JP4874767B2 - Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board - Google Patents

Description

  The present invention relates to a photosensitive composition capable of efficiently forming a high-definition permanent pattern, a photosensitive film, a method for forming a permanent pattern, and a printed board.

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

In the photosensitive composition for forming the solder resist, a high molecular weight modified epoxy resin is used as a binder, and it is used for a rigid substrate having high thermal shock resistance and storage stability in a film state (Patent Document 1). And a photosensitive composition for forming a solder resist in dry film applications (see Patent Document 2 and Patent Document 3) has been proposed. However, since these proposed photosensitive compositions have low sensitivity, there has been a problem that when digital imaging (DI) exposure is performed, this takes a lot of time and productivity is poor.
Therefore, in order to increase productivity when performing digital imaging (DI) exposure, the photosensitivity suitable for film curability in a blue-violet laser having a wavelength of about 405 nm is used as a highly sensitive photopolymerization initiator. A composition has been proposed (see Patent Document 4). However, this proposal has a problem in that it is difficult to prepare a photosensitive composition in advance and use it as necessary, because the sensitivity is not stable over time.

  Therefore, a photosensitive composition, a photosensitive film, and a photosensitive film that have high sensitivity and high resolution, have good sensitivity over time, film curability, and thermal shock resistance, and can efficiently form a high-definition permanent pattern. At present, it is desired to develop a permanent pattern forming method using a conductive composition and a printed circuit board on which a pattern is formed by the permanent pattern forming method.

JP 2006-208835 A JP 2006-208824 A JP 2006-208553 A JP 2005-182004 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is a photosensitive composition, photosensitivity, high sensitivity, high resolution, good sensitivity over time, film curability, and thermal shock resistance, and capable of efficiently forming a high-definition permanent pattern. An object is to provide a film, a permanent pattern forming method using the photosensitive composition, and a printed board on which a pattern is formed by the permanent pattern forming method.

Means for solving the problems are as follows. That is,
<1> A binder, a polymerizable compound, and a photopolymerization initiator, wherein the binder includes a modified epoxy resin having a repeating unit represented by the following general formula (I), and the photopolymerization initiator includes an oxime compound. It is the photosensitive composition characterized by the above-mentioned.
In the general formula (I), R ¹ represents a divalent organic group which is a diglycidyl ether type epoxy compound residue, R ² represents a divalent organic group which is a dibasic acid residue radical, R ³ represents a hydrogen atom or the following general formula (i).
In the general formula (i), R ⁴ represents an acid anhydride residue.
<2> The modified epoxy resin having a repeating unit represented by the general formula (I) is the photosensitive composition according to the above <1> represented by the following general formula (II).
In the general formula ^(II), R 1 ~R ³ denote the same meaning as the general formula (I).
<3> An intermediate production step in which the modified epoxy resin obtains an intermediate by a polymerization reaction of a diglycidyl ether type epoxy compound and a dibasic acid, an acid anhydride addition step in which an acid anhydride is added to the intermediate, It is the photosensitive composition in any one of said <1> to <2> obtained through this.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the oxime compound is a compound having at least an aromatic group.
<5> The above-mentioned <1>, wherein the oxime compound has a partial structure represented by any one of the following general formula (III) and general formula (IV), or is a compound represented by the following general formula (V): To <4>.
However, in said general formula (III) and (IV), Ar represents either an aromatic group or a heterocyclic group. Y ¹ represents any ^one of a hydrogen atom and a monovalent substituent, and Y ² represents any one of an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , and CONY ⁴ Y ^5. . Y ³ , Y ⁴ , and Y ^{5 each} represent an aliphatic group, an aromatic group, or a heterocyclic group. m represents an integer of 1 or more.
However, in said general formula (V), R < ¹ > represents either the acyl group, alkoxycarbonyl group, and aryloxycarbonyl group which may have a substituent. m represents an integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.
<6> The photosensitive composition according to <5>, wherein Ar in the general formula (III) and the general formula (IV) has either a phenyl group or a naphthyl group.
<7> The photosensitive composition according to any one of <5> to <6>, wherein Ar in the general formula (III) and the general formula (IV) has any one of naphthyl groups.
<8> The photosensitive composition according to any one of <5> to <7>, wherein the general formula (III) is further represented by any one of the following general formula (VI) and general formula (VII): .
However, the general formula (VI) and the general formula _{(VII), R 101} represents the same meaning as ^{Y 1} in the general formula (III) and the general formula ^{(IV), Y 12} is the general formula (III) and the general formula This represents the same meaning as Y ² in (IV).
The compound represented by <9> General formula (V) is a photosensitive composition as described in said <5> further represented by the following general formula (VIII).
However, in said general formula (VIII), R < ¹ >, R < ² >, m, and Ar represent the same meaning as in general formula (V). X represents either O or S. A represents either a 5- or 6-membered ring.
<10> The photosensitive composition according to <9>, wherein the compound represented by the general formula (VIII) is further represented by any one of the following general formula (IX) and general formula (X).
However, R < ³ > represents the alkyl group which may have a substituent in the said general formula (IX) and general formula (X). l represents an integer of 0 to 6. R ⁴ represents any one of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group. When l is 2 or more, the R ⁴ may be the same or different. It may be. X and A represent the same meaning as in the general formula (VIII).

<11> The photosensitive composition according to any one of <1> to <10>, wherein the polymerizable compound includes at least one selected from monomers having a (meth) acryl group.
<12> The photosensitive composition according to any one of <1> to <11>, including a thermal crosslinking agent.
<13> The thermal crosslinking agent according to <12>, 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. Of the photosensitive composition.
<14> The thermal crosslinking agent includes an epoxy compound, and the epoxy compound is at least one selected from a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic group-containing type epoxy resin, and a poorly soluble epoxy resin. <13> The photosensitive composition according to <13>.
<15> The photosensitive composition according to any one of <1> to <14>, including a sensitizer.
<16> The photosensitive composition according to <15>, wherein the sensitizer includes a hetero-fused ring compound.
<17> The photosensitive composition according to <16>, wherein the hetero-fused ring compound is a thioxanthone compound.
<18> The photosensitive composition according to any one of <1> to <17>, including a filler.

<19> A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <18> on a support.
<20> The photosensitive film according to <19>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<21> The photosensitive film according to any one of <19> to <20>, wherein the support includes a synthetic resin and is transparent.
<22> The photosensitive film according to any one of <19> to <21>, wherein the support has an elongated shape.
<23> The photosensitive film according to any one of <19> to <22>, which is long and wound in a roll.
<24> The photosensitive film according to any one of <19> to <23>, which has a protective film on the photosensitive layer.

<25> A method for forming a permanent pattern, comprising exposing the photosensitive layer formed of the photosensitive composition according to any one of <1> to <18>.
<26> The method for forming a permanent pattern according to <25>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <19> to <24>.
<27> The method for forming a permanent pattern according to any one of <25> to <26>, wherein the exposure is performed without using a photomask.
<28> The method for forming a permanent pattern according to <27>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
<29> Exposure is emitted from the light irradiation unit to the photosensitive layer while moving at least one of the exposure head including at least a light irradiation unit and a light modulation unit, and the photosensitive layer. The permanent pattern forming method according to any one of <27> to <28>, wherein the light is irradiated from the exposure head while modulating light according to pattern information by the light modulation means.
<30> The light modulation unit is capable of controlling any less than n pixel elements arranged continuously from n pixel elements in accordance with pattern information. This is a permanent pattern forming method.
<31> The method for forming a permanent pattern according to any one of <29> to <30>, wherein the light modulator is a spatial light modulator.
<32> The method for forming a permanent pattern according to <31>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<33> The permanent pattern forming method according to any one of <29> to <32>, wherein the exposure is performed through an aperture array.
<34> The permanent pattern forming method according to any one of <29> to <33>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<35> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams irradiated from the plurality of lasers to the multimode optical fiber. The permanent pattern forming method according to any one of <29> to <34>.
<36> The method for forming a permanent pattern according to any one of <25> to <35>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 420 nm.

<37> The method for forming a permanent pattern according to any one of <25> to <36>, wherein the photosensitive layer is developed after the exposure.
<38> The method for forming a permanent pattern according to <37>, wherein a permanent pattern is formed after development.

<39> A permanent pattern formed by the method for forming a permanent pattern according to any one of <25> to <38>.
<40> The permanent pattern according to <39>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.

  <41> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to any one of <25> to <38>.

