KR20080066845A - Photosensitive composition, phososensitive film, permanent pattern, and method for formation of the permanent pattern - Google Patents

Abstract

Disclosed is a photosensitive composition comprising a compound which causes no reaction under a low temperature or ambient temperature employed for storage, has excellent storage stability, can cause a cross-linking reaction by heating to enhance the curing of a resin, and can impart a good film hardness to a cured film containing the compound. The composition can form an image by the exposure to UV ray, shows a low surface tacking property, has a good laminating property and a good handling property, is excellent in storage stability, has a high sensitivity, is excellent in image-developing property, and can exert excellent chemical resistance, surface hardness, heat resistance, dielectric properties and the like after being developed. Also disclosed is a photosensitive film using the composition. Further disclosed is a highly precise permanent pattern. Still further disclosed is a method for formation of the pattern with good efficiency. The photosensitive composition comprises (A) a polymer having at least one carboxyl group and/or ester group per molecule, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) a specific compound having at least two oxirane groups per molecule.

Description

Photosensitive composition, photosensitive film, permanent pattern, and method for forming the same {PHOTOSENSITIVE COMPOSITION, PHOSOSENSITIVE FILM, PERMANENT PATTERN, AND METHOD FOR FORMATION OF THE PERMANENT PATTERN}

The present invention contains a compound which does not cause a reaction at normal temperature at the time of storage, initiates a crosslinking reaction by heating, obtains a good film hardness of a cured film, is imageable by UV exposure, and has a tacking property on the surface. This small, good lamination and handling property, excellent storage stability, high sensitivity and developability, and after the development, a photosensitive composition expressing excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, and the like, and It relates to a used photosensitive film and a high-precision permanent pattern (protective film, interlayer insulating film, solder resist pattern, etc.) and an efficient forming method thereof.

In the field of a printed wiring board, components such as a semiconductor, a capacitor, and a resistor are soldered onto the printed wiring board. In this case, for example, in the soldering process such as IR reflow, in order to prevent the solder from adhering to unnecessary portions of the solder, a method of forming a permanent pattern corresponding to the unnecessary portion of the solder as a protective film and an insulating film is provided. It is adopted. As the permanent pattern of the protective film, a solder resist is preferably used.

Conventionally, many thermosetting materials are used as a soldering resist, and the method of printing and performing this by the screen printing method was common. However, in recent years, as the wiring density of printed wiring boards is increased, limitations arise in terms of resolution in the screen printing method, and many photo solder resists which perform image formation by the photolithography method have been used. Especially, the alkali developing type photo solder resist which can be developed by weak alkali solution, such as a soda carbonate solution, has become mainstream from the point of work environment and global environment conservation. Moreover, generally, the manufacturing method of apply | coating and drying a liquid solder resist to one side of the board | substrate with which wiring formation was completed by screen printing, a spray coat, a dip coat, etc., and then apply | coating on the opposite side and drying is used.

In addition, as an alkali developing type photo solder resist as mentioned above, the compound (epoxy acrylate) and ethylenically unsaturated double bond which introduce | transduced the ethylenically unsaturated double bond and acid group for providing alkali developability to an epoxy compound as a main component are used. The composition containing the addition polymeric compound (monomer) which has is generally used, and is specifically described by patent document 1. As shown in FIG. However, the solder resist described in Patent Literature 1 obtains high surface hardness after post-baking and is excellent in chemical resistance, but has a tack on the surface and foreign matters tend to adhere, resulting in increased defects or contaminating the photomask. There is a problem such as worsening the handleability. Here, it is considered that the tack remains on the surface because the molecular weight of the epoxy acrylate, which is a soluble binder in an aqueous alkali solution, is low molecular weight (around 100) and the monomer is usually a liquid or semisolid having a high boiling point.

Moreover, the exposure sensitivity of such a soldering resist is 300-1,000mJ / cm <^2> normally low, and it becomes an obstacle of the speed increase of a manufacturing line, and the sensitivity increase is requested | required further. Although the increase of the compounding quantity of a monomer is effective in order to raise the said sensitivity, when a lot of monomers are mix | blended, the problem that the said surface tack will worsen arises, and the solution is not devised.

