JP5255504B2 - 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, a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed circuit board suitable as a solder resist material for forming an image by laser exposure.

  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.

  The solder resist is used in the production of printed wiring boards and the like, but has recently been used in new LSI packages such as BGA and CSP. The solder resist is a material required as a protective film for preventing the solder from adhering to unnecessary portions in the soldering process and as a permanent mask.

Various studies have been made in order to impart storage stability, sensitivity enhancement, substrate adhesion, heat resistance, and the like required for such solder resists.
For example, in Patent Document 1, a polyfunctional SH compound is applied to a solder resist to obtain effects such as sensitivity improvement. However, in this proposal, when an epoxy compound is used as the thermal cross-linking agent, there is a problem that the storage stability of the photosensitive composition is lowered.
Further, Patent Documents 2 and 3 show effects such as development margin in a color filter using a sterically hindered polyfunctional SH compound having a methyl group adjacent to SH. Moreover, an ionic or basic initiator is used. However, these proposals are intended for application to color filters, are not added with a thermal crosslinking agent, and are not planned to be applied to solder resists.

JP 2006-259150 A Japanese Patent Laid-Open No. 10-253815 JP 2004-149755 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 uses a polyfunctional mercapto compound, particularly a polyfunctional SH compound in which a sterically hindered group is introduced at the adjacent position of SH, and also uses a thermal cross-linking agent, so that not only high sensitivity but also substrate adhesion is achieved. And a photosensitive composition capable of improving heat resistance and storage stability, a photosensitive film using the photosensitive composition, a photosensitive laminate, a method for forming a permanent pattern, and a printed circuit board. To do.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a neutral oxime ester system has been started in order to provide the storability, high sensitivity, substrate adhesion, heat resistance, etc. required for the solder resist. It has been found that the above-mentioned problems can be solved by combining an agent with a polyfunctional mercapto compound, particularly a polyfunctional thiolactic acid ester compound or an α-substituted mercaptoacetic acid ester compound.

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> It contains a binder, a polymerizable compound, a photopolymerization initiator, a chain transfer agent, and a thermal crosslinking agent,
The said chain transfer agent is a compound represented by the following general formula (A), It is a photosensitive composition characterized by the above-mentioned.
However, in the general formula (A), R ₁ and R ₂ both represent a hydrogen atom and an organic functional group, and at least one of R ₁ and R ₂ represents an organic functional group, R ₁ and R ₂ may form a ring. Y represents either an oxygen atom or a sulfur atom. n represents 2 to 8, and Z represents an n-functional organic linking chain.
<2> The photosensitive composition according to <1>, wherein the chain transfer agent is an ester or a thioester of a compound represented by the following general formula (B).
However, in said general formula (B), R < ₁ > and R < ₂ > represent the same meaning as the said general formula (A).
<3> The photosensitive composition according to any one of <1> to <2>, wherein the binder is a polymer compound having at least one ethylenically unsaturated double bond in a side chain.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the binder is a polymer compound having at least one ethylenically unsaturated double bond and a carboxyl group in a side chain.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the photopolymerization initiator is a neutral photopolymerization initiator.
<6> The photosensitive composition according to any one of <1> to <5>, wherein the photopolymerization initiator is a neutral oxime ester compound.
<7> From the above <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 6>. The photosensitive composition according to any one of 6).
<8> A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <7> on a support.
<9> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <7> on a substrate.
<10> 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 <7>.
<11> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to <10>.

  According to the present invention, various problems in the prior art can be solved, and high sensitivity is achieved by using a polyfunctional mercapto compound, particularly a polyfunctional SH compound having a sterically hindered group introduced at the adjacent position of SH, and using a thermal crosslinking agent in combination. Photosensitive composition capable of improving not only substrate adhesion, heat resistance and storage stability, photosensitive film using the photosensitive composition, photosensitive laminate, permanent pattern forming method, and printed circuit board Can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains a binder, a polymerizable compound, a photopolymerization initiator, a chain transfer agent, and a thermal crosslinking agent, and further contains other components as necessary.

<Chain transfer agent>
The chain transfer agent is a compound represented by the following general formula (A).
The polyfunctional mercapto compound represented by the general formula (A) does not react with the epoxy compound as a thermal crosslinking agent, the storage stability of the photosensitive composition is not deteriorated, and compared with the monofunctional mercapto compound. Thus, it is possible to achieve higher sensitivity with respect to photopolymerization.
However, in the general formula (A), R ₁ and R ₂ both represent a hydrogen atom and an organic functional group, and at least one of R ₁ and R ₂ represents an organic functional group, R ₁ and R ₂ may form a ring. Y represents either an oxygen atom or a sulfur atom. n represents 2 to 8, and Z represents an n-functional organic linking chain.

Examples of the organic functional group in R ₁ and R ₂ include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an aralkyloxycarbonyl group.
As said alkyl group, a C1-C10 linear or branched thing is preferable, for example, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group. , Tert-butyl group, n-hexyl group, n-octyl group and the like. Among these, a methyl group and an ethyl group are particularly preferable.
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.