  The photosensitive composition of this invention contains a binder, a polymeric compound, and a photoinitiator, the said binder contains a specific modified epoxy resin, and the said photoinitiator contains an oxime compound. For this reason, it has high sensitivity and high resolution, has good sensitivity over time, film curability, and thermal shock resistance, and can efficiently form a high-definition permanent pattern.

  According to the present invention, conventional problems can be solved, high sensitivity and high resolution, sensitivity stability over time, film curability and thermal shock resistance are good, and high-definition permanent patterns are efficiently formed. A possible photosensitive composition, a photosensitive film, a permanent pattern forming method using the photosensitive composition, and a printed board on which a pattern is formed by the permanent pattern forming method can be provided.

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

〔binder〕
As the binder, a modified epoxy resin having a repeating unit represented by the following general formula (I) is used. The modified epoxy resin is a polyester resin having an ester bond (—COO—) in the main chain, as is apparent from the following general formula (I).
In the general formula (I), R ¹ represents a divalent organic group which is a diglycidyl ether type epoxy compound residue, R ² represents a divalent organic group which is a dibasic acid residue radical, R ³ represents a hydrogen atom or the following general formula (i).
In the general formula (i), R ⁴ represents an acid anhydride residue.

The modified epoxy resin having a repeating unit represented by the general formula (I) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the modified epoxy resin represented by the following general formula (II) Is mentioned.
In the general formula ^(II), R 1 ~R ³ denote the same meaning as the general formula (I).

  The molecular weight of the modified epoxy resin is 10 in terms of mass average molecular weight from the viewpoint of coating properties (difficulty in stickiness), developability with a dilute aqueous alkali solution, and mechanical properties such as tensile strength and elongation. It is preferably 8,000 to 80,000, more preferably 15,000 to 70,000, still more preferably 20,000 to 60,000, and 25,000 to 50,000. Is particularly preferred.

The photosensitive composition of the present invention can be sufficiently dissolved in a dilute alkali developer even if it contains a relatively high molecular weight modified epoxy resin. In particular, the solubility of the modified epoxy resin tends to improve as the amount of the linear polyester resin represented by the general formula (II) increases. Moreover, when the modified epoxy resin contains a large amount of linear polyester resin, various properties such as solubility of the photosensitive composition in a solvent tend to be improved.
In the structural formula of the modified epoxy resin represented by the general formula (II) described above, the upper limit value of n varies depending on the types of residues of R ¹ , R ² , R ³ , and R ⁴ . It is preferable to set the value of n as the upper limit such that the mass average molecular weight is 80,000.

Here, the said mass mean molecular weight can be measured on the following gel permeation chromatograph (GPC) conditions, for example.
GPC condition pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Detector: Hitachi L-4000 UV [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-S300MDT-5 (two in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Column size: 8mmφ × 300mm
Eluent: DMF / THF = 1/1 + phosphoric acid 0.06M + lithium bromide 0.06M
Sample concentration: 5 mg / 1 mL
Injection volume: 5 μL
Pressure: 343 Pa (35 kgf / cm ² )
Flow rate: 1.0 mL / min

  The acid value of the epoxy-modified resin is preferably 50 to 200 mgKOH / g from the viewpoints of developability with a dilute aqueous alkali solution and from the viewpoints of electrical insulation, chemical resistance and plating resistance of the resulting cured film. 90 to 150 mgKOH / g is more preferable.

The acid value of the epoxy-modified resin can be measured, for example, by the following method.
First, about 1 g of a polyester resin solution is precisely weighed, 30 g of acetone is added to the resin solution, and the resin solution is uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. Then, the acid value is calculated from the titration result using the following formula.
Formula A = 10 × Vf × 56.1 / (Wp × I)
In the above formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of phenolphthalein, Wp represents the mass (g) of the polyester resin solution, and I represents the polyester resin solution. Represents the ratio (% by mass) of the non-volatile content.

  5-80 mass% is preferable and, as for solid content content in the said photosensitive composition of the said binder, 10-70 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 80% by mass, the exposure sensitivity is increased. May decrease.

<Synthesis method>
The method for synthesizing the modified epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the modified epoxy resin is synthesized by an intermediate production step and an acid anhydride addition step. A method is mentioned.

-Intermediate production process-
The intermediate generation step is a step of obtaining an intermediate by a polymerization reaction between a diglycidyl ether type epoxy compound having two glycidyl groups in one molecule and a dibasic acid.
The diglycidyl ether type epoxy compound is not particularly limited, but preferably has one or more phenoxy groups in one molecule, and further has two or more phenoxy groups in one molecule. More preferred.

Examples of the diglycidyl ether type epoxy compound include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, and bisphenol S type epoxy resins such as bisphenol S diglycidyl ether. , Biphenol type epoxy resins such as biphenol diglycidyl ether, bixylenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, and their dibasic acid-modified diesters Examples thereof include glycidyl ether type epoxy resins. Among these, bisphenol A type epoxy resins are preferable because they are excellent in heat resistance and chemical resistance and do not relatively shrink due to curing. The said diglycidyl ether type epoxy compound may be used individually by 1 type, and may use 2 or more types together.
In addition, the diglycidyl ether type epoxy compound residue represented by R ¹ in the general formula (I) described above is a portion excluding the glycidyl group in the structure of these epoxy compounds.

A commercially available product may be used as the diglycidyl ether type epoxy compound. As said commercial item, what is shown below is mentioned, for example.
(1) Bisphenol A diglycidyl ether Epicoat 828, Epicoat 1001, Epicoat 1002 (above, product name manufactured by Japan Epoxy Resin Co., Ltd.) (2) Bisphenol F diglycidyl ether Epicoat 807 (product name manufactured by Japan Epoxy Resin Co., Ltd.) (3) Bisphenol S diglycidyl ether EBPS-200 (Nippon Kayaku Co., Ltd., trade name), Epicron EXA-1514 (Dainippon Ink Chemical Co., Ltd., trade name), etc. (4) Biphenol diglycidyl ether YL6121 (Japan) (5) Bixylenol diglycidyl ether YX4000 (Japan Epoxy Resin, trade name), etc. (6) Hydrogenated bisphenol A glycidyl ether ST-2004, ST-2007 Tohto Kasei Co., Ltd., trade name), etc. (7) a dibasic acid modified diglycidyl ether type epoxy resin ST-5100, ST-5080 (or, Tohto Kasei Co., Ltd., trade name), etc.

The epoxy equivalent of the diglycidyl ether type epoxy compound is preferably 160 to 3,300, and more preferably 180 to 980, from the viewpoint of developability with a dilute aqueous alkali solution.
The epoxy equivalent can be measured, for example, by determining the gram mass of the compound containing 1 equivalent of the epoxy group according to JIS K 7236 “How to determine the epoxy equivalent of an epoxy resin”.

Although there is no restriction | limiting in particular as said dibasic acid, For example, dicarboxylic acid is mentioned suitably. Examples of the dicarboxylic acid include maleic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and methylendomethylenetetrahydrophthalic acid, Etc. Among these, tetrahydrophthalic acid is preferable. The dibasic acid may be used alone or in combination of two or more.
In addition, the dibasic acid residue represented by R ² in the general formula (I) described above is a portion excluding a dibasic acid functional group (a carboxyl group in the case of dicarboxylic acid) in the structure of these compounds. Become.

  There is no restriction | limiting in particular in the polymerization reaction in the said intermediate body production | generation process, It can carry out by a conventional method. The compounding ratio of the diglycidyl ether type epoxy compound and the dibasic acid is functional, from the viewpoint of the molecular weight of the polyester resin, the viewpoint of developability with a dilute alkaline aqueous solution, the viewpoint of storage stability, and the viewpoint of coating properties. The group equivalent ratio (carboxyl group / epoxy group, molar ratio) is preferably 1.03 to 1.30. By adjusting the blending ratio of the diglycidyl ether type epoxy compound and the dibasic acid in this way, the carboxyl group becomes excessive with respect to the epoxy group, so that the resulting modified epoxy resin is at the end. It tends to have a carboxyl group.

Examples of the catalyst used in the polymerization reaction include phosphines, alkali metal compounds, amines, and the like.
Specifically, for example, phosphines such as tributylphosphine and triphenylphosphine, alkali metal compounds such as sodium hydroxide, lithium hydroxide and potassium hydroxide, triethanolamine, N, N′-dimethylpiperazine, triethylamine , Tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide, and the like. These may be used individually by 1 type and may use 2 or more types together.