In addition, in recent years, high-density mounting is rapidly progressing, and in order to realize high-density mounting, the problem of solder resists is the expansion and contraction of the substrate and the change in temperature and humidity of the photomask film in the photolithography process in which wet phenomenon and wet etching are repeated. This is a misalignment of the wiring pattern and the through hole land pattern due to the expansion and contraction.

Until now, countermeasures have been adopted so far in order to prevent lot misalignment, to select a lot having a small degree of deformation of the substrate, to prepare a plurality of film masks previously modified with various parameters, or to use an expensive glass mask. In addition, in order to solve this position shift problem, application of the laser direct imaging system (LDI) is progressing. Here, LDI is based on the technique of forming the exposure pattern corresponding to the deformation | transformation of a board | substrate by the correction by the high speed processing of digital data.

The soldering resist used for the LDI requires an exposure sensitivity of 100 mJ / cm ² or more in order to correspond to a UV laser such as 365 nm or 405 nm. For this reason, the film-type soldering resist which is easy to obtain a high sensitivity has been required. However, when the solder resist described in Patent Literature 1 is formed into a film, the surface tackiness is strong, the support, the protective film and the photosensitive layer are hardly peeled off, the handleability is poor, and even in cryopreservation at -20 ° C or lower, for two or three months. Can only be preserved and there is a problem of storage stability. Moreover, it has the drawback that there is no sensitivity with respect to the laser beam of wavelength 405nm.

On the other hand, Patent Literature 2 discloses a solder resist having a small surface tack, excellent heat resistance, and relatively good storage stability using a soluble binder in a relatively high molecular weight alkali aqueous solution having a molecular weight of 10,000 or more. However, the solder resist has a problem of low surface hardness and poor lamination properties. Therefore, it is necessary to apply a liquid monomer as an underlayer to the outermost layer of the printed wiring board on which the wiring formation is completed, without generating bubbles, and the process is complicated and the handling is poor. As a reason for using the copolymer component (Tg of each homopolymer is 105 degreeC or more and 100 degreeC) which forms hard polymers, such as methyl methacrylate and styrene, as a result, a cured film lacks flexibility and is weak, and surface hardness Is not increased, and in the heat lamination step under vacuum conditions, sufficient fluidity is not obtained, which is considered to cause bubble generation. In addition, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.

In addition, in the field of leading electronic devices, high-speed propagation in a high frequency environment is required. In particular, in electronic devices represented by an electronic calculator or a mobile communication device, in accordance with the increase in the processing speed, the signal propagation speed, and the high frequency of the use band, Low dielectric constant and low dielectric loss tangent are demanded for a laminated plate material. Low dielectric constant and low dielectric loss tangent have been required for the solder resist in the manufacture of printed wiring boards. However, in the alkali developing solder resist of the present situation, the dielectric property in the high frequency region is bad, and it is a present state that the characteristic satisfy | filled as resin for high frequency is not obtained.

In addition, as a film-type soldering resist, in general, a commercially available product has a problem that a crosslinking reaction occurs and the storage stability is insufficient in order to mix a binder, a monomer, and a thermal crosslinking agent in the photosensitive layer. have.

On the other hand, as a curing accelerator of thermosetting resin compositions such as epoxy resin compositions, from the viewpoint of the above storage stability, a proposal using a so-called latent curing accelerator, which does not cause a reaction at the time of storage but has a property of reacting and curing by heating, have. For example, there exists the proposal which mix | blended the salt which consists of 2-ethylhexyl acid zinc and triethanolamine, and the salt which consists of triethylenediamine and aliphatic carboxylic acid (refer nonpatent literature 1 and patent document 3). These are intended to reduce the solubility, suppress the reaction activity and improve the storage stability by making the curing accelerator complexed.

Moreover, the adduct obtained by making dimethylamine and dialkylamine react with an epoxy resin (refer patent document 4, and patent document 5), and the adduct obtained by making tertiary amine react with an epoxy resin (refer patent document 6 and patent document 7) There is also a proposal using such a method. Thus, by adding an amine compound to an epoxy resin and polymerizing and insolubilizing, improvement of storage stability is aimed at.

However, these documents do not disclose a compound used as a thermal crosslinking agent without any disclosure used in the soldering resist, a satisfactory satisfactory high storage stability performance is obtained, and a low-cost raw material is not yet provided. This is further demanded.