  Z represents an n-functional organic linking chain, and examples thereof include an ethylene glycol residue, a trimethyleneethanol residue, a pentaerythritol residue, and a dipentaerythritol residue.

The polyfunctional mercapto compound represented by the general formula (A) is preferably an ester or thioester of a compound represented by the following general formula (B), and a compound represented by the following general formula (B): An ester with an alcohol or a thioester of a compound represented by the following general formula (B) and a thiol is more preferable, and a polyfunctional thiolactic acid ester compound or an α-substituted mercaptoacetic acid ester compound is particularly preferable.
However, in said general formula (B), R < ₁ > and R < ₂ > represent the same meaning as the said general formula (A).
The α-substituted thio structure is a structure in which the carbon atom at the α-position with respect to the mercapto group has a substituent, and is a structure branched at the carbon at the α-position with respect to the mercapto group, in other words, the carbon at the α-position of the mercapto group. Means a so-called branched structure in which is bonded to three or more atoms other than hydrogen.

  Examples of the mercapto group-containing carboxylic acid represented by the general formula (B) include mercapto lactic acid, 2-mercaptoisovaleric acid, 2-mercaptopropionic acid, 2-mercaptoisobutyric acid, 2-mercapto-3,3-dimethyl. Examples include butyric acid, 2-mercapto-3-methylbutyric acid, 2-mercapto-2-phenylpropionic acid, and 2-mercaptohexanoic acid.

  There is no restriction | limiting in particular as said alcohol, Although it can select suitably according to the objective, For example, a polyfunctional alcohol is preferable. By using the polyfunctional alcohol, the compound after the esterification reaction can be a polyfunctional mercapto compound.

Examples of the polyfunctional alcohol include alkylene glycol (wherein the alkylene group preferably has 2 to 10 carbon atoms, and the carbon chain thereof may be branched), diethylene glycol, glycerin, dipropylene glycol, trimethylolpropane, Examples include pentaerythritol and dipentaerythritol.
Examples of the alkylene glycol include ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and tetramethylene glycol. .
Among these, 1,2-propylene glycol, 1,2-butanediol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol are particularly preferable.
There is no restriction | limiting in particular as said thiols, According to the objective, it can select suitably, For example, methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, allyl mercaptan, benzyl mercaptan etc. are mentioned.

There is no restriction | limiting in particular in the molecular weight of the polyfunctional mercapto compound represented by the said general formula (A), Although it can select suitably according to the objective, 200-1,000 are preferable.
The method for producing the polyfunctional mercapto compound is not particularly limited and may be appropriately selected depending on the intended purpose. The ester of a mercapto group-containing carboxylic acid and an alcohol is represented by the general formula (B). The mercapto group-containing carboxylic acid and alcohol are reacted by a conventional method to form an ester or thioester, and the conditions for the ester or thioester reaction are not particularly limited, and conventionally known reaction conditions Can be selected as appropriate. Alternatively, it can be obtained by converting a halogen atom into a mercapto group after esterification or thioesterification of a halogen group-containing carboxylic acid and an alcohol.

Next, although the specific compound of the polyfunctional mercapto compound represented by the said general formula (A) is shown below, it is not limited to these.

  Among these, the compounds represented by the following formulas (R-1), (R-2), (R-3), (R-4), and (R-5) are particularly preferable. Details thereof will be described below.

(R-1): Bifunctional mercapto compound having a secondary mercapto group: As a raw material, glycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) and mercapto lactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are 1: 2.2 ( The bifunctional mercapto compound (R-1) in which the mercapto lactic acid represented by the following formula is secondary by removing excess mercapto lactic acid by dehydration condensation by a conventional method at a molar ratio) and treating with alkaline water. ) Is obtained.
<Chain transfer agent (R-1)>

(R-2): A trifunctional mercapto compound having a secondary mercapto group: As a raw material, trimethylolethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and mercaptolactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are used at 1: 3. 2 (molar ratio) by dehydration condensation by a conventional method, excess mercaptolactic acid is removed by treatment with alkaline water, and a tetrafunctional mercapto compound (R) in which the mercapto group represented by the following formula is secondary. -2) is obtained.
<Chain transfer agent (R-2)>

(R-3): Tetrafunctional mercapto compound having a secondary mercapto group: As a raw material, pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) and mercaptolactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are 1: 4.3. (Molar ratio) by dehydration condensation by a conventional method, excess mercaptolactic acid is removed by treatment with alkaline water, and a tetrafunctional mercapto compound (R-) having a secondary mercapto group represented by the following formula: 3) is obtained.
<Chain transfer agent (R-3)>

(R-4): a tetrafunctional mercapto compound having a secondary mercapto group as a raw material, pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-mercaptoisovaleric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) : 4.3 (molar ratio) by dehydration-condensation by a conventional method, and by treating with weak alkaline water, excess 2-mercaptoisovaleric acid is removed to obtain a tetrafunctional halogen compound.
The resulting tetrafunctional halogen compound was reacted with potassium thioacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) in N-methylpyrrolidone at 50 ° C. After confirming the disappearance of the tetrafunctional halogen compound by thin layer chromatography, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate and concentrated. Purification by silica gel column chromatography gives a tetrafunctional thioacetic acid compound.
The obtained thioacetic acid compound was dissolved in N-methylpyrrolidone, and 6 equivalents of morpholine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted at 70 ° C. After confirming the disappearance of the tetrafunctional thioacetic acid compound by thin layer chromatography, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate and concentrated. Purification by silica gel column chromatography gives a tetrafunctional mercapto compound (R-4) represented by the following formula (yield 72%).
<Chain transfer agent (R-4)>