  As the catalyst, among the above-described compounds, a tertiary amine having a pKa of 9.0 or less is preferable, and a tertiary amine having a pKa of 7.3 or less is more preferable. By using such a catalyst, finally, the epoxy-modified resin represented by the general formula (I) and the general formula (II) described above can be synthesized more selectively. The molecular weight of the epoxy-modified resin Tend to be larger. Among the specific catalysts described above, from the viewpoint of preventing gelation due to bond types in the resulting epoxy-modified resin, that is, ether type network bonds and ester type network bonds, phosphines, alkalis It is preferable to use one other than a metal compound or a tertiary amine having a pKa of 9.0 or less.

  The intermediate produced by the polymerization reaction has, in its molecule, a chain structure by an ester bond produced by a reaction between a carboxyl group and a glycidyl group, a network structure by an ether bond produced by a reaction between a hydroxyl group and a glycidyl group, and A network structure can be formed by ester bonds formed by the reaction between a hydroxyl group and a carboxyl group. When the obtained intermediate has a large number of network structures based on ether bonds and network structures based on ester bonds among these structures, it is considered that the resulting intermediate tends to form a three-dimensional structure as a whole. Accordingly, since the intermediate product and the modified epoxy resin obtained after the acid anhydride step described later tend to gel, the uncured portion of the resist film formed by using such a resin is diluted with a dilute alkali. It tends not to be removed even by development using an aqueous solution or the like.

  On the other hand, the intermediate synthesized by using the above-described catalyst is further subjected to an acid anhydride step using the intermediate, thereby starting from those represented by the general formula (I), and by an ester bond in the molecule. Since a polyester resin having a lot of chain bonds and a chain structure as a whole can be obtained, it is considered that gelation tends to be difficult. Therefore, the uncured portion of the permanent pattern formed by using such a polyester resin is easily removed by development using a dilute alkaline aqueous solution or the like.

  The reaction temperature in the intermediate production step is preferably 100 to 150 ° C. from the viewpoint of the polymerization reaction rate and the prevention of the side reaction.

  The amount of the catalyst used is the diglycidyl ether type epoxy compound and the dibasic acid from the viewpoints of the polymerization reaction rate and the heat resistance and electric corrosion resistance of the cured film obtained from the photosensitive resin composition. It is preferable that it is 1-10 mass parts with respect to 100 mass parts of total amount.

-Acid anhydride addition step-
The acid anhydride addition step is a step of adding an acid anhydride to the intermediate produced by the intermediate production step.
The acid anhydride is not particularly limited. For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, anhydrous Dibasic acid anhydrides such as endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride Aromatic polyvalent carboxylic acid anhydrides such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride And polyvalent carboxylic acid anhydride derivatives. Among these, dibasic acid anhydrides are preferable, and dicarboxylic acid anhydrides are more preferable. The said acid anhydride may be used individually by 1 type, and may use 2 or more types together.
In addition, the acid anhydride residue represented by R ⁴ in the general formula (I) described above is a portion excluding the acid anhydride functional group in the structure of these compounds.

  The reaction temperature in the acid anhydride addition step is preferably 80 to 130 ° C. from the viewpoint of reaction rate and the prevention of side reactions.

  The addition amount of the acid anhydride is equivalent to a functional group equivalent ratio (acid anhydride to be added from the viewpoint of developability with a dilute alkaline aqueous solution, the heat resistance of the finally obtained cured film, and the resistance to electrical corrosion resistance). Middle acid anhydride group / hydroxyl group of intermediate product produced in the first step, molar ratio) is preferably 0.6 to 1.3.

  In the method for synthesizing the epoxy-modified resin, an appropriate amount of solvent is usually used. Specific examples of the solvent include ketone compounds such as methyl isobutyl ketone, cyclohexanone, and methylcyclohexanone, aromatic hydrocarbon compounds such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, and carbonic acid. Toluene, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Ester compounds, ethylene glycol, propylene glycol, alcohol compounds such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, sol Ntonafusa, petroleum solvents, etc., and the like.

(Photopolymerization initiator)
An oxime compound is used as the photopolymerization initiator. Moreover, you may contain another photoinitiator as needed.

<Oxime compound>
The oxime compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferably a compound having at least an aromatic group, and any one of the following general formulas (III) and (IV) More preferably, the compound has a partial structure represented by Two or more oxime compounds may be used in combination.

However, in said general formula (III) and (IV), Ar represents either an aromatic group or a heterocyclic group. Y ¹ represents any ^one of a hydrogen atom and a monovalent substituent, and Y ² represents any one of an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , and CONY ⁴ Y ^5. . Y ³ , Y ⁴ , and Y ^{5 each} represent an aliphatic group, an aromatic group, or a heterocyclic group. m represents an integer of 1 or more.

Y ¹ is preferably a hydrogen atom, an aliphatic group, or an aromatic group.
Y ² includes an aliphatic group, —CO— (aliphatic group), —CO— (aromatic group), —CO— (heterocyclic group), —CO ₂ — (aliphatic group), —CO _2. - (aromatic group), and -CO ₂ - is preferably any one of (heterocyclic group).
Y ³ and Y ⁴ are preferably either an aliphatic group or an aromatic group.

  The oxime compound may be a compound in which a plurality of structures represented by the general formula (III) and the general formula (IV) are bonded through a linking group.

  In the general formula (III) and general formula (IV), the aliphatic group represents an alkyl group, an alkenyl group, and an alkynyl group, each of which may have a substituent, and the aromatic group is Represents an aryl group or a heterocyclic (heterocyclic) group which may have a substituent. Examples of the monovalent substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, and a hydroxyl group. , An ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group, each representing an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group.

Examples of the aromatic group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, Examples thereof include a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among them, a group having any one of a phenyl group and a naphthyl group is preferable, and a group having a naphthyl group is particularly preferable.
In addition, these aromatic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Examples of the group composed of a monovalent non-metallic atomic group excluding the hydrogen atom include those described below as a substituent in an alkyl group, a substituted alkyl group, or a substituted alkyl group.

The heterocyclic (heterocyclic) group includes a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, and an isothiazole ring. Group, indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, Quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring group, purine ring group, Pyran ring group, piperidine ring group, piperazine ring group, morpholine ring group, India Ring group, indolizine ring group, chromene ring group, cinnoline ring group, acridine ring group, phenothiazine ring group, tetrazole ring group, triazine ring group, etc., among which furan ring group, thiophene ring group, imidazole ring group , Thiazole ring group, benzothiazole ring group, pyridine ring group, indole ring group, and acridine ring group are particularly preferable.
Moreover, these heterocyclic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Examples of the group composed of a monovalent non-metallic atomic group excluding the hydrogen atom include those shown as the substituents in the alkyl group, substituted alkyl group, and substituted alkyl group described below.

  Examples of the monovalent substituent include a halogen atom, an amino group that may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a hydrogen atom is preferred.

  In addition, the monovalent substituent composed of the nonmetal atom is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent.

  Examples of the alkyl group that may have a substituent include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl A group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group Can do. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

Examples of the substituent of the alkyl group which may have a substituent include a substituent composed of a monovalent nonmetallic atom excluding a hydrogen atom, and preferable examples include a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcal Moyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diary Ru-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl- N-arylcarbamoyl group, al Killsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N— Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group _(-PO 3 _{H 2)} and its conjugated base group (a phosphonato group Referred), a dialkyl phosphono group _(-PO 3 _{(alkyl) 2)} "alkyl = alkyl group, hereinafter the" diarylphosphono group _(-PO 3 _{(aryl) 2)} "aryl = aryl group, hereinafter the" alkyl An arylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as an alkylphosphonato group), a monoarylphosphono group (— PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO) ₃ H _{(alkyl) 2),} diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl Suhonookishi group _(-OPO 3 (alkyl) (aryl)), monoalkyl phosphono group _(-OPO 3 H (alkyl)) and (referred to as alkylphosphonato group) a conjugate base group thereof, monoarylphosphono group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. , Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group , Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylpheny Group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphate Hona preparative phenyl group.

Examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of the alkynyl group in the substituent Examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
Examples of the silyl group in the substituent include a trimethylsilyl group.
The substituent may include an acyl group (R ⁰¹ CO—), and examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the above alkyl group, or an aryl group.

Examples of R ⁰¹ of the acyl group (R ⁰¹ CO—) include a hydrogen atom, and the alkyl group and aryl group. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-aryl sulf Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatooxy group, an aryl group, and an alkenyl group.

  On the other hand, the alkylene group in the substituted alkyl group includes a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms, Examples thereof include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group , A naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
As the substituted aryl group, those having a group consisting of a monovalent non-metallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group described above are used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples include methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, and 3-butynylphenyl group.

