), 4.91 g (0.03 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 17.43 g of glycerol monomethacrylate. (0.11 mol) and hexamethylene glycol 10.99 g (0.03 mol)
Change the cyclohexanone 73g to 61g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). Polyurethane resin U-7 represented by the following formula in the same manner as in Synthesis Example 1 except that 53.27 g (0.21 mol) and hexamethylene diisocyanate (HMDI) 3.98 g (0.02 mol) were used. A solution (solid content: 45% by mass) was synthesized.
The obtained polyurethane resin U-7 solution had a solid content acid value of 66 mgKOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 12,000.
<Polyurethane resin U-7>
However, a, b, c, d, f, and k in the said formula represent a composition ratio (mass%).

(Synthesis Example 8)
-Synthesis of polyurethane resin UX-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) is changed to 16.7 g (0.12 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 26.8 g (0.17 mol) of glycerol monomethacrylate,
Change the cyclohexanone 73g to 67g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). Polyurethane resin UX represented by the following formula in the same manner as in Synthesis Example 1 except that 39.3 g (0.16 mol) and 17.6 g (0.10 mol) of hexamethylene diisocyanate (HMDI) were used. A solution (solid content: 45% by mass) was synthesized.
The resulting polyurethane resin UX solution had a solid content acid value of 72 mg KOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 8,500.

<Polyurethane resin UX>
However, in said formula, a10, b10, c10, and d10 represent a composition ratio (mass%).

(Synthesis Example 9)
-Synthesis of polyurethane resin UY-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) was changed to 16.2 g (0.09 mol) of polybutylene glycol and 5.23 g (0.09 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA),
Change the cyclohexanone 73g to 65g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). A polyurethane resin U-Y solution (solid content: 45% by mass) represented by the following formula was synthesized in the same manner as in Synthesis Example 1, except that the amount was changed to 33.2 g (0.14 mol).
The obtained polyurethane resin UY solution had a solid content acid value of 75 mgKOH / g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 8,200.

<Polyurethane resin UY>
However, in the said formula, a11, b11, and c11 represent a composition ratio (mass%).

(Synthesis Example 10)
-Synthesis of polyurethane resin U-Z-
In Synthesis Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate. Mol) is 0.89 g (0.007 mol) of malic acid, 8.05 g (0.06 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 33.51 g (0 of mol) of polypropylene glycol (PPG1000). 0.033 mol) and 7.08 g (0.061 mol) of hexamethylene glycol,
Change cyclohexanone 73g to 103g,
4,4′-diphenylmethane diisocyanate (MDI) and 30.03 g (0.12 mol) and 1,4-phenylene diisocyanate (PDI) 4.80 g (0.03 mol) were mixed with 4,4′-diphenylmethane diisocyanate (MDI). Polyurethane resin UZ represented by the following formula in the same manner as in Synthesis Example 1 except that 20.85 g (0.083 mol) and hexamethylene diisocyanate (HMDI) 14.02 g (0.083 mol) were used. A solution (solid content: 45% by mass) was synthesized.
The obtained polyurethane resin UZ solution had a solid content acid value of 40 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 18,000.

<Polyurethane resin U-Z>
However, in the formula, a7, b7, c7, e7, f7, and h7 represent a composition ratio (mass%).

(Synthesis Example 11)
-Synthesis of polyester resin E-1-
699 parts by weight of dimethyl terephthalate, 524 parts by weight of dimethyl isophthalate, 226 parts by weight of dimethyl adipate, 553 parts by weight of dimethyl sebacate, 417 parts by weight of 2,2-dimethylpropanediol, 324 parts by weight of butanediol, 769 parts by weight of ethylene glycol As an antioxidant, 2 parts by mass of Irganox 1330 (manufactured by Ciba Japan Co., Ltd.) and 0.9 parts by mass of tetrabutyl titanate were mixed in the reactor, and the temperature was raised from room temperature to 260 ° C. over 2 hours with stirring. Then, the mixture was heated at 260 ° C. for 1 hour to conduct a transesterification reaction. Next, the pressure in the reactor was gradually reduced and the temperature was raised, and an initial polycondensation reaction was performed at 245 ° C. and 0.5 to 2 torr over 30 minutes. Furthermore, after conducting a polymerization reaction at 245 ° C. and 0.5 to 2 torr for 4 hours, the pressure was returned to normal pressure over 30 minutes while introducing dry nitrogen, and the polyester was taken out into pellets to obtain polyester resin E-1. Obtained. The obtained polyester resin E-1 was diluted and dissolved with propylene glycol monomethyl ether acetate so as to have a solid content concentration of 60% by mass to obtain a polyester resin E-1 solution.
The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography of the obtained polyester resin E-1 was 34,000.