Moreover, what aimed at the improvement of storage stability is disclosed by making the epoxy resin compound as a heat crosslinking agent into poor solubility (refer patent document 8 and patent document 9). In this case, however, the exposure sensitivity was low at ³⁰⁰ to 500 mJ / cm ³ , and it was difficult to achieve both good balance between storage stability, high sensitivity, and developability.

Therefore, it contains a thermal crosslinking agent which initiates a crosslinking reaction by heating without causing a reaction at normal temperature, and is capable of forming an image by UV exposure, has a small surface tack, excellent peelability with a support, etc., lamination and Good handleability, excellent storage stability, high sensitivity and developability, and a photosensitive composition capable of expressing excellent chemical resistance, surface hardness, heat resistance, dielectric properties, and the like after development, a photosensitive film using the same, and a highly detailed permanent pattern And it is the present state that the efficient formation method is not yet provided with what is satisfactory enough.

Patent Document 1: Japanese Patent Application Laid-Open No. 61-243869

Patent Document 2: Japanese Patent Application Laid-Open No. 02-097502

Patent Document 3: Japanese Patent Application Laid-Open No. 11-246651

Patent Document 4: Japanese Patent Application Laid-open No. 56-155222

Patent Document 5: Japanese Patent Application Laid-Open No. 57-100127

Patent Document 6: Japanese Patent Application Laid-Open No. 59-053526

Patent Document 7: Japanese Patent Application Laid-Open No. 2000-001526

Patent Document 8: Japanese Patent No. 2746009

Patent Document 9: Japanese Patent No. 2707495

[Non-Patent Document 1] Yuji, Endo Takeshi (Tokyo University of Technology) Network Polymer vol. 19, No. 4, P228-235, 1998

This invention solves all the said problems in the past, and makes it a subject to achieve the following objectives. That is, this invention does not produce reaction at normal temperature at the time of preservation, contains a compound which starts a crosslinking reaction by heating, and obtains the favorable film hardness of a cured film, is image-formable by UV exposure, surface tackiness is small, Photosensitive composition having good lamination and handling properties, excellent storage stability, high sensitivity and developability, and excellent after chemical development, surface hardness, heat resistance, dielectric properties, photosensitive film using the same, high precision permanent It is an object to provide a pattern (protective film, interlayer insulating film, solder resist pattern, etc.) and an efficient forming method thereof.

Means for solving the above problems are as follows. In other words,

<1> (A) A polymer having at least one of at least one carboxyl group and ester group in one molecule, (B) polymerizable compound, (C) photopolymerization initiator, and (D) the following general formulas (1) to (3 It is a photosensitive composition characterized by containing at least 1 sort (s) of compound chosen from the compound represented by ().

However, in said General Formula (1), (2), and (3), P represents either an oxygen atom, a carbonyl group, an amide group, a urethane group, alkylene, and arylene. Q represents any one of a boron atom, a nitrogen atom, alkylene and arylene. W represents naphthalene having a bond with two X moieties. A ^{1 to} A ⁵ represent any one of a single bond, alkylene and arylene, and X ^{1 to} X ⁶ represent any one of -OCONH-, -NHCOO-, -NHCO- and -CONH-. R ¹ to R ⁶ represent any one of a hydrogen atom, a halogen atom, an alkyl group and an aryl group.

In the photosensitive composition as described in said <1>, it does not produce hardening at the time of low temperature or normal temperature, it is excellent in storage stability, handleability, etc., it raises reaction by heating, and the excellent film hardness of a cured film is obtained. When a permanent pattern is formed using the said photosensitive composition, highly sensitive pattern formation is possible, the chemical-resistance, surface hardness, heat resistance, and dielectric property of a cured film are aimed at, and a high precision permanent pattern is obtained.

<2> Photosensitive composition as described in said <1> whose at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3) is a compound represented by following structural formula (1)-(10) to be.

<3> Photosensitive composition as described in said <1> or <2> whose content of content of at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3) is 1-50 mass%. to be.

<4> Photosensitive property in any one of said <1> to <3> which further contains the thermal crosslinking agent used together with at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3). Composition.