Examples of the alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group (-C (R ⁰² ) = C (R ⁰³ ) (R ⁰⁴ ) and -C≡C (R ⁰⁵ )) include R ^{A group in which 02} , R ⁰³ , R ⁰⁴ and R ⁰⁵ are monovalent non-metallic atoms can be used.
R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and specific examples thereof are shown in the above examples. Things. Among these, a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms are more preferable.
Specifically, vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenylethynyl group and the like.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted oxy group (R ⁰⁶ O—), a group in which R ⁰⁶ is a group composed of a monovalent nonmetallic atom excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy, aryloxy, acyloxy, carbamoyloxy, N-alkylcarbamoyloxy, N-arylcarbamoyloxy, N, N-dialkylcarbamoyloxy, N, N-diarylcarbamoyloxy. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy, phenylsulfonyloxy group, a phosphonooxy groups, phosphonatooxy group, and the like.

As the substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Can be used. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group in these groups include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. R ⁰⁷ of the acyl group (R ⁰⁷ CO-) is as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —), those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group can be used. More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

As described above, the sulfonate group (—SO ₃ ^— ) means a conjugated base anion group of the sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

As the substituted carbonyl group (R ⁰¹³ —CO—), a group in which R ⁰¹³ is a monovalent nonmetallic atom can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—), a group in which R ⁰¹⁴ is a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups. Preferred examples include the above-mentioned dialkylphosphono group, diarylphosphono group, and alkylaryl. Examples thereof include a phosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

As described above, the phosphonato group (—PO ₃ H ₂ ^— , —PO ₃ H ⁻ ) is a conjugate base anion derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). An ionic group is meant. Usually, it is preferable to use it with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

The substituted phosphonate group is a conjugated base anion group obtained by substituting one organic hydroxyl group with an organic oxo group among the aforementioned substituted phosphono groups. Specific examples thereof include the aforementioned monoalkylphosphono group (—PO ₃ H (Alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

As said oxime compound, the compound represented by either the following general formula (VI) or general formula (VII) is still more preferable.
However, the general formula (VI) and the general formula _{(VII), R 101} represents the same meaning as ^{Y 1} in the general formula (III) and the general formula ^{(IV), Y 12} is the general formula (III) and general This represents the same meaning as Y ² in formula (IV).

As R ₁₀₁ , either a hydrogen atom or an aliphatic group is more preferable, and an aliphatic group having 1 to 10 carbon atoms is particularly preferable.
Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, an octyl group, and an allyl group.
Y ¹² is particularly preferably —CO— (aliphatic group). The aliphatic group in Y ¹² is preferably an aliphatic group having 1 to 10 carbon atoms.
Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclohexyl group, a benzyl group and the like are preferable.

  Other specific examples of the oxime compound include, for example, compounds disclosed in JP-A No. 2001-233842, JP-A No. 2004-534797, JP-A No. 2002-519732, and the following structural formula The compound etc. which are represented by these are mentioned. Examples of commercially available products include Irgacure OXE01 (manufactured by Ciba Specialty Chemicals).

In the above structural formula, R represents any one of n-C ₃ H ₇ , n-C ₈ H ₁₇ , camphor, and p-CH ₃ C ₆ H ₄ .

In the above structural formula, R represents either nC ₃ H ₇ or p-CH ₃ C ₆ H ₄ .

As said oxime compound, the oxime compound represented by the following general formula (V) is also used suitably.
However, in said general formula (V), R < ¹ > represents either the acyl group, alkoxycarbonyl group, and aryloxycarbonyl group which may have a substituent. m represents an integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.

Among the oxime compounds represented by the general formula (V), compounds represented by the following general formula (VIII) are more preferable, and compounds represented by any one of the following general formulas (IX) and (X) are particularly preferable. preferable.
However, in said general formula (VIII), R < ¹ >, R < ² >, m, and Ar represent the same meaning as in general formula (V). X represents either O or S. A represents either a 5- or 6-membered ring.
However, R < ³ > represents the alkyl group which may have a substituent in the said general formula (IX) and general formula (X). l represents an integer of 0 to 6. R ⁴ represents any one of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group. When l is 2 or more, the R ⁴ may be the same or different. It may be. X and A represent the same meaning as in the general formula (VIII).

In the general formulas (V) and (VIII), the acyl group represented by R ¹ may be aliphatic, aromatic, or heterocyclic, and may further have a substituent.
Examples of the aliphatic acyl 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 acyl group include a benzoyl group, a naphthoyl group, a methoxybenzoyl group, and a nitrobenzoyl group. Examples of the heterocyclic acyl group include a furanoyl group and a thiophenoyl group. As the substituent, for example, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable.
The acyl group preferably has 2 to 30 total carbon atoms, more preferably 2 to 20 total carbon atoms, and particularly preferably 2 to 16 total carbon atoms. 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, furanoyl group, A thiophenoyl group, a methacryloyl group, an acryloyl group, and the like can be given.

In the general formulas (V) and (VIII), the alkyloxycarbonyl group represented by R ¹ may have a substituent, and is preferably an alkoxycarbonyl group having 2 to 30 total carbon atoms. More preferably, those having 2 to 20 carbon atoms are more preferable, and those having 2 to 16 carbon atoms are particularly preferable. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, aryloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. , Etc.

In the general formulas (V) and (VIII), the aryloxycarbonyl group represented by R ¹ may have a substituent, and is preferably an alkoxycarbonyl group having 7 to 30 carbon atoms in total. Those having 7 to 20 total carbon atoms are more preferable, and those having 7 to 16 total carbon atoms are particularly preferable. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.

In the general formulas (V) and (VIII), the substituent represented by R ² is not particularly limited, and examples thereof include alkyl groups, alkoxy groups, aryloxy groups, halogen atoms, sulfonyl groups, acyloxy groups, nitro groups. Group, acylamino group, and the like. Among these, any of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group is preferable.

Here, specific examples of the oxime compound represented by the general formula (V) include compounds represented by the following structural formulas (1) to (54). However, the present invention is not limited to these. It is not something.
However, in the structural formulas (1) to (54), Me represents a methyl group. Ph represents a phenyl group. Ac represents an acetyl group.

  For example, the content of the oxime compound is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1.0 to 8.0% by mass in terms of solid content. When the amount is less than 0.1% by mass, the sensitivity is lowered, and it may be difficult to obtain a cured film having sufficient hardness. When the amount is more than 15% by mass, the tackiness when formed into a film is deteriorated. In addition, the cured film may become brittle because Tg is lowered.

<Other photopolymerization initiators>
The other 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 from known photopolymerization initiators. It is preferable that it has photosensitivity to visible light, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and initiates cationic polymerization depending on the type of monomer. It may be an initiator.
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 to 800 nm. The wavelength is more preferably 330 to 500 nm.

  Examples of the other photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thio compounds, ketones. Compounds, acridine compounds, metallocenes and the like. Specific examples include compounds described in JP-A-2005-258431. Among these, ketone compounds and acridine compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate. The said other photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  The solid content of the photopolymerization initiator in the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass. .

[Sensitizer]
It is preferable that the photosensitive composition further contains a sensitizer. The sensitizer is used in combination when the photosensitive layer is exposed and developed to improve the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferred.
The sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.).
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of
The sensitizer is at least one selected from a condensed ring compound, an aminophenyl ketone compound, a polynuclear aromatic, an acid nucleus, a basic nucleus, and a fluorescent brightener nucleus. It contains seeds and may contain other sensitizers as needed. As the sensitizer, a hetero-fused compound and an aminobenzophenone compound are more preferable in terms of improving sensitivity, and a hetero-fused compound is particularly preferable.

<Fused ring compound>
Among the above exemplary compounds, hetero-fused ring compounds are preferred as compounds in which an aromatic ring or a heterocyclic ring is fused (fused ring-based compounds). The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are more preferable, and among these, a thioxanthone compound is particularly preferable.
Specific examples of the hetero-fused ketone compound include, for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (for example, 10-n-butyl). 2-chloroacridone), etc .; thioxanthone compounds such as thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX; 3- (2-benzofuroyl)- 7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4- Dimethylaminobenzoyl -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3 -(2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-di Propoxycoumarin, 7-benzotriazol-2-ylcoumarin, 7-diethylamino-4-methylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207 , JP 2002-363208 A, JP 2002-363209 A, etc. Coumarin compounds of the mounting, coumarins and the like; and the like.
In addition, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), and the like.