(R-5): a tetrafunctional mercapto compound having a tertiary mercapto group as a raw material, pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-mercaptoisobutyric acid (manufactured by Sakai Chemical Industry Co., Ltd.) 1: At 4.3 (molar ratio), dehydration-condensation is conducted by a conventional method, and excess 2-mercaptoisobutyric acid is removed by treatment with alkaline water to form a tetrafunctional mercapto compound having a secondary mercapto group (illustrated above) Compound (R-5)) is obtained.
<Chain transfer agent (R-5)>

  The solid content of the compound represented by the general formula (A) as the chain transfer agent in the solid content of the photosensitive composition is preferably 0.01% by mass to 10% by mass, and 0.05% by mass. -7 mass% is more preferable. When the solid content is less than 0.01% by mass, sufficient sensitivity, resolution, and substrate adhesion may not be obtained. May become brittle

<Binder>
The binder is not particularly limited as long as it is a compound into which a photosensitive group and an acid group for imparting alkali developability are introduced, and can be appropriately selected according to the purpose. For example, two or more epoxy A polymer obtained by reacting an epoxy resin having a group with unsaturated (meth) acrylic acid and further reacting with a polybasic acid anhydride; containing a (meth) acrylic acid ester and an unsaturated group, and at least Modified copolymer obtained by adding glycidyl (meth) acrylate to some acid groups of a copolymer obtained from a compound having one acid group; carboxyl group-containing (meth) acrylic copolymer resin and fat Examples thereof include a polymer obtained by a reaction with a cyclic epoxy group-containing unsaturated compound.

  Among these, since the tackiness is low when the photosensitive composition is formed into a dry film to form a photosensitive layer, the compound contains a (meth) acrylic acid ester and an unsaturated group and has at least one acid group. A modified copolymer obtained by adding glycidyl (meth) acrylate to some of the acid groups of the copolymer obtained from the above is more preferable.

  The solid content in the photosensitive composition solid content of the binder is preferably 5% by mass to 80% by mass, and more preferably 30% by mass to 60% by mass. When the solid content is 5% by mass or more, developability and exposure sensitivity are good, and when it 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, For example, the compound which has one or more ethylenically unsaturated bonds is preferable.

  Examples of the ethylenically unsaturated bond include (meth) acryloyl groups, (meth) acrylamide groups, styryl groups, vinyl groups such as vinyl esters and vinyl ethers; and allyl groups such as allyl ethers and allyl esters.

  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, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. When the solid content is 5% by mass or more, developability and exposure sensitivity are good, and when the solid 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 the photopolymerization initiator, a neutral photopolymerization initiator is used. 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 and esters 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. Compounds, and the like. 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 Compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are preferred.

Examples of the (bis) acylphosphine oxide include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6 -Dichlorobenzoylphenylphosphine oxide, 2,6-dimethylmethyoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethyl) And benzoyl) -phenylphosphine oxide.
Examples of the acetophenone compounds include acetophenone, methoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and the like.
Examples of the benzophenone compounds include benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, and diphenoxybenzophenone.
Examples of the benzoin ether compounds include benzoin ethyl ether and benzoin propyl ether.
Examples of the ketal derivative compound include benzyldimethyl ketal.
Examples of the thioxanthone compound include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, and the like.

As an oxime derivative used suitably by this invention, it represents with following General formula (1), for example.

However, in the general formula (1), R ¹ represents any ^one of a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. , R ² each independently represents a substituent. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. A represents any of 4, 5, 6, and 7-membered rings. A is preferably either a 5- or 6-membered ring.

  Moreover, as an oxime derivative (oxime compound) used by this invention, what is represented by following General formula (2) is more preferable.

However, in the general formula (2), R ¹ represents any of a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. , R ² each independently represents a substituent. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. X represents any of CH ₂ , O, and S. A represents either a 5- or 6-membered ring.

In the general formulas (1) and (2), the acyl group represented by R ¹ may be any of aliphatic, aromatic, and heterocyclic, and may further have a substituent.
Examples of the aliphatic group include an acetyl group, a propanoyl group, a butanoyl group, a hexanoyl group, a decanoyl group, a phenoxyacetyl group, and a chloroacetyl group. Examples of the aromatic group include a benzoyl group, a naphthoyl group, a methoxybenzoyl group, and a nitrobenzoyl group. Examples of the heterocyclic group include a furanoyl group and a thiophenoyl group.
As the substituent, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable. As the acyl group, those having 2 to 30 carbon atoms are preferable, those having 2 to 20 carbon atoms are more preferable, and those having 2 to 16 carbon atoms are particularly preferable. Examples of the acyl group include acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl Group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, methacryloyl group , An acryloyl group, and the like.