Example 1
-Production of photosensitive film-
A photosensitive composition solution 1 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, dried, and a photosensitive layer having a thickness of 30 μm was formed on the support. Formed. On the photosensitive layer, as a protective layer, a polypropylene film having a thickness of 20 μm (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated to produce a photosensitive film.

-Composition of photosensitive composition solution 1-
-Polyurethane resin U-1 solution of Synthesis Example 1 (solid content: 45% by mass) ... 37.2 parts by mass-Polymerizable compound (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) ... 11.15 masses Part ・ Thermal crosslinking agent (Epototo YDF-170, manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin) 2.0 parts by mass Photopolymerization initiator represented by the following structural formula C-1 1 .0 parts by mass

-Diethylthioxanthone-0.7 parts by mass-Pigment dispersion (hereinafter referred to as "G-1")-36.1 parts by mass-Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.) 30% by mass methyl ethyl ketone solution 0.13 parts by mass Methyl ethyl ketone (solvent) 12.0 parts by mass In addition, the pigment dispersion (G-1) is silica (manufactured by Admatechs Co., Ltd., SO-C2). ) 30 parts by mass, 48.2 parts by mass of the polyurethane resin U-1 solution of Synthesis Example 1, 0.51 parts by mass of phthalocyanine blue, 0.14 parts by mass of anthraquinone yellow pigment (CI PY24), After 59.0 parts by mass of cyclohexanone was mixed in advance, the motor mill M-250 (manufactured by Eiger) was used for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm. Prepared by dispersing.

-Lamination on substrate-
The substrate was prepared by subjecting a surface of a copper clad laminate (no through hole, copper thickness: 12 μm) to chemical polishing. 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 laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order was prepared.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

  About the obtained laminated body, surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness were evaluated as follows. The results are shown in Table 1.

<Measurement of surface hardness>
A solder resist layer made of each photosensitive composition was formed on the substrate. According to the test method of JIS K-5400, the highest hardness at which a film was not damaged when a load of 1 kg was applied using a pencil hardness tester was evaluated according to the following criteria.
〔Evaluation criteria〕
○: More than 4H, excellent surface hardness Δ: 3H-4H, slightly inferior surface hardness ×: Less than 2H, inferior surface hardness

<Evaluation of fine pattern formability>
In order to evaluate the fine pattern formability in the produced permanent pattern shape, the photosensitive laminate after the formation of the permanent pattern is cut, and the support 2 side surface 2 and the permanent pattern are cut from the cut surface of the permanent pattern 10 shown in FIG. The cross section of the angle θ formed with the side surface 3 was observed using a scanning electron microscope (S-4100, manufactured by Hitachi, Ltd.).
〔Evaluation criteria〕
◎: formed angle θ is less than 80 ° ○: formed angle θ is 80 ° or more and less than 90 ° ○ △: formed angle θ is 90 ° or more and less than 100 ° △: formed angle θ is 100 ° or more and less than 110 ° ×: eggplant Angle θ is 110 ° or more

<Evaluation of resolution>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). Optimum light energy using a pattern forming device so that round holes with a diameter of 50 μm to 200 μm can be formed from a round hole pattern on the polyethylene terephthalate film (support) of the obtained photosensitive laminate. 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: A round hole with a diameter of 80 μm or less can be resolved, and the resolution is excellent. ○: A round hole with a diameter of 100 μm or less can be resolved, and the resolution is good. Δ: A round hole with a diameter of 200 μm or less. Can be resolved and resolution is slightly inferior ×: Round hole is not resolvable and resolution is inferior