The content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and 0.05 to 1% by mass with respect to the total solid content of the photosensitive composition. Particularly preferred.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.

The mass ratio of the sensitizer and the photopolymerization initiator content in the photosensitive composition is [(sensitizer) / (oxime compound)] = 1 / 0.1 to 1/100. Is preferable, and it is more preferable that it is 1/1 to 1/50.
When the mass ratio between the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may be lowered and the change in sensitivity over time may be deteriorated.

(Polymerizable compound)
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. A compound is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably. In the present invention, the “polymerizable compound” does not include a polymerizable compound that can be contained in the binder.

  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. The said polymeric compound may be used individually by 1 type, and may use 2 or more types together. Examples of commercially available products obtained by subjecting polyfunctional alcohols such as bisphenol to (meth) acrylate after addition reaction of ethylene oxide or propylene oxide include BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.). .

  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. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

(Thermal crosslinking agent)
The photosensitive composition preferably further contains a 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. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
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 resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, Hydrogenated 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 & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (diglycidyl phthalate) Ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4) Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak 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 are “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”) "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin Reaction product of 4-vinylcyclohexene-1-oxide ring-opened polymer with peracetic acid or the like, epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methyl Stilbene liquid crystal epoxy resin, dibenzoyloxybenzene liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, azine epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP − 50S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. 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.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among them, a β-methylglycidyl group is preferable from the viewpoint of improving the storage stability of the photosensitive composition and from the viewpoint of ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol F Bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates 1 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate and the like, and C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate, bisphenol A-formalde De polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ether of dinaphthol, di-β-alkyl glycidyl ether of binaphthol; poly- of phenol-formaldehyde polycondensate β-alkyl glycidyl ethers; poly-β-alkyl glycidyl ethers of monoalkyl substituted phenol-formaldehyde polycondensates of 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ethers of cresol-formaldehyde polycondensates; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ethers such as poly-β-alkyl glycidyl ethers of condensates; poly-β-alkyl glycidyl ethers of bisphenol A-formaldehyde polycondensates Bisphenol compounds such as poly-β-alkyl glycidyl ethers of formaldehyde polycondensates; poly-β-alkyl glycidyl ethers of polyaddition products of phenol compounds and divinylbenzene; The
Among these, β-alkylglycidyl ether derived from a bisphenol compound represented by the following general formula (D-1) and a polymer obtained from this and epichlorohydrin, and the following general formula (D-2) Poly-β-alkyl glycidyl ether of a phenol compound-formaldehyde polycondensate represented by
However, in said general formula (D-1), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
However, the general formula (D-2), R represents any of an alkyl group having 1 to 6 carbon hydrogen and carbon, R "represents either hydrogen atoms, and CH _3, n is 0 Represents an integer of 20.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  The skeleton of the epoxy compound is preferably at least one selected from bisphenol type epoxy resins, novolac type epoxy resins, alicyclic group-containing type epoxy resins, and poorly soluble epoxy resins.

  Examples of the oxetane compound include 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, oligomers or copolymers thereof, and compounds having an oxetane group , Novolac resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds with hydroxyl group resins such as silsesquioxane, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

Further, in order to promote the thermal curing of the epoxy compound or the oxetane compound, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N , N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives Cyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl) Midazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S- Triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric An acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic 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. In addition, as a commercial item of the said polyisocyanate compound, BL317 (made by Sumitomo Bayer Urethane Co., Ltd.) etc. are mentioned, for example.

Furthermore, for the purpose of improving the storage stability of the photosensitive film of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols (eg, 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 ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.). 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.

  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.

  1-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said thermal crosslinking agent, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.

[Filler]
It is preferable to add a filler to the photosensitive composition. The filler can improve the surface hardness of the permanent pattern, keep the coefficient of linear expansion low, or keep the dielectric constant and dielectric loss tangent of the cured film itself low.
There is no restriction | limiting in particular as said filler, It can select suitably from well-known things, For example, an inorganic pigment, organic particulates, etc. are mentioned.
Examples of the inorganic pigment include kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, gas phase method silica, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, and carbonic acid. Examples include magnesium, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and the like. As a commercial item of the said barium sulfate, B-30 (made by Sakai Chemical Industry Co., Ltd.) etc. are mentioned, for example.
The average particle size of the inorganic filler is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 0.01 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  As for the addition amount of the said filler, 1-60 mass% is preferable. When the addition amount is less than 1% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

[Other ingredients]
Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and further adhesion promoters and other auxiliaries (for example, conductive materials). Particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

<Thermal polymerization inhibitor>
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The content of the thermal polymerization inhibitor is preferably 0.001 to 5 mass%, more preferably 0.005 to 2 mass%, and particularly preferably 0.01 to 1 mass% with respect to the polymerizable compound.
When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

<Plasticizer>
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  The content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive composition.

<Coloring pigment>
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), C.I. I. Pigment Yellow 55, Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1), carbon, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content of the color pigment in the photosensitive composition can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation, and varies depending on the type of the color pigment. Generally, 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.

<Adhesion promoter>
In order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate, a known so-called adhesion promoter can be used for each layer.

  Preferable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and 0.1% by mass to 5% by mass with respect to all components of the photosensitive layer. Is particularly preferred.

(Photosensitive layer)
When the photosensitive layer formed of the photosensitive composition is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is: it is preferably 0.1~200mJ / cm ^2, more preferably 0.2~100mJ / cm ^2, and particularly preferably 0.5~50mJ / cm ^2.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 200 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

Here, the “minimum energy of light used for the exposure in which the thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development” (hereinafter sometimes simply referred to as “minimum energy of light”). The so-called development sensitivity, for example, the relationship between the amount of energy (exposure amount) of light used for the exposure when the photosensitive layer is exposed and the thickness of the cured layer generated by the development process following the exposure It can obtain | require from the graph (sensitivity curve) which shows.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring machine (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

Further, the variation rate (%) of the minimum energy of light in light having a wavelength of 400 to 410 nm (hereinafter also referred to as “sensitivity variation”) is preferably within 20%. If the variation rate exceeds 20%, the pattern shape in the surface may vary.
Here, for example, after measuring the minimum energy of the light in a light having a wavelength of 400 nm, the variation rate is measured by sequentially measuring the minimum energy of the light up to a light having a wavelength of 410 nm by shifting the wavelength by 1 nm. From the difference between the maximum value (Emax) and the minimum value (Emin) of the minimum energy, the following equation can be used.
〔formula〕
(Emax-Emin) / Emax

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

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer made of the photosensitive composition of the present invention formed on the support, and if necessary, such as a thermoplastic resin layer. It is preferable to have other layers. The photosensitive layer is as described above.
<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, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable. The support may be a single layer or may have a multilayer structure.

  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.

<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, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-30 micrometers is 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.
When the coefficient of static friction is less than 0.3, slipping is excessive, and thus when the roll is formed, winding deviation may occur. Sometimes.

  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 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 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 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.

<Other layers>
The other layers in the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, You may have layers, such as a surface protective layer. These layers may be used alone or in combination of two or more. Moreover, you may have a protective film on the said photosensitive layer.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling thru | or soluble with respect to alkaline liquid may be sufficient, and it may be insoluble.

  When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylate ester copolymer, a copolymer of styrene and a (meth) acrylate ester Saponification of coalescence, saponification of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate And a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 80 ° C. or lower.
As the thermoplastic resin having a softening point of 80 ° C. or lower, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less, which are soluble in an alkaline solution. In addition, even in an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer substance are added to the organic polymer substance so that a substantial softening point is 80 ° C. or lower. It is also possible to lower it.

  Further, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. Of the interlayer adhesive strength of each layer, it is preferable that the interlayer adhesive strength between the support and the cushion layer is the smallest. By setting such an interlayer adhesive force, only the support is peeled off from the photosensitive film, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. can do. In addition, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, adhesion improver, surfactant in the thermoplastic resin, The method of adding a mold release agent etc. is mentioned.

  The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl Examples thereof include alcohols and esters such as phosphate and biphenyldiphenyl phosphate; amides such as toluenesulfonamide.

When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is ethylene as an essential copolymer component.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate. A copolymer (EEA) etc. are mentioned.

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and may be appropriately selected depending on the intended purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. With such an interlayer adhesive strength, the support and the cushion layer are peeled off from the photosensitive film, and after the photosensitive layer is exposed, the photosensitive layer can be developed using an alkaline developer. . Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer are peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer. .