  The alkyloxycarbonyl group may have a substituent and is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms in total, more preferably having 2 to 20 carbon atoms in total, and 2 to 16 carbon atoms in total. Those are particularly preferred. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. .

  The aryloxycarbonyl group may have a substituent and is preferably an alkoxycarbonyl group having a total carbon number of 7 to 30, more preferably a total carbon number of 7 to 20, and a total carbon number of 7 to 16. Is particularly preferred. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.

  The alkylsulfonyl group may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group, and a heterocyclic group. Preferably mentioned. Particularly preferred examples of the alkylsulfonyl group include a methylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a decylsulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group, and a trifluoromethylsulfonyl group.

  The arylsulfonyl group may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group, and a heterocyclic group. Preferably mentioned. Particularly preferred examples of the arylsulfonyl group include a benzenesulfonyl group, a toluenesulfonyl group, a chlorobenzenesulfonyl group, a butoxybenzenesulfonyl group, a 2,5-dibutoxybenzenesulfonyl group, a paranitrobenzenesulfonyl group, and a perfluorobenzenesulfonyl group.

In the general formulas (1) and (2), examples of the substituent represented by R ² include aliphatic, aromatic, heteroaromatic, halogen atom, —OR ³ , —SR ³ , —NR ³ R ⁴ . Can be mentioned. R ³ and R ⁴ may be linked to each other to form a ring. R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heteroaromatic group. When m is 2 or more and are connected to each other to form a ring, each R ² may form a ring, and a ring may be formed via at least one of R ³ and R ^4. Also good.

In the case where a ring is formed via the substituent R ² , the following structures are exemplified.

In the structural formula, Y and Z represent any one of CH ₂ , —O—, —S—, and —NR—.

Specific examples of the aliphatic group, aromatic group, and heteroaromatic group of R ² , R ³ , and R ⁴ include the same groups as those described above for R ¹ .

  Specific examples of the oxime compound represented by the general formula (1) include compounds represented by the following structural formulas (1) to (51), but the present invention is not limited thereto. .

In addition, the oxime compound used by this invention can be identified by measuring a < ¹ > H-NMR spectrum and a UV-vis absorption spectrum.

As a method for producing the oxime compound, a corresponding oxime compound and an acyl chloride or an anhydride in the presence of a base (for example, triethylamine, pyridine) in an inert solvent such as THF, DMF, acetonitrile, or pyridine It can be easily synthesized by reacting in such a basic solvent. The reaction temperature is preferably −10 ° C. to 60 ° C.
Further, by using chloroformate, alkylsulfonyl chloride, and arylsulfonyl chloride as the acyl chloride, various corresponding oxime ester compounds can be synthesized.

  As a method for synthesizing the oxime compound used as a starting material in the production of the oxime compound, standard chemistry textbooks (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992), or a professional monograph For example, S.M. R. Sandler & W. Karo, Organic functional group preparations, Vol. 3, can be obtained by various methods described in Academic Press.

  As a particularly preferable synthesis method of the oxime compound, for example, a method of reacting an aldehyde or ketone with hydroxylamine or a salt thereof in a polar solvent such as ethanol or ethanol water can be mentioned. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and the base can be added at the start or continuously during the reaction. A basic solvent such as pyridine can also be used as the base and / or solvent or cosolvent. The reaction temperature is generally preferably the reflux temperature of the mixture, that is, about 60 to 120 ° C.

Another different preferred method of synthesis of the oxime compound is by nitrosation of an “active” methylene group with nitrous acid or alkyl nitrite. See, for example, Organic Synthesis coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp. 199 and 840 and alkaline conditions such as those described in Organic Synthesis coll. Vol. V, pp. 32 and 373, coll. Vol. III, pp. 191 and 513, coll. Vol. II, pp. Both acidic conditions, as described in 202, 204 and 363, are suitable for the synthesis of oxime compounds used as starting materials.
The nitrous acid is usually produced from sodium nitrite.
Examples of the alkyl nitrite include methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.

  The oxime ester group may exist in two types of configuration (Z) or (E). The isomers may be separated by conventional methods, or the isomer mixture may be used as it is as a photoinitiating seed. Therefore, the oxime compound of the present invention may be a mixture of isomers on the configuration of the compounds of the structural formulas (1) to (51).

  The oxime compound has excellent storage stability and high sensitivity, and when added to the polymerizable composition, it has excellent storage stability without causing polymerization during storage, and is active when irradiated with energy rays, particularly light. It is possible to obtain a highly sensitive polymerizable composition capable of efficiently generating polymerization by generating radicals and capable of polymerizing the polymerizable compound efficiently in a short time.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
The content of the photopolymerization initiator in the photosensitive composition is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and 0.5% by mass to 15% by mass. Is particularly preferred.

<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 formed using the photosensitive film, developability, etc. In the range that does not adversely affect the above, for example, a compound containing an epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), or an oxetane compound having at least two oxetanyl groups in one molecule is used. An epoxy compound having an oxirane group as described in JP-A-2007-47729, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate and derivatives thereof Compounds obtained by reacting a blocking agent with the isocyanate group of It is below.