<Evaluation of insulation>
The copper foil of the printed circuit board obtained by laminating a copper foil having a thickness of 12 μm on a glass epoxy substrate is etched, the line width / space width is 50 μm / 50 μm, the lines are not in contact with each other, and the same facing each other A comb electrode on the surface was obtained. A solder resist layer was formed on the comb-shaped electrode of this substrate by a conventional method, and exposure was performed with an optimum exposure amount (300 mJ / cm ^{2 to 1} J / cm ² ). Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist was formed.
After connecting the polytetrafluoroethylene shield wires to the comb electrodes with Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation laminate after heating, 5 V is applied to the evaluation laminate. With the voltage applied, the laminate for evaluation was allowed to stand in a super accelerated high temperature and high humidity life test (HAST) bath of 85% RH at 130 ° C. for 200 hours. Thereafter, the degree of migration of the solder resist in the laminate for evaluation was observed with a 100-fold metal microscope.
〔Evaluation criteria〕
A: The occurrence of migration cannot be confirmed, and the insulation is excellent. ○: The occurrence of migration is confirmed slightly on copper, but the insulation is good. Δ: The occurrence of migration is confirmed, and the insulation is slightly inferior. : Short circuit between electrodes and poor insulation

<Evaluation of development residue removability>
In the evaluation of the resolution, among the formed round hole patterns, the residue at the bottom of the round holes of 80 μm and 120 μm was observed with SEM, and thus obtained copper-clad laminate with a cured resin pattern Observe the surface of the plate with an optical microscope, measure the minimum round hole pattern width that there is no residue at the bottom of the round hole of the pattern, there is no abnormality such as blistering / peeling of the pattern part, and space can be formed. Evaluated by criteria.
〔Evaluation criteria〕
A: There is no development residue on the substrate having a round hole with a diameter of 80 μm, and the development residue removal property is excellent. ○: There is no development residue on the substrate having a round hole with a diameter of 120 μm, and the development residue removal property is good. The development residue is slightly inferior on the substrate having a round hole with a diameter of 120 μm, and the development residue removal property is slightly inferior.

<Heat resistance>
An evaluation substrate on which a solder resist layer made of each photosensitive composition is formed on a substrate and a rosin-based flux is applied is immersed in a solder bath previously set at 260 ° C. for 30 seconds, and the flux is washed with denatured alcohol. The resist layer was swollen, peeled, and discolored by the following criteria.
〔Evaluation criteria〕
◎: No change is observed and heat resistance is particularly excellent ○: Swelling, peeling, and discoloration are slightly observed, but heat resistance is excellent ○ △: Swelling and peeling are slightly observed, but heat resistance △: Partial swelling and peeling are observed, heat resistance is poor ×: The coating film is swollen and peeled

<Toughness>
The photosensitive laminate having a solder resist layer is formed on a printed circuit board obtained by laminating a copper foil having a thickness of 12 μm on a glass epoxy base material by a conventional method, and a HMW-201GX type exposure manufactured by Oak Seisakusho through a 2 mm square photomask. The exposure was performed with an optimum exposure dose (300 mJ / cm ^{2 to 1} J / cm ² ) that can form a 2 mm square pattern. Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist having a 2 mm square opening was formed.
The obtained substrate was exposed to an atmosphere of −65 ° C. for 15 minutes, then exposed to an atmosphere of 150 ° C. for 15 minutes, and then exposed to the air of −65 ° C. again for 1,000 times. . Cracks (cracks) on the solder resist of the evaluation substrate through the thermal cycle and the degree of peeling were observed with an optical microscope and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Solder resist has no cracks (cracks) and peeling, and is particularly excellent in toughness ○: The solder resist has cracks (cracks) and peeling slightly, but has good toughness △: Solder The resist has slight cracks (cracks) and peeling, and the toughness is slightly inferior. X: The solder resist has obvious cracks (cracks) and peeling, and the toughness is inferior.

(Example 2)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content 45 mass%) of Synthesis Example 1 was replaced with the polyurethane resin U-2 solution (solid content 45 mass%) of Synthesis Example 2 in Example 1. In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Example 3)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content 45% by mass) in Synthesis Example 1 was replaced with the polyurethane resin U-3 solution (solid content 45% by mass) in Synthesis Example 3 in Example 1. In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

Example 4
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content 45% by mass) of Synthesis Example 1 was replaced with the polyurethane resin U-4 solution (solid content 45% by mass) of Synthesis Example 4 in Example 1. In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Example 5)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content 45% by mass) in Synthesis Example 1 was replaced with the polyurethane resin U-5 solution (solid content 45% by mass) of Synthesis Example 5 in Example 1. In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Example 6)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content 45% by mass) of Synthesis Example 1 was replaced with the polyurethane resin U-6 solution (solid content 45% by mass) of Synthesis Example 6 in Example 1. In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Example 7)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
In Example 1, the photosensitive film, the laminated body, and the permanent pattern were manufactured like Example 1 except having replaced the photosensitive composition solution 1 with the following photosensitive composition solution 2. FIG.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