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting an ethylene copolymerization ratio described below.

The ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 to 90% by mass is preferable, and 60 to 80 is preferable. % By mass is more preferable, and 65 to 80% by mass is particularly preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are very easily peeled off, including the cushion layer. Production of the photosensitive film may be difficult.

There is no restriction | limiting in particular in the thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, and 15-40 micrometers is especially preferable.
If the thickness is less than 5 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be deteriorated, and a high-definition permanent pattern may not be formed. Such a problem may occur.

-Oxygen barrier layer (PC layer)-
The oxygen barrier layer is preferably formed usually with polyvinyl alcohol as a main component, and is preferably a film having a thickness of about 0.5 to 5 μm.

[Method for producing photosensitive film]
The said photosensitive film can be manufactured as follows, for example.
First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution for a photosensitive film.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive composition solution is applied on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

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 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 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. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer on the substrate and other layers appropriately selected according to the purpose.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

[Method for producing photosensitive laminate]
Examples of the method for producing the photosensitive laminate include, as the first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as the second aspect, at least the photosensitive film of the present invention. Examples of the method include transferring and laminating the photosensitive layer while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent on the surface of the substrate. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said photosensitive film is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing 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, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is 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 VP-II, Nichigo Morton VP130) , Hitachi Chemical Co., Ltd. HLM-V570).

  Since the photosensitive film and the photosensitive laminate of the present invention use the photosensitive composition of the present invention, the photosensitive film and the photosensitive laminate have high sensitivity and high resolution, sensitivity over time, film curability, and thermal shock resistance. Good, high-definition permanent patterns can be efficiently formed, for various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, color filters, pillar materials, rib materials, spacers, It can be suitably used for the production of liquid crystal structural members such as partition walls, pattern formation for holograms, micromachines, proofs, and the like, and in particular, it can be suitably used for permanent pattern formation on printed circuit boards.

  In particular, since the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned, the high acceleration test is performed. In (HAST), there is no occurrence of ion migration, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

(Pattern forming apparatus and permanent pattern forming method)
The pattern forming apparatus of the present invention includes the photosensitive layer and includes at least light irradiation means and light modulation means.

The permanent pattern forming method of the present invention includes at least an exposure step, and includes other steps such as an appropriately selected development step.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention.

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer of this invention. The photosensitive layer and substrate material of the present invention are as described above.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. For example, as described above, the photosensitive composition is heated and pressurized on the substrate. It is preferable to carry out with respect to the photosensitive layer in the photosensitive laminate formed by laminating while performing at least one of the above.

  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.

  The analog exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, exposure with a (super) high pressure mercury lamp, xenon lamp, halogen lamp, etc. through a photomask having a predetermined pattern. The method of performing is mentioned.

  The digital exposure is not particularly limited as long as it is performed without using the photomask, and can be appropriately selected according to the purpose. For example, an exposure head including at least a light irradiation unit and a light modulation unit; The exposure head irradiates the photosensitive layer with light emitted from the light irradiation means while modulating at least one of the photosensitive layers according to pattern information by the light modulation means. It is preferable.

  The light source used in the digital exposure is not particularly limited as long as it is a light source that emits ultraviolet to near infrared rays, and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp , Fluorescent lamps for use in halogen lamps and copying machines, or known light sources such as laser light are used. Among these, (ultra) high pressure mercury lamps and laser light are preferable, and laser light is more preferable.

  The (super) high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube or the like, and has a higher vapor pressure to increase luminous efficiency. Among the emission line spectra, an emission line spectrum of only one wavelength may be used using an ND filter or the like, or a light beam having a plurality of emission line spectra may be used.

“Laser” of the laser light is an acronym for Light Amplification by Stimulated Emission of Radiation. As an apparatus for emitting the laser light, an oscillator and an amplifier that generate monochromatic light having higher coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in a material having an inversion distribution, are preferably used. Can be mentioned.
Examples of the excitation medium for the laser light include crystals, glass, liquid, pigment, gas, and the like, and known lasers such as solid laser, liquid laser, gas laser, and semiconductor laser can be used.
Specifically, examples of the gas laser include an Ar ion laser (364 nm, 351 nm), a Kr ion laser (356 nm, 351 nm), and a He—Cd laser (325 nm), and examples of the solid laser include a YAG laser and a YVO ₄ laser (1, 064 nm), YAG laser or YVO ₄ laser, 2nd harmonic (532 nm), 3rd harmonic (355 nm), 4th harmonic (266 nm), a combination of a waveguide wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 nm to 400 nm) ), A combination of a waveguide wavelength conversion element and AlGaInP or an AlGaAs semiconductor t (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like. Among these, preferable laser light includes an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm) in terms of cost, and a 355 nm laser having high output in terms of productivity.

  The wavelength of the laser beam is, for example, preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 350 to 420 nm.

-Light modulation means-
As the light modulation means, a typical method is a method having n pixel parts and controlling the pixel parts according to the pattern information. Specifically, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect. And liquid crystal light shutter (FLC). Among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. If the light spot is not exposed between the light spots, the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction. The light spot in the rear row exposes between the light spot and the light spot, so that the entire surface of the photosensitive layer can be exposed. The DMD can form an image pattern by controlling the angle of each mirror and controlling the light spot on and off. By using such exposure heads having the DMD side by side, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed by using a mirror gradation spatial modulation element.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

  On the other hand, another typical method of the light modulation means is a method using a polygon mirror. Here, the polygon mirror is a rotating member having a series of plane reflecting surfaces around it. The polygon mirror reflects and irradiates light from the light source onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. Then, an image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. At this time, the scanning time can be shortened by using a plurality of lights from the light source.

  As the light modulation means of the present invention, in addition, an example of drawing using a polygon mirror described in JP-A-5-150175, as described in JP-T-2004-523101 (International Publication No. 2002/039793 pamphlet). An example in which a part of the image of the lower layer is visually acquired, and exposure is performed by aligning the position of the upper layer with the position of the lower layer with an apparatus using a polygon mirror, and exposure with the DMD described in JP-A-2004-56080 For example, an exposure apparatus provided with a polygon mirror described in JP-T-2002-523905, an exposure apparatus provided with a polygon mirror described in JP-A-2001-255661, DMD, LD, and multiple exposure described in JP-A-2003-50469 An example of a combination of an exposure method in which the exposure amount is changed depending on the part of the substrate described in JP-A-2003-156653 , Etc. Examples of an exposure method for performing a positional deviation adjustment described in JP 2005-43576 Publication and the like.

-Light irradiation means-
There is no restriction | limiting in particular as said light irradiation means, ie, the light irradiation method, Although the above-mentioned exposure light source can be selected suitably according to the objective, Two or more light from these light sources is synthesize | combined and irradiated. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by combining two or more lights.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of composing and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber is preferable.

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the dark color separation partition wall, the Gaussian beam 1 / e ² value is preferably 5 to 30 μm, 7-20 micrometers is more preferable.
In the present invention, it is preferable to spatially modulate laser light according to image data. Therefore, it is preferable to use the DMD which is a spatial light modulator for this purpose.

  Examples of the exposure apparatus having the light modulating unit and the light irradiating unit are described in JP-A-2005-222039, JP-A-2005-258431, JP-A-2006-30966, and the like. However, the exposure apparatus in the present invention is not limited to this.

[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.

For example, the pH of the weakly alkaline aqueous solution is preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 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.

  In the formation of the pattern, for example, a curing process, an etching process, a plating process, and the like may be included. These may be used alone or in combination of two or more.

[Curing process]
When the pattern formation method is a permanent pattern formation method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter, the photosensitive layer is cured after the development step. It is preferable to provide the hardening process process which processes.
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.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a UV exposure machine such as an ultra-high pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine and the like are preferable. It is mentioned in. The exposure amount is usually 10 to 2,000 mJ / cm ² .

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.
120-250 degreeC is preferable and the heating temperature in the said whole surface heating has more preferable 120-200 degreeC. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 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.

  The pattern forming method can be used for forming various patterns that require prevention of sensitivity reduction of the photosensitive layer by oxygen in direct writing by laser exposure of 405 nm, and has high density and high productivity. It can be suitably used for forming a compatible pattern.

  In the permanent pattern forming method, if the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from impact and bending from the outside. In the case of the interlayer insulating film, for example, it is useful for high-density mounting of semiconductors and components on a multilayer wiring board, a build-up wiring board, and the like.