  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.

  The solid content in the photosensitive composition solid content of the thermal crosslinking agent is preferably 1% by mass to 50% by mass, and more preferably 3% by mass to 30% by mass. When the solid content is 1% by mass or more, the film strength of the cured film is improved, and when it is 50% by mass or less, the developability and the exposure sensitivity are improved.

  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 in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), 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 novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin) , Brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP- 7200, HP-7200H; manufactured by Dainippon Ink and Chemicals, Inc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (phthalic acid) Diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; Daicel Chemical Industry Co., Ltd. "), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl Ethane resin, naphthalene group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-36” 0; manufactured by Nippon Steel Chemical Co., Ltd. ”,“ HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink and Chemicals Co., Ltd. ”), phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of polyphenol compound obtained by addition reaction and epichlorohydrin, epoxidation of ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid, epoxy resin having linear phosphorus-containing structure, cyclic containing Epoxy resin having phosphorus structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type 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 Metaacryl Copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis Examples thereof include (glycidyloxyphenyl) adamantane type epoxy resin, but are not limited thereto. These epoxy resins 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 having at least two oxetanyl groups in one molecule.
Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group; Novolac resin, poly (p-hydroxystyrene), cardo type bisphenol , Calixarenes, calixresorcinarenes, and ether compounds such as silsesquioxane and other hydroxyl group-containing resins. In addition to these, an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate A polymer etc. are also mentioned.

  Moreover, as the polyisocyanate compound, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is an aliphatic, cycloaliphatic or aromatic group containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

  As an isocyanate group blocking agent in a compound obtained by reacting a blocking agent with the polyisocyanate compound, that is, a compound obtained by reacting a blocking agent with an isocyanate group of polyisocyanate and derivatives thereof, alcohols (for example, isopropanol, tert-butanol etc.), lactams (eg ε-caprolactam etc.), phenols (eg phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol, p -Nonylphenol etc.), heterocyclic hydroxyl compounds (eg 3-hydroxypyridine, 8-hydroxyquinoline etc.), active methylene compounds (eg dialkyl malonate, methyl ethyl ketoxy) , Acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.) and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  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.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a filler, a thermosetting accelerator, a thermal-polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye) etc. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tensions) You may use together a regulator, a chain transfer agent, etc.).
By appropriately containing these components, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.
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, for example, in 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, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  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 10-20,000m length 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, methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol etc. Alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, and the like ketones; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy Esters such as propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride Halogenated hydrocarbons such as monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. Is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

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 it is made into a roll shape due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. .

  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 at 30 ° C. 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 substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and is appropriately selected depending on the purpose. For example, 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. product, VP-II, Nichigo Morton Co., Ltd. product, VP130) is preferable.

  The photosensitive film and the photosensitive laminate of the present invention have a uniform film thickness and an extremely low occurrence rate of planar defects such as pinholes and repellency, so that they have excellent insulation reliability and high-definition permanent patterns (protection) Film, 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, Among these, digital exposure is preferable.

<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. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

(Printed board)
The printed circuit board of the present invention comprises at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
There is no restriction | limiting in particular as another structure, 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.

(Synthesis Example 1)
-Synthesis of binder (B-1)-
In a 1,000 mL three-necked flask, 90.6 g of 1-methoxy-2-propanol was placed and heated to 90 ° C. under a nitrogen stream. To this, 105.8 g of benzyl methacrylate and 156 g of 1-methoxy-2-propanol in 120.6 g of methacrylic acid, and 7.24 g of 1-methoxy-2-propanol in 50 g solution of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Were added dropwise over 3 hours. After completion of the dropwise addition, the reaction was further continued by heating for 1 hour. Subsequently, 2.00 g of 1-methoxy-2-propanol 20 g solution of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 1 hour. After completion of the dropwise addition, the reaction was continued by heating for 3 hours, and then the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (30/70 mol% ratio).
Next, 105.2 g of glycidyl methacrylate and 20 g of 1-methoxy-2-propanol were added to the dropping funnel, and 0.34 g of p-methoxyphenol was added to the flask, and the mixture was stirred and dissolved. After dissolution, 0.82 g of triphenylphosphine was added and heated to 100 ° C., and then glycidyl methacrylate was dropped from the dropping funnel over 1 hour to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 45.8 g of 1-methoxy-2-propanol was added. By the above, the binder (B-1) solution (solid content 45 mass%) represented by the following formula was synthesized.
The acid value of the obtained binder (B-1) was 121 mgKOH / g, and the mass average molecular weight was 31,000.

(Synthesis Example 2)
—Synthesis of Chain Transfer Agent (Exemplary Compound (R-1)) —
As raw materials, glycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) and mercaptolactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are dehydrated and condensed in a conventional manner at a molar ratio of 1: 2.2 and treated with alkaline water. Then, excess mercaptolactic acid was removed to synthesize a bifunctional mercapto compound having the mercapto group secondary (the exemplified compound (R-1) above).