-Composition of photosensitive composition solution 2-
The following each component was mixed and the photosensitive composition solution 2 was prepared.
・ Polyurethane resin U-4 solution of Synthesis Example 4 (solid content 45 mass%) 20.3 mass parts Polymerizable compound: DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 5.3 mass parts Cross-linking agent: Epototo YDF-170 (manufactured by Toto Kasei Co., Ltd.) 2.9 parts by mass Initiator: Irgacure 907 (manufactured by BASF) ... 0.6 parts by mass Sensitizer: DETX-S (Japan) Manufactured by Kayaku Co., Ltd.) 0.005 parts by mass Reaction aid: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 0.019 parts by mass Pigment dispersion (hereinafter referred to as “G-2”)・ ・ 30.1 parts by mass ・ Coating aid: Megafac F-780F... 0.2 parts by mass (Dainippon Ink Chemical Co., Ltd .: 30% by mass methyl ethyl ketone solution)
-Elastomer: Polyester resin E-1 of Synthesis Example 11 (solid content 60% by mass) ... 2.7 parts by mass In addition, the pigment dispersion (G-2) is silica (manufactured by Admatechs, SO-C2 ) 32.0 parts by mass, Solsperse 24000GR (manufactured by Louvresol) 0.44 parts by mass, polyurethane resin U-4 solution of Synthesis Example 4 (solid content 45% by mass) 12.0 parts by mass, phthalocyanine blue 0. 21 parts by mass, 0.06 parts by mass of anthraquinone yellow pigment (CI PY24), 1.65 parts by mass of IXE-6107 (manufactured by Toagosei), and melamine (manufactured by Wako Pure Chemical Industries, Ltd.) After 35 parts by mass and 77.4 parts by mass of cyclohexanone were mixed in advance, a motor mill M-250 (manufactured by Eiger) was used to obtain zirconia beads having a diameter of 1.0 mm and a peripheral speed of 9 m / s. Prepared by time dispersion.

(Example 8)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 7 is the same as Example 7 except that the polyurethane resin U-4 solution (solid content 45% by mass) in Synthesis Example 4 is changed to the polyurethane resin U-5 solution (solid content 45% by mass) in Synthesis Example 5. Similarly, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

Example 9
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 7 is the same as Example 7 except that the polyurethane resin U-4 solution (solid content 45% by mass) of Synthesis Example 4 is replaced with the polyurethane resin U-7 solution (solid content 45% by mass) of Synthesis Example 7. Similarly, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Example 10)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
In Example 7, a thermal crosslinking agent (Epototo YDF-170, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin) was used as a thermal crosslinking agent (TECHMORE VG-3101, manufactured by Printec Co., Ltd., bisphenol condensation type epoxy resin). Except having replaced, it carried out similarly to Example 7, and manufactured the photosensitive film, the laminated body, and the permanent pattern.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Comparative Example 1)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
In Example 1, the photosensitive film, the laminate, and the same as in Example 1 except that the thermal crosslinking agent (Epototo YDF-170, manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin) was not added. A permanent pattern was produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Comparative Example 2)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content 45 mass%) of Synthesis Example 1 was replaced with the polyurethane resin U-Z solution (solid content 45 mass%) of Synthesis Example 10 in Example 1. In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Comparative Example 3)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content: 45% by mass) of Synthesis Example 1 was replaced with the polyurethane resin U-X solution of Synthesis Example 8 (solid content: 45% by mass). In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

(Comparative Example 4)
-Production and evaluation of photosensitive film, laminate and permanent pattern-
Example 1 Example 1 except that the polyurethane resin U-1 solution (solid content 45% by mass) of Synthesis Example 1 was replaced with the polyurethane resin UY solution of Synthesis Example 9 (solid content 45% by mass) in Example 1. In the same manner, a photosensitive film, a laminate, and a permanent pattern were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and toughness. The results are shown in Table 1.