The thermal crosslinking agent used together with <5> is the photosensitive composition as described in said <4> which is at least 1 sort (s) chosen from the compound obtained by making a blocking agent react with an epoxy compound, an oxetane compound, a polyisocyanate compound, and a polyisocyanate compound.

The thermal crosslinking agent used together with <6> is the photosensitive composition as described in said <4> or <5> which is an epoxy compound derived from a polyhydric phenol compound and (beta) -alkyl epihalohydrin.

The thermal crosslinking agent used together with <7> is the photosensitive composition in any one of said <4> to <6> which is an epoxy compound which has two or more oxirane groups in a molecule | numerator.

The thermal crosslinking agent used together with <8> is the photosensitive composition in any one of said <4> to <7> which is an oxetane compound which has two or more oxetanyl groups in a molecule | numerator.

The heat crosslinking agent used together with <9> is the photosensitive composition in any one of said <4> to <8> represented by either of following structural formula (I) and (II).

However, in said structural formula (I), R represents either a hydrogen atom and a C1-C6 alkyl group, and n represents the integer of 0-20.

Of the stage, the structural formula (II), R represents one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, R 'represents either a hydrogen atom, and CH _3, n is an integer of 0 to 20 .

The thermal crosslinking agent used together with <10> is the photosensitive composition in any one of said <4> to <6> which is hexamethylated methylol melamine.

<11> (A) Polymer is a photosensitive composition in any one of said <1> to <10> which is an epoxy acrylate compound.

<12> Photosensitive composition in any one of said <1> to <11> in which (A) polymer contains at least 1 sort (s) of the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain.

The photosensitive property in any one of said <1> to <12> in which a <13> (A) polymer contains at least 1 sort (s) of an epoxy acrylate compound and the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain. Composition.

<14> (A) A polymer is a photosensitive composition in any one of said <11> to <13> represented by the following structural formula (III).

In the formula (III), X represents any one of a substituent containing a hydrogen atom and at least an acidic group, Y represents any one of a methylene group, an isopropylidene group, and a sulfonyl group, and n represents 1-20. Represents an integer.

The photosensitive composition as described in any one of said <1>-<5> and <10> which is a copolymer obtained by making a <15> (A) polymer react with 0.1-1.2 equivalent primary amine compound with respect to the anhydride group of a maleic anhydride copolymer. to be.

<16> The polymer (A) is an air comprising (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, wherein the vinyl monomer having a glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. It is a photosensitive composition in any one of said <1>-<5>, <10>, and <15> which is a copolymer obtained by making a 0.1-1.0 equivalent primary amine compound react with the anhydride group of a copolymer.

<17> (B) Polymeric compound is the photosensitive composition in any one of said <1> to <16> containing at least 1 sort (s) chosen from the monomer which has a (meth) acryl group.

(C) The photopolymerization initiator is at least one selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaaryl biimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and ketooxime ethers. It is the photosensitive composition in any one of said <1> to <17> to contain.

It has a photosensitive layer formed by laminating | stacking the photosensitive composition in any one of said <1>-<18> on a <19> support body and the said support body.

<20> In the case of exposing and developing the photosensitive layer, the minimum energy of light used for the exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 mJ / cm ² . It is a photosensitive film as described in <19>.

<21> support body is a photosensitive film in any one of said <19> to <21> which contains a synthetic resin and is transparent.

The <22> support body is the photosensitive film in any one of said <19>-<21> which is a long picture.

It is a <23> elongate shape and is the photosensitive film in any one of said <19> to <22> which is wound up in roll shape.

It is the photosensitive film in any one of said <19> to <23> which comprises a protective film on a <24> photosensitive layer.

It is a photosensitive film in any one of said <19> to <24> whose thickness of a <25> photosensitive layer is 3-100 micrometers.

<26> Deformation of the exit surface in the drawing section after modulating the light from the light irradiation means by the light modulating means having n ridges for receiving the light from the light irradiation means and emits light It is a photosensitive film as described in said <19>-<25> exposed by the light which passed through the microlens array which arrange | positioned the microlens which has the aspherical surface which can correct aberration by this.