(Synthesis Example 3)
—Synthesis of Chain Transfer Agent (Exemplary Compound (R-2)) —
As raw materials, trimethylolethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and mercaptolactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are dehydrated and condensed in a conventional manner at a molar ratio of 1: 3.2 and treated with alkaline water. Thus, excess mercaptolactic acid was removed to synthesize a tetrafunctional mercapto compound having the mercapto group secondary (the above exemplary compound (R-2)).

(Synthesis Example 4)
—Synthesis of Chain Transfer Agent (Exemplary Compound (R-3) —)
As raw materials, pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) and mercaptolactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are dehydrated and condensed by a conventional method at a ratio of 1: 4.3 (molar ratio) and treated with alkaline water. In this way, excess mercaptolactic acid was removed, and a tetrafunctional mercapto compound (the above exemplified compound (R-3)) having a secondary mercapto group was synthesized.

(Synthesis Example 5)
—Synthesis of Chain Transfer Agent (Exemplary Compound (R-4) above) —
As raw materials, pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-mercaptoisovaleric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are dehydrated and condensed by a conventional method at a ratio of 1: 4.3 (molar ratio). Excess 2-mercaptoisovaleric acid was removed by treatment with alkaline water to obtain a tetrafunctional halogen compound.
The resulting tetrafunctional halogen compound was reacted with potassium thioacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) in N-methylpyrrolidone at 50 ° C. After confirming the disappearance of the tetrafunctional halogen compound by thin layer chromatography, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate and concentrated. Purification by silica gel column chromatography gave a tetrafunctional thioacetic acid compound.
The obtained thioacetic acid compound was dissolved in N-methylpyrrolidone, and 6 equivalents of morpholine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted at 70 ° C. After confirming the disappearance of the tetrafunctional thioacetic acid compound by thin layer chromatography, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate and concentrated. The product was purified by silica gel column chromatography to synthesize a tetrafunctional mercapto compound (the above exemplary compound (R-4)) (yield 72%).

(Synthesis Example 6)
—Synthesis of Chain Transfer Agent (Exemplary Compound (R-5) above) —
As raw materials, pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-mercaptoisobutyric acid (manufactured by Sakai Chemical Industry Co., Ltd.) are dehydrated and condensed in a conventional manner at a ratio of 1: 4.3 (molar ratio), and alkaline water Excess 2-mercaptoisobutyric acid was removed by treatment with a tetrafunctional mercapto compound having the mercapto group secondary (the exemplified compound (R-5)).

(Synthesis Example 7)
-Synthesis of chain transfer agent (RX)-
As raw materials, pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are dehydrated and condensed by a conventional method at a ratio of 1: 4.3 (molar ratio), and alkaline water Excess 3-mercaptopropionic acid was removed by treatment with a tetrafunctional mercapto compound (chain transfer agent (RX)) having a secondary mercapto group.
<Chain transfer agent (RX)>

Example 1
-Production of photosensitive film-
On a 16 μm thick polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) as a support, a photosensitive composition solution having the following composition was applied and dried, and a 30 μm thick photosensitive film was formed on the support. A layer was 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-
-Solution of binder (B-1) of Synthesis Example 1 (solid content 45 mass%) ... 37.2 parts by mass-Polymerizable compound (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter, polymerizable compound) 11.15 mass parts Epototo YDF-170 (manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin, hereinafter referred to as thermal crosslinking agent “N-1”). 0 part by mass-Photopolymerization initiator represented by the following formula <K-1>: 1.0 part by mass <K-1>
DETX-S (manufactured by Nippon Kayaku Co., Ltd., diethylthioxanthone, hereinafter referred to as “D-1”) 0.5 parts by mass Chain transfer agent (exemplified compound (R-1)) 1 0.0 part by mass-Pigment dispersion (hereinafter referred to as "G-1") ... 36.1 parts by mass-30% by mass methyl ethyl ketone solution of MegaFac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.13 parts by mass Methyl ethyl ketone (solvent) 12.0 parts by mass The pigment dispersion (G-1) was synthesized with 30 parts by mass of silica (manufactured by Admatex Co., Ltd., SO-C2). 48.2 parts by mass of the binder (B-1) solution of Example 1, 0.51 parts by mass of phthalocyanine blue, 0.14 parts by mass of anthraquinone yellow pigment (PY24), 59.0 parts by mass of normal propyl acetate, Premixed After that, using a motor mill M-250 (manufactured by Eiger), zirconia beads having a diameter of 1.0 mm were used and dispersed for 3 hours at a peripheral speed of 9 m / s.

-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.

  The resulting laminate was evaluated for sensitivity, developability, resolution, storage stability, heat resistance, and substrate adhesion as follows. The results are shown in Table 1.