  Since the method for forming a permanent pattern of the present invention uses the photosensitive composition of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, a color filter, and a column material. It can be suitably used for the production of liquid crystal structural members such as ribs, spacers, partition walls, etc., and the production of holograms, micromachines, proofs, etc., and in particular, it can be suitably used for the formation of permanent patterns on printed boards.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
In the following synthesis examples, the mass average molecular weight and acid value of the binder were measured as follows.

<Measurement of mass average molecular weight>
It measured on the following gel permeation chromatograph (GPC) conditions.
GPC condition pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Detector: Hitachi L-4000 UV [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-S300MDT-5 (two in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Column size: 8mmφ × 300mm
Eluent: DMF / THF = 1/1 + phosphoric acid 0.06M + lithium bromide 0.06M
Sample concentration: 5 mg / 1 mL
Injection volume: 5 μL
Pressure: 343 Pa (35 kgf / cm ² )
Flow rate: 1.0 mL / min

<Measurement of acid value>
First, about 1 g of a polyester resin solution is precisely weighed, 30 g of acetone is added to the resin solution, and the resin solution is uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. Then, the acid value is calculated from the titration result using the following formula.
Formula A = 10 × Vf × 56.1 / (Wp × I)
In the above formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of phenolphthalein, Wp represents the mass (g) of the polyester resin solution, and I represents the polyester resin solution. Represents the ratio (% by mass) of the non-volatile content.

(Synthesis Example 1)
-Synthesis of binder 1-
In a flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube, 182.7 parts by mass of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, Epicoat 1001, epoxy equivalent 479 g / eq), cyclohexanone 64. 0 mass parts and 30.0 mass parts of toluene were charged, and it stirred in the state heated at 130 degreeC, blowing nitrogen gas, and the reflux dehydration of the water | moisture content contained in an epoxy resin was performed.
Subsequently, 34.9 parts by mass of tetrahydrophthalic acid (manufactured by Shin Nippon Rika Co., Ltd.) and 3.6 parts by mass of dimethylparatoluidine (manufactured by Samsung Chemical Co., Ltd.) were added thereto, and the mixture was kept at 140 ° C. for 4 hours. Then, 108.0 parts by mass of tetrahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd.) was added and kept at 120 ° C. for 3 hours, and then diluted with 127.0 parts by mass of methyl ethyl ketone to obtain binder 1 as a modified epoxy resin. Obtained. The obtained binder 1 had a mass average molecular weight of 49,000, a solid content of 57.0% by mass, and an acid value of 133 mgKOH / g.

(Synthesis Example 2)
-Synthesis of binder 2-
In a flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, 9,9-bis (4′-glycidyloxyphenyl) fluorene (BF-103, produced by Yixing Precision Chemical Co., Ltd., epoxy equivalent 243 g / eq) , Trade name) 120.0 parts by mass, 64.0 parts by mass of cyclohexanone, and 30.0 parts by mass of toluene were charged, and stirred in a state heated to 130 ° C. while blowing nitrogen gas. The water was refluxed and dehydrated.
Next, 44.0 parts by mass of tetrahydrophthalic acid (manufactured by Shin Nippon Rika Co., Ltd.) and 3.6 parts by mass of dimethyl paratoluidine (manufactured by Samsung Chemical Co., Ltd.) were added thereto, and the mixture was kept at 140 ° C. for 4 hours. Then, 72.0 parts by mass of tetrahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd.) was added, and the mixture was kept at 120 ° C. for 3 hours, and then diluted with 127.0 parts by mass of methyl ethyl ketone to obtain binder 2 as a modified epoxy resin. Obtained. The obtained binder 2 had a mass average molecular weight of 25,000, a solid content of 48.0% by mass, and an acid value of 125 mgKOH / g.

( Reference Example 1)
-Preparation of photosensitive composition-
Each component was mix | blended in the following quantity and the photosensitive composition solution was prepared.
[Each component amount of photosensitive composition solution]
Binder 1 ... 131.6 parts by mass Dipentaerythritol hexaacrylate (DPHA, polymerizable compound) (manufactured by Nippon Kayaku Co., Ltd.) ... 20 parts by mass BPA monomer (manufactured by Shin-Nakamura Chemical Co., BPE-500) ... 5.0 parts by mass Oxime compound (photopolymerization initiator) represented by the following formula I-1 4.0 parts by mass 10-n-butyl-2-chloroacridone (NBCA, sensitizer) ) (Manufactured by Kurokin Kasei Co., Ltd.) 0.7 mass parts Polyisocyanate compound (thermal crosslinking agent, 75 mass% methyl ethyl ketone solution of hexamethylene diisocyanate methyl ethyl ketone oxime block) (BL3175, manufactured by Sumika Bayer Urethane Co., Ltd.) ..30 parts by mass C.I. I. Pigment Blue 15: 3 (non-halogen blue pigment) (manufactured by BASF, copper phthalocyanine blue)... 0.15 parts by mass C.I. I. Pigment Yellow 55 (non-halogen yellow pigment) (Daizo Seika Kogyo Co., Ltd., Disazo Yellow AAPT) 0.15 parts by mass

-Production of photosensitive film-
The obtained photosensitive composition solution was applied with a bar coater onto a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., 16FB50) having a thickness of 16 μm, a width of 300 mm, and a length of 200 m as the support, and hot air at 80 ° C. It dried in the circulation type dryer, and formed the 30-micrometer-thick photosensitive layer. Next, a polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated as a protective film on the photosensitive layer by lamination to produce a photosensitive film.

-Preparation of photosensitive laminate-
Next, the surface of the base material, that is, a copper-clad laminate having a wiring formed as a printed board (no through hole, copper thickness 12 μm) was prepared by subjecting it to a chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order.
Lamination conditions were as follows: vacuuming time 40 seconds, pressure bonding temperature 70 ° C., pressure bonding pressure 0.2 MPa, pressure time 10 seconds.
The photosensitive laminate was evaluated for sensitivity, raw storage, resolution, solder heat resistance, plating property, pencil hardness, and flexibility. The results are shown in Table 2.

<Evaluation of sensitivity>
From the support side to the photosensitive layer of the photosensitive film in the prepared photosensitive laminate, INPREX IP-3000 (manufactured by Fuji Photo Film Co., Ltd., pixel pitch = 1.0 μm) is used from 5 mJ / cm ² to 2 Double exposure was performed by irradiating light having different light energy amounts up to 500 mJ / cm ² at ^½ times intervals to cure a part of the photosensitive layer. 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 sprayed for 60 seconds to dissolve and remove the uncured region, and the thickness of the remaining cured region was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was 30 μm was determined as the amount of light energy necessary for curing the photosensitive layer.

<Evaluation of raw preservation>
The amount of light energy necessary to cure the photosensitive layer obtained by the sensitivity evaluation is defined as the minimum energy (E ₀ ) of light after being stored for 30 minutes while being shielded from light immediately after preparation of the photosensitive laminate. The photosensitive laminate was sealed in a moisture-proof bag (black polyethylene cylindrical bag, film thickness: 80 μm, water vapor transmission rate: 25 g / m ² · 24 hr or less) at 24 ° C. and 60% RH, and then 40 in after storage for 3 days at ° C., and measuring the light energy (E ₁₎ necessary for curing the photosensitive layer by the same method as in the evaluation of the sensitivity variation with respect to the E ₀ of the E ₁ the rate _was determined by _E 1 / E _0. The smaller the obtained value, the higher the sensitivity can be maintained even after the storage, which means that the raw storage is excellent.

<Evaluation of resolution>
The photosensitive laminate was allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, exposure was performed for each line width in increments of 5 μm from line / space = 1/1 to a line width of 10 to 100 μm using the pattern forming apparatus. .
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 was sprayed with a 1 mass% sodium carbonate aqueous solution at 30 ° C. as the developer at a spray pressure of 0.15 MPa for 60 seconds to dissolve and remove uncured regions.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way as a permanent pattern is observed with an optical microscope. The line width was measured and used as the resolution. The smaller the numerical value, the better the resolution.