<27> After applying the photosensitive composition in any one of said <1>-<18> to the surface of a base material, drying and forming a photosensitive layer, it exposes, develops, and heats, The permanent pattern formation characterized by the above-mentioned. Way. In the permanent pattern formation method as described in said <27>, the said photosensitive composition is apply | coated to the surface of the said base material, and the said photosensitive composition is dried and the said photosensitive layer is formed. The photosensitive layer is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated. By heating the said photosensitive layer, a crosslinking reaction is started and the film strength of the hardened area | region of the said photosensitive layer becomes high. As a result, a permanent pattern which is high in surface hardness and is optimal for a protective film, an interlayer insulating film, a solder resist pattern, or the like is formed. The heat treatment may be a whole surface heat treatment, or may be a pattern heating.

<28> A permanent film characterized in that the photosensitive film according to any one of the above <19> to <26> is laminated on the surface of the substrate under at least one of heating and pressurization, followed by exposure, development and heating. Pattern formation method. In the permanent pattern formation method as described in said <28>, the said photosensitive film is laminated | stacked on the surface of the said base material under heating and pressurization. The photosensitive layer in the laminated photosensitive film is exposed, the exposed photosensitive layer is developed, and the developed photosensitive layer is heated. The film strength of the hardened area | region of the said photosensitive layer improves by the crosslinking effect of the compound represented by the said General Formula (1)-(3) by heating the said photosensitive layer. As a result, a permanent pattern which is high in surface hardness and is optimal for a protective film, an interlayer insulating film, a solder resist pattern, or the like is formed.

<29> base material is a permanent pattern formation method in any one of said <27> or <28> which is a printed wiring board in which wiring formation was completed. By using the permanent pattern forming method described above, high-density mounting on a multilayer wiring board, a buildup wiring board, or the like of a semiconductor component is possible.

It is a permanent pattern formation method in any one of said <27>-<29> performed in image shape based on the pattern information formed by <30> exposure.

It is a permanent pattern formation method in any one of said <27> to <30> which produces | generates a control signal based on the pattern information formed by <31> exposure, and uses the light modulated according to the said control signal.

<32> Any one of the above <27> to <31> performed using light irradiation means for irradiating light and light modulating means for modulating the light irradiated from the light irradiation means on the basis of the pattern information to be formed. It is a permanent pattern formation method of description.

And a pattern signal generating means for generating a control signal based on the pattern information formed by the light modulating means, wherein the light irradiated from the light irradiation means is generated in accordance with the control signal generated by the pattern signal generating means. It is a permanent pattern formation method as described in said <32> which modulates.

The light modulating means has n drawing parts and is controllable in accordance with the pattern information for forming any less than n drawing parts arranged consecutively among the n drawing parts. It is a permanent pattern formation method in any one of. In the permanent pattern forming method according to the above <34>, the light from the light irradiation means is controlled by controlling any less than n seedling portions continuously arranged among the n drawing portions in the light modulating means according to the pattern information. This is modulated at high speed.

<35> light modulation means is a permanent pattern formation method in any one of said <32> to <34> which is a spatial light modulation element.

The <36> spatial light modulator is a permanent pattern formation method as described in said <35> which is a digital micro mirror device (DMD).

<37> drawing parts are the permanent pattern formation methods in any one of said <34> to <36> which is a micro mirror.

After the exposure modulates the light by the light modulating means, the aberration caused by the deformation of the exit face of the drawing part in the light modulating means is passed through a microlens array in which the microlenses having the aspherical surface correctable are arranged. Paper is the permanent pattern formation method in any one of said <34>-<37>.

<39> aspherical surface is a toric surface, The permanent pattern formation method as described in said <38>. In the method for forming a permanent pattern according to the above <39>, since the aspherical surface is a toric surface, aberration due to deformation of the radiation surface in the tomb is effectively corrected, and deformation of an image formed on the photosensitive layer is effectively suppressed. . As a result, exposure to the photosensitive layer is performed with high precision. Thereafter, the photosensitive layer is developed to form a high-precision permanent pattern.

<40> exposure is a permanent pattern formation method in any one of said <27> to <39> which is performed through an aperture array. In the permanent pattern formation method as described in said <40>, an extinction ratio improves because exposure is performed through the said aperture array. As a result, exposure is performed very precisely. Thereafter, by developing the photosensitive layer, a very high precision permanent pattern is formed.