<Sensitivity>
The laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). Pattern data of L / S (line / space) = 50 μm / 50 μm was applied to the surface of the photosensitive layer of the obtained laminate using INPREX IP-3000 (manufactured by Fuji Film Co., Ltd., pixel pitch = 1.0 μm). 0.5 mJ / cm ² from being irradiated with light energy of different light at ^{2 1/2} times intervals until 500 mJ / cm ² was exposed, cured L / S (line / space) = 50 [mu] m / 50 [mu] m line pattern I let you. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. And spray development for 2 to 3 times the shortest development time (or 40 to 60 seconds) to dissolve and remove uncured areas. The line width of the L = 50 μm pattern thus obtained was measured using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 times), and the exposure amount at which the line width was 50 μm was determined with sensitivity (optimal). Exposure amount) and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Sensitivity higher than 10 mj, very excellent sensitivity ○: Sensitivity of 10 mj to 14 mj, excellent sensitivity ○ Δ: Sensitivity of 14 mj to 20 mj, good sensitivity Δ: 20 mj to 40 mj Sensitivity is slightly inferior x: Sensitivity is lower than 40 mj and sensitivity is inferior

<Developability (shortest development time)>
The polyethylene terephthalate film (support) is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time and evaluated according to the following criteria. The shorter the shortest development time, the better the developability.
〔Evaluation criteria〕
○: Development time is 20 seconds or less and developability is good Δ: Development time is 30 seconds or less and developability is slightly inferior ×: Development time is 30 seconds or more and developability is inferior

<Evaluation of resolution>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, exposure is performed so that a round hole having a diameter of 50 to 200 μm can be formed using a round hole pattern using the pattern forming apparatus. went.
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation. 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 the developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve the uncured region. Removed.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, there is no residue at the bottom of the round hole of the pattern, there are no abnormalities such as blistering / peeling of the pattern, and space The minimum round hole pattern width that can be formed was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution.
〔Evaluation criteria〕
○: A round hole with a diameter of 120 μm or less is resolvable, and the resolution is good. Δ: A round hole with a diameter of 200 μm or less is resolvable, and the resolution is slightly inferior. Inferior resolution

<Storage stability>
The photosensitive film was stored at 40 ° C. for 5 days. The laminate was laminated on a copper clad laminate, and the shortest development time _tr was measured. The smaller the ratio r = t _r / t ₀ to the shortest development time t ₀ before storage, the better the storage stability.
〔Evaluation criteria〕
○: r is 1.5 or less and excellent in storage stability ○ Δ: r is 2.0 or less and storage stability is good Δ ×: r is 2.5 or less and storage stability Slightly inferior ×: r is 2.5 or more and inferior in storage stability

<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 swelling, peeling, and discoloration of the resist layer due to were evaluated according to the following criteria.
〔Evaluation criteria〕
○: No change is observed and heat resistance is excellent. Δ: Although some swelling and peeling are observed, heat resistance is good. ×: The coating film is swollen and peeled.

<Board adhesion>
A solder resist layer made of each photosensitive composition was formed on the substrate. The inside of a 1 cm square section was divided by lines with 1 mm vertical and horizontal intervals, and only the film was cut with a cutter knife so that 100 1 mm square sections could be formed, and cut so as not to cut the substrate. Next, a cellophane tape (product name cellophane tape No. 29, manufactured by Nitto Denko Corporation) was applied to the cut film, and the film was pulled up to an angle of 90 degrees, and at that time, how many 1 mm square sections were peeled off was measured. . One having no peeling and no defect in each section is good. The peelability and defect were evaluated according to the following criteria.
〔Evaluation criteria〕
○: No peeling / defects and excellent substrate adhesion △: No peeling, but some defects and slightly inferior to substrate adhesion ×: Partial peeling occurs, resulting in poor substrate adhesion

(Example 2)
Except having changed the chain transfer agent (the said exemplary compound (R-1)) in the photosensitive composition solution of Example 1 into the chain transfer agent (the above exemplary compound (R-2)), it was carried out similarly to Example 1. , Photosensitive films, laminates, and permanent patterns were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

(Example 3)
Except having changed the chain transfer agent (the said exemplary compound (R-1)) in the photosensitive composition solution of Example 1 into the chain transfer agent (the above exemplary compound (R-3)), it was carried out similarly to Example 1. , Photosensitive films, laminates, and permanent patterns were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

Example 4
Except having changed the chain transfer agent (the said exemplary compound (R-1)) in the photosensitive composition solution of Example 1 into the chain transfer agent (the above exemplary compound (R-4)), it was carried out similarly to Example 1. , Photosensitive films, laminates, and permanent patterns were produced.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

(Example 5)
Example 1 except that the photopolymerization initiator represented by the above formula <K-1> in the photosensitive composition solution of Example 1 was changed to a photopolymerization initiator represented by the following formula <K-2>. 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 sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.
<K-2>

(Example 6)
The photopolymerization initiator represented by the above formula <K-1> in the photosensitive composition solution of Example 1 was changed to a photopolymerization initiator represented by the above formula <K-2>, and a chain transfer agent (above exemplified) A photosensitive film, a laminate, and a permanent pattern were produced in the same manner as in Example 1 except that the compound (R-1) was changed to a chain transfer agent (the above exemplary compound (R-3)).
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