  From the results of Table 1, Examples 1 to 10 have higher development residue removability and can form fine patterns than Comparative Examples 1 to 4, and are excellent in resolution, heat resistance, toughness, and insulation. I found out.

The photosensitive composition of the present invention has a high development residue removability, can form a fine pattern, and is excellent in heat resistance, toughness, resolution, and insulation, so it is particularly suitable for use in a solder resist. it can.
Since the photosensitive film of the present invention can efficiently form a high-definition permanent pattern, various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, BGA (ball grid array), CSP Suitable for semiconductor package formation such as (chip size package) and TCP (tape carrier package), manufacturing of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc. In particular, it can be suitably used for forming a permanent pattern of a printed circuit board, forming a semiconductor package such as BGA (ball grid array), CSP (chip size package), TCP (tape carrier package).
Since the permanent pattern forming method of the present invention uses the photosensitive composition, it is used for forming semiconductor packages such as BGA (ball grid array), CSP (chip size package), TCP (tape carrier package), protective film, interlayer insulation. Suitable for forming various patterns such as films and permanent patterns such as solder resist patterns, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. In particular, it can be suitably used for forming a permanent pattern of a printed circuit board, forming a semiconductor package such as BGA (ball grid array), CSP (chip size package), and TCP (tape carrier package).

DESCRIPTION OF SYMBOLS 1 Support body 2 Support side surface 3 Permanent pattern side surface 10 Permanent pattern θ angle

Claims (16)

A photosensitive composition containing an alkali-developable resin, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent,
The alkali-developable resin is a polyurethane resin linked by a urethane group, has at least one carboxyl group at the end of the main chain of the polyurethane resin, and has an ethylenically unsaturated group in the side chain. A photosensitive composition.   The photosensitive composition of Claim 1 which has 2 or more and 5 or less carboxyl groups at the terminal of the principal chain of a polyurethane resin. The photosensitive composition in any one of Claim 1 to 2 which has a structure represented by the following general formula (I) at the terminal of the principal chain of a polyurethane resin.
-L ¹ - _(COOH) n ··· general formula (I)
In the general formula (I), L ¹ represents an (n + 1) -valent organic connecting chain, and n represents an integer of 1 or more.   The photosensitive composition in any one of Claim 1 to 3 with which alkali developable resin has the alkali developable unit which has a carboxyl group in the side chain of a polyurethane resin. The photosensitive composition according to claim 4, wherein the alkali-developable unit is represented by the following general formula (II).
However, in the general formula (II), R ¹ represents a hydrogen atom or an alkyl group, and R ² and R ³ each independently have a single bond, an ether group, an ester group, an amide group, or a carbonate group. It represents either an alkylene group that may be present or an arylene group that may have a carbonate group. The photosensitive composition according to any one of claims 1 to 5, wherein the alkali-developable resin has a structural unit represented by the following general formula (VI).
However, in the general formula (VI), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. Y represents —NH—, —NHCO—, —NHCOO—, —CONH—, or —OCONH—. R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ may be the same as or different from each other, and are each a hydrogen atom, a monovalent organic group, a halogen atom, —OR ¹⁵ , —N (R ^{16) (R 17),} or an ^{-SR 18, R 15, R 16} , R 17, and ^{R 18} represents a hydrogen atom, or a monovalent organic group.   The photosensitive composition according to claim 1, wherein the functional group having an ethylenically unsaturated group is a (meth) acryloyl group.   The photosensitive composition according to any one of claims 1 to 7, wherein the alkali-developable resin is obtained by introducing a carboxylic acid compound having at least one carboxyl group at the terminal of the main chain of the polyurethane resin.   The photosensitive composition according to claim 1, wherein the alkali-developable resin is obtained by polymerizing a diisocyanate compound, a diol compound, and a carboxylic acid compound having at least one carboxyl group.   The photosensitive composition according to claim 8, wherein the carboxylic acid compound is a dicarboxylic acid compound.   The photosensitive composition according to claim 10, wherein the diisocyanate compound is an aromatic diisocyanate compound.   The photosensitive composition according to claim 1, wherein the alkali-developable resin has a weight average molecular weight of 5,000 to 60,000.   A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a support.   A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a substrate.   A method for forming a permanent pattern comprising at least exposing a photosensitive layer formed of the photosensitive composition according to claim 1.   A printed circuit board comprising a permanent pattern formed by the permanent pattern forming method according to claim 15.