<Evaluation of solder heat resistance>
A rosin-based flux (MH-820V, Tamura Chemical Research, trade name) was applied to the cured resin pattern and immersed in a solder bath at 260 ° C. for 10 seconds. This was defined as one cycle, and after repeating 6 cycles, the appearance of the coating film was visually observed.
○ ・ ・ ・ There is no abnormality (peeling, blistering) in the appearance of the coating film, and there is no solder peeling ×… There is an abnormality (peeling, blistering) in the coating film appearance, or there is solder peeling

<Evaluation of plating properties>
The cured resin pattern was dipped in an acidic degreasing solution at 40 ° C. (manufactured by Ebara Eugilite Co., Ltd., PB242D 10% diluted solution) for 3 minutes, and then washed with water.
Next, an activator solution (Okuno Pharmaceutical Co., Ltd.) at 30 ° C. in a soft etch solution at 30 ° C. (Meltex Co., Ltd., AD485 10% diluted solution) for 30 seconds, in a 10% sulfuric acid aqueous solution at 25 ° C. for 30 seconds. ) And ICP Axela 15% diluted solution) for 30 seconds. In addition, it washed with water between each process so far. Thereafter, electroless Ni plating (manufactured by Nippon Kanisen Co., Ltd., 20% diluted solution of S-810) is performed at 80 ° C. for 40 minutes. After washing with water, displacement gold plating (Kojima Chemical ( Co., Ltd., OEL 2000 20% diluted solution). The surface was observed using the cured resin pattern after plating, and the evaluation substrate having no problem in the surface observation was further subjected to a peel test with reference to JIS K 5600-5-6 and evaluated according to the following criteria.
○ ・ ・ ・ No abnormality after peel test.
Δ: There was no problem in the surface observation, but peeling was observed during the peel test.
X: Liquid peeling to the pattern part or peeling of the pattern was observed in the surface observation.

<Evaluation of pencil hardness>
About the said cured resin pattern, pencil hardness was measured based on JISK-5400.

<Evaluation of flexibility>
The method for forming the cured resin pattern, except that the substrate used for the evaluation was changed to a flexible printed wiring board substrate (trade name “F30VC1” manufactured by Nikkan Kogyo Co., Ltd.) in which a 18 μm thick copper foil was laminated on a polyimide substrate. By the same method, FPC for evaluation which formed the coverlay was obtained.
The obtained FPC for evaluation was folded 180 ° by goblet folding, the crack generation state in the coverlay at that time was visually observed, and evaluated according to the following criteria.
○ ・ ・ ・ No cracks in the coverlay ×× No cracks

( Reference Example 2)
In Reference Example 1, as shown in Table 1, except that the binder was changed to 156.25 parts by mass of the binder 2, sensitivity, raw storage stability, resolution, solder heat resistance, plating property, pencil hardness, And the flexibility was evaluated. The results are shown in Table 2.

( Reference Example 3)
In Reference Example 1, as shown in Table 1, the polymerizable compound was replaced with 25.0 parts by mass of DPHA, BPE-500 was not used, and the sensitizer was CPTX (SPEEDCURE).
CPTX, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.7 parts by mass, and the thermal crosslinking agent was changed to 30 parts by mass of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., ZX1059). , Resolution, solder heat resistance, plating property, pencil hardness, and flexibility were evaluated. The results are shown in Table 2.

( Reference Example 4)
In Reference Example 1, as shown in Table 1, sensitivity, raw storage stability, resolution, solder heat resistance were similarly changed except that the thermal crosslinking agent was changed to 30 parts by mass of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., ZX1059). , Plating properties, pencil hardness, and flexibility were evaluated. The results are shown in Table 2.

( Reference Example 5)
In Reference Example 4, as shown in Table 1, the photopolymerization initiator was 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (Ciba Specialty Chemicals). The sensitivity, raw storage stability, resolution, solder heat resistance, plating property, pencil hardness, and flexibility were evaluated in the same manner except for 4.0 parts by mass, manufactured by Irgacure OXE01). The results are shown in Table 2.

(Example 6)
In Reference Example 4, as shown in Table 1, the photopolymerization initiator was similarly replaced with 4.0 parts by mass of the compound represented by the following formula I-2. The heat resistance, plating property, pencil hardness, and flexibility were evaluated. The results are shown in Table 2.

( Reference Example 7)
In Reference Example 4, as shown in Table 1, the photopolymerization initiator was replaced by 4.0 parts by mass of CGI-325 (manufactured by Ciba Specialty Chemicals), and the sensitivity, Evaluation of storage stability, resolution, solder heat resistance, plating property, pencil hardness, and flexibility was performed. The results are shown in Table 2.

( Reference Example 8)
In Reference Example 1, as shown in Table 1, the evaluation of sensitivity, raw storage stability, resolution, solder heat resistance, plating property, pencil hardness, and flexibility was similarly performed except that no thermal crosslinking agent was used. It was. The results are shown in Table 2.

(Comparative Example 1)
In Reference Example 8, as shown in Table 1, the photopolymerization initiator was 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by Ciba Specialty Chemicals, Irgacure 369). The evaluation of sensitivity, raw storability, resolution, solder heat resistance, plating property, pencil hardness, and flexibility was similarly performed except that the content was changed to 4.0 parts by mass. The results are shown in Table 2.

(Comparative Example 2)
In Reference Example 8, as shown in Table 1, except that the binder was replaced with 112 parts by mass of Lipoxy PR-300 (Showa Polymer Chemical Co., Ltd.) having a concentration of 67% by mass, sensitivity, raw storage stability, resolution Solder heat resistance, plating property, pencil hardness, and flexibility were evaluated. The results are shown in Table 2.

(Comparative Example 3)
In Reference Example 4, as shown in Table 1, except that the binder was replaced with 112 parts by mass of a lipoxy PR-300 (Showa Polymer Chemical Co., Ltd.) having a concentration of 67% by mass, sensitivity, raw storage stability, resolution Solder heat resistance, plating property, pencil hardness, and flexibility were evaluated. The results are shown in Table 2.

(Comparative Example 4)
In Reference Example 4, as shown in Table 1, the binder was replaced with 112 parts by mass of lipoxy PR-300 (Showa Polymer Chemical Co., Ltd.) having a concentration of 67% by mass, and the photopolymerization initiator was 2-benzyl-2-dimethyl. Amino-1- (4-morpholinophenyl) -butanone-1 (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 369) is similarly replaced with 4.0 parts by mass, sensitivity, raw storage stability, resolution, solder heat resistance, Plating property, pencil hardness, and flexibility were evaluated. The results are shown in Table 2.

In Table 1, the unit of numerical values is parts by mass.

From the results in Table 2, Reference Examples 1 to 5 using a photosensitive composition containing a modified epoxy resin having a repeating unit represented by the general formula (I) and a photopolymerization initiator containing an oxime compound were carried out. In Example 6 and Reference Examples 7 to 8, it was found that sensitivity, raw storage stability, resolution, solder heat resistance, pencil hardness, and flexibility were good. Moreover, in Reference Examples 1-5, Example 6, and Reference Example 7 using the photosensitive composition containing a thermal crosslinking agent, it was found that the plating property was also good.

The photosensitive composition and photosensitive film of the present invention have high sensitivity and high resolution, have good sensitivity over time, film curability, and thermal shock resistance, and can efficiently form high-definition permanent patterns. Therefore, various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, and proofs It can be suitably used for the manufacture of a substrate, and can be particularly suitably used for forming a permanent pattern on a printed circuit board.
Since the permanent pattern forming method of the present invention uses the photosensitive composition of the present invention, 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 column material, It can be suitably used for the production of liquid crystal structural members such as ribs, spacers and 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 (8)

A binder, a polymerizable compound, and a photopolymerization initiator, wherein the binder contains a modified epoxy resin having a repeating unit represented by the following general formula (I), and the photopolymerization initiator is represented by the following general formula (V) The photosensitive composition characterized by including the oxime compound represented .
In the general formula (I), R ¹ represents a divalent organic group which is a diglycidyl ether type epoxy compound residue, R ² represents a divalent organic group which is a dibasic acid residue radical, R ³ represents a hydrogen atom or the following general formula (i).
In the general formula (i), R ⁴ represents an acid anhydride residue.
However, in said general formula (V), R < ¹ > represents either the acyl group, alkoxycarbonyl group, and aryloxycarbonyl group which may have a substituent. m represents an integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.   A modified epoxy resin is obtained through an intermediate production step for obtaining an intermediate by a polymerization reaction of a diglycidyl ether type epoxy compound and a dibasic acid, and an acid anhydride addition step for adding an acid anhydride to the intermediate. The photosensitive composition according to claim 1. The photosensitive composition in any one of Claim 1 to 2 containing a sensitizer. The photosensitive composition in any one of Claim 1 to 3 containing a thermal crosslinking agent. The photosensitive composition in any one of Claim 1 to 4 containing a filler. A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to claim 1 on a support. A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive composition according to claim 1. A printed circuit board, wherein a permanent pattern is formed by the method for forming a permanent pattern according to claim 7.