<41> exposure is the permanent pattern formation method in any one of said <27> to <40> performed while moving exposure light and a photosensitive layer relatively. In the permanent pattern formation method as described in said <41>, exposure is performed at high speed by exposing and moving the modulated light and the said photosensitive layer relatively.

<42> exposure is the permanent pattern formation method in any one of said <27> to <41> performed with respect to the some area | region of a photosensitive layer.

<43> light irradiation means is a permanent pattern formation method in any one of said <32> to <42> which can synthesize | combine two or more lights, and can irradiate. In the permanent pattern formation method as described in said <43>, since the said light irradiation means synthesize | combines and irradiates two or more lights, exposure is performed as exposure light with a deep depth of focus. As a result, exposure to the photosensitive layer is performed with high accuracy. Thereafter, by developing the photosensitive layer, a very high precision permanent pattern is formed.

<44> Any of the above <32> to <43>, wherein the light irradiation means has a plurality of lasers, a multi-mode optical fiber, and a collective optical system for collecting and coupling the laser light irradiated from the plurality of lasers, respectively, to the multi-mode optical fiber It is a permanent pattern formation method of one. In the method for forming a permanent pattern according to the above <44>, exposure is focused by allowing the laser light irradiated from the plurality of lasers to be received by the collective optical system and coupled to the multi-mode optical fiber by the light irradiation means. Depth is performed with deep exposure light. As a result, exposure to the photosensitive layer is performed with high accuracy. Thereafter, by developing the photosensitive layer, an extremely high precision permanent pattern is formed.

<45> exposure is the permanent pattern formation method in any one of said <27> to <44> performed using the laser beam of the wavelength of 395-415 nm.

<46> heating is a permanent pattern formation method in any one of said <27> to <45> performed at 120-250 degreeC. In the permanent pattern formation method as described in said <46>, the film strength of a cured film becomes high in the heat processing performed on the said temperature conditions.

After <47> image development is performed, it is a permanent pattern formation method as described in said <27>-<46> which performs a whole surface exposure process with respect to a photosensitive layer. In the permanent pattern formation method as described in said <46>, hardening of resin in the said photosensitive composition is accelerated in the said whole surface exposure process.

It is a permanent pattern formation method in any one of said <27> to <47> which forms at least any one of a <48> protective film, an interlayer insulation film, and a soldering resist pattern. In the method for forming a permanent pattern described in the above <48>, at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed, so that the wiring is protected from an impact or bending from the outside due to insulation, heat resistance, and the like of the film.

<49> It is a permanent pattern formed by the permanent pattern formation method in any one of said <27>-<48>. Since the permanent pattern described in the above <49> is formed by the above-mentioned permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and is highly accurate, and has high density to a multilayer wiring board, a buildup wiring board, or the like of a semiconductor component. Useful for mounting.

It is a permanent pattern as described in said <49> which is at least any one of a <50> protective film, an interlayer insulation film, and a soldering resist pattern. The permanent pattern described in the above <50> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, so that the wiring is protected from external shock, bending, or the like due to insulation, heat resistance, and the like of the film.

(Effects of the Invention)

According to the present invention, a problem in the prior art can be solved, and the compound does not cause a reaction under normal temperature at the time of storage, contains a compound which starts a crosslinking reaction by heating, and obtains a favorable film hardness of the cured film, and by UV exposure. It is capable of forming an image, has low surface tack, good lamination and handling properties, excellent storage stability, high sensitivity and developability, and shows excellent chemical resistance, surface hardness, heat resistance and dielectric properties after development. The photosensitive composition, the photosensitive film using the same, and high-precision permanent pattern (protective film, an interlayer insulation film, a soldering resist pattern, etc.), and its efficient formation method can be provided.

(Photosensitive composition)

The photosensitive composition of this invention is a polymer which has any one or more of carboxyl groups and an ester group in (A) 1 molecule, (B) polymeric compound, (C) photoinitiator, and (D) general formula (1) mentioned later It may contain at least one compound selected from the compounds represented by (3) at least and may contain a thermal crosslinking agent to be used in combination, and if necessary, color pigments, extender pigments, thermal polymerization inhibitors, surfactants and the like. It is made by containing other components of.