(Example 7)
The photopolymerization initiator represented by the above formula <K-1> in the photosensitive composition solution of Example 1 was changed to a photopolymerization initiator represented by the above formula <K-2>, and a chain transfer agent (above exemplified) A photosensitive film, a laminate, and a permanent pattern were produced in the same manner as in Example 1 except that the compound (R-1) was changed to a chain transfer agent (the exemplified compound (R-4)).
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

(Example 8)
The photopolymerization initiator represented by the above formula <K-1> in the photosensitive composition solution of Example 1 was changed to a photopolymerization initiator represented by the following formula <K-3>, and a chain transfer agent (above exemplified) A photosensitive film, a laminate, and a permanent pattern were produced in the same manner as in Example 1 except that the compound (R-1) was changed to a chain transfer agent (the exemplified compound (R-4)).
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.
<K-3>

Example 9
The photopolymerization initiator represented by the above formula <K-1> in the photosensitive composition solution of Example 1 was changed to a photopolymerization initiator represented by the above formula <K-2>, and a chain transfer agent (above exemplified) A photosensitive film, a laminate, and a permanent pattern are produced in the same manner as in Example 1 except that the compound (R-1) is changed to a chain transfer agent (the above exemplary compound (R-5); Synthesis Example 6). did.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

(Comparative Example 1)
A photosensitive film, a laminate, and a permanent pattern were produced in the same manner as in Example 1 except that the chain transfer agent (the above exemplary compound (R-1)) in the photosensitive composition solution of Example 1 was not added. .
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

(Comparative Example 2)
The photopolymerization initiator represented by the above formula <K-1> in the photosensitive composition solution of Example 1 was changed to a photopolymerization initiator represented by the following formula (K-4), and a chain transfer agent (illustrated above). A photosensitive film, a laminate, and a permanent pattern were obtained in the same manner as in Example 1 except that the compound (R-1)) was changed to the chain transfer agent represented by the above formula (RX; Synthesis Example 7). Manufactured.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.
<K-4>

(Comparative Example 3)
The photopolymerization initiator represented by the above formula <K-1> in the photosensitive composition solution of Example 1 was changed to a photopolymerization initiator represented by the above formula (K-3), and a chain transfer agent (illustrated above). The compound (R-1)) is changed to a chain transfer agent (the above exemplary compound (R-3)), and the photosensitive film, laminate, and permanent are the same as in Example 1 except that no thermal crosslinking agent is added. A pattern was manufactured.
About the obtained laminated body, it carried out similarly to Example 1, and evaluated sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.

(Comparative Example 4)
Except having changed the chain transfer agent (the said exemplary compound (R-1)) in the photosensitive composition solution of Example 1 into the chain transfer agent (RY, Showa Denko Co., Ltd.) represented by the following formula. In the same manner as in Example 1, 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 sensitivity, developability, resolution, storage stability, heat resistance, and board | substrate adhesiveness. The results are shown in Table 1.
<R-Y>

From the result of Table 1, Examples 1-9 are excellent in sensitivity, developability, and resolution compared with Comparative Examples 1-4, and also improve storage stability, heat resistance, and board | substrate adhesiveness together. I found out that

The photosensitive composition of the present invention enables high sensitivity and negative patterning, is excellent in sensitivity, developability, and resolution, and can further improve both storage stability, heat resistance, and substrate adhesion. Therefore, it can be suitably used for a film-type solder resist that requires particularly high storage stability.
Since the photosensitive film of the present invention has improved heat resistance and storage stability and can efficiently form a high-definition permanent pattern, various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern It can be suitably used for forming liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., particularly for forming permanent patterns on printed circuit boards. be able to.
Since the pattern forming method of the present invention uses the photosensitive composition, it is used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of permanent patterns on printed boards.

Claims (11)

A binder, a polymerizable compound, a photopolymerization initiator, a chain transfer agent, and a thermal crosslinking agent;
The said chain transfer agent is a compound represented by the following general formula (A), The photosensitive composition characterized by the above-mentioned.
However, in the general formula (A), R ₁ and R ₂ both represent a hydrogen atom and an organic functional group, and at least one of R ₁ and R ₂ represents an organic functional group, R ₁ and R ₂ may form a ring. Y represents either an oxygen atom or a sulfur atom. n represents 2 to 8, and Z represents an n-functional organic linking chain. The photosensitive composition according to claim 1, wherein the chain transfer agent is an ester or thioester of a compound represented by the following general formula (B).
However, in said general formula (B), R < ₁ > and R < ₂ > represent the same meaning as the said general formula (A).   The photosensitive composition according to claim 1, wherein the binder is a polymer compound having at least one ethylenically unsaturated double bond in the side chain.   The photosensitive composition according to any one of claims 1 to 3, wherein the binder is a polymer compound having at least one ethylenically unsaturated double bond and a carboxyl group in the side chain.   The photosensitive composition according to claim 1, wherein the photopolymerization initiator is a neutral photopolymerization initiator.   The photosensitive composition according to any one of claims 1 to 5, wherein the photopolymerization initiator is a neutral oxime ester compound.   The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The photosensitive composition as described.   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 the photosensitive layer formed of the photosensitive composition according to claim 1.   A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 10.