[(A) Binder (Polymer)]

As said binder, the compound which shows swelling property with respect to alkaline aqueous solution is preferable, and the compound which is soluble with respect to alkaline aqueous solution is more preferable.

As a binder which shows swelling property or solubility with respect to alkaline aqueous solution, what has an acidic group is mentioned preferably, for example, The compound (epoxyacrylate compound) which introduce | transduced an ethylenically unsaturated double bond and an acidic group into an epoxy compound specifically, a side chain The vinyl copolymer which has an (meth) acryloyl group and an acidic group, the mixture of an epoxy acrylate compound and the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain, a maleamic acid type copolymer, etc. are preferable.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, Among these, a carboxyl group is preferably listed from a viewpoint of the availability of a raw material, etc. among these. .

<Epoxyacrylate Compound>

There is no restriction | limiting in particular as a compound (epoxy acrylate compound) which introduce | transduced ethylenically unsaturated double bond and an acidic group into the said epoxy compound, According to the objective, it can select suitably, For example, a polyfunctional epoxy compound and a carboxyl group-containing monomer are used. It is made to react, and also obtained by the method of adding a polybasic acid anhydride.

As said polyfunctional epoxy compound, the heterocyclic epoxy resin ("TEPIC; Nissan") which has a bixylenol type or bisphenol-type epoxy resin ("YX4000; Japan epoxy resin company", etc.) or these mixtures, an isocyanurate skeleton etc. Chemical industry production "," Araldite PT810; Chiba specialty chemicals company production ", bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type Epoxy resin, cresol novolak type epoxy resin, halogenated phenol novolak type epoxy resin, glycidyl amine type epoxy resin (for example, tetraglycidyl diaminodiphenylmethane, etc.), hydantoin type epoxy resin, alicyclic type Epoxy resin, trihydroxy phenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylethane type epoxy resin, gly Dyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin ("ESN-190, ESN-360; the product made by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; Dainippon) Ink chemical company ", etc.) Epoxy resins having a dicyclopentadiene skeleton (" HP-7200, HP-7200H; Dainippon ink chemical company ", etc.); Reactant of the polyphenol compound and epichlorohydrin obtained by condensation reaction of phenol compounds, such as a phenol, o-cresol, a naphthol, and aromatic aldehyde which has a phenolic hydroxyl group (for example, p-hydroxybenzaldehyde); Reactant of the polyphenol compound and epichlorohydrin obtained by addition reaction of a phenol compound and diolefin compounds, such as divinylbenzene and dicyclopentadiene; Epoxidation of the ring-opened polymer of 4-vinylcyclohexene-1-oxide with peracetic acid or the like; Epoxy resins having heterocycles such as triglycidyl isocyanurate; The glycidyl methacrylate copolymer type epoxy resin ("CP-50S, CP-50M; the Japan oil company make", etc.), the copolymerization epoxy resin of cyclohexyl maleimide, glycidyl methacrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the carboxyl group-containing monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano cinnamic acid, acrylic acid dimers; In addition, addition reaction products of monomers which have hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic acid anhydrides, such as maleic anhydride, a phthalic anhydride, cyclohexane dicarboxylic anhydride; The reaction product of a halogen containing carboxylic acid compound, (omega)-carboxy polycaprolactone mono (meth) acrylate, etc. are mentioned. Moreover, as a commercial item, NK ester CB-1 and CBX-1 by Aronikkusu M-5300, M-5400, M-5500, and M-5600, Shin-Nakamura Chemical Co., Ltd., HOA-MP and HOA-MS manufactured by Kyoesha Oil & Chemicals Co., Ltd., and Biscoat # 2100 produced by Osaka Organic Chemicals Co., Ltd. can be used. These may be used individually by 1 type and may use 2 or more types together.

Moreover, as said polybasic acid anhydride, for example, succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, maleic anhydride , Methyl maleic anhydride, 2,3-dimethyl maleic anhydride, 2-chloro maleic anhydride, 2,3-dichloro maleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaconic anhydride, phthalic anhydride, tetra Hydrophthalic anhydride, tetrachloro phthalic anhydride, tetrabromo phthalic anhydride, hexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, endomethylenetetrahydro phthalic anhydride, methylendomethylenetetrahydro phthalic anhydride, chlorine anhydride Acids and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Polybasic acid anhydrides, such as a dibasic acid anhydride, a trimellitic anhydride, a pyromellitic anhydride, and a 3,3 ', 4,4'- benzophenone tetracarboxylic acid, etc. can also be used. These may be used individually by 1 type and may use 2 or more types together.

Each reacted sequentially to obtain an epoxy acrylate, but the ratio of reacting them was 0.8 to 1.2 equivalents, preferably 0.9 to 1.1 equivalents, of the carboxyl group-containing monomer relative to 1 equivalent of the epoxy group of the polyfunctional epoxy compound. 0.1-1.0 equivalent, Preferably it is 0.3-1.0 equivalent.

Moreover, the compound etc. which are obtained by adding the said polybasic acid anhydride to the epoxy acrylate (compound which does not have a carboxyl group) which have a fluorene frame | skeleton of Unexamined-Japanese-Patent No. 5-70528 can also be used as an epoxy acrylate of this invention.

Among the compounds in which an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound, an epoxy acrylate compound represented by the following structural formulas (III) and (IV) is preferable.

In the above general formula (III), X represents any one of a substituent containing a hydrogen atom and at least an acidic group, Y represents any one of a methylene group, an isopropylidene group and a sulfonyl group, and n represents 1 to 1 The integer of 20 is shown.

However, in said general formula (IV), n represents the integer of 1-20.

As the epoxy acrylate compound represented by the structural formula (III), specifically, a bisphenol F-type epoxy acrylate compound represented by the following structural formula (V) and a bisphenol A type epoxy acrylate compound represented by the following structural formula (VI) More preferred.

As molecular weight of the said epoxy acrylate compound, 1,000-100,000 are preferable and 2,000-50,000 are more preferable. When the said molecular weight is less than 1,000, the tackiness of the surface of a photosensitive layer may become strong, and after hardening of the photosensitive layer mentioned later, a film quality may become soft or surface hardness may deteriorate, and when it exceeds 100,000, developability will be It may deteriorate. In addition, the synthesis of the resin also becomes difficult.

<Vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain>

As a vinyl copolymer which has a (meth) acryloyl group and an acidic group in the said side chain, For example, (1) the vinyl monomer which has an acidic group, (2) the vinyl monomer which has a functional group which can be used for the polymer reaction mentioned later as needed, and (3) Synthesizing (co) polymers obtained by vinyl (co) polymerization of other copolymerizable vinyl monomers as necessary, and (4) at least one of the acidic groups in the (co) polymers or functional groups available for polymer reactions. It is obtained by making high molecular reaction of the compound which has the functional group and (meth) acryloyl group which are reactive with respect to a species.

There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has the said (1) acidic group, According to the objective, it can select suitably, For example, the compound described in Unexamined-Japanese-Patent No. 2005-258431, etc. This is listed. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, a citraconic acid anhydride, as a precursor of a carboxyl group.

As a functional group which can be used for the polymer reaction in the vinyl monomer which has a functional group which can be used for the polymer reaction of said (2), a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. are mentioned. Moreover, the carboxyl group and acid anhydride of above-mentioned (1) are also listed as a functional group which can be used.

As a vinyl monomer which has the said hydroxyl group, the compound described in [0182]-[0192] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.

As a vinyl monomer which has the said amino group, vinylbenzylamine, aminoethyl methacrylate, etc. are mentioned, for example.

As a monomer which has the said isocyanate group, the compound described in [0176]-[0180] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.

As a vinyl monomer which has the said epoxy group, glycidyl (meth) acrylate, the compound represented by following structural formula (45), etc. are mentioned, for example.

However, in the formula (45), R represents any one of H and Me.

As a vinyl monomer which has the said acid halide group, (meth) acrylic acid chloride etc. are mentioned, for example.

As a vinyl monomer which has the said active halide group, chloromethyl styrene etc. are mentioned, for example.

As these commercial items, it is "Kaneka resin AXE; Kanegafuchi Chemical Co., Ltd. product "," CYCLOMER A-200; Daicel Chemical Co., Ltd. product "," CYCLOMER M-200; Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; "Showa Polymer Co., Ltd." etc. can be used.

In addition, each said monomer may be used individually by 1 type, and may use 2 or more types together.

There is no restriction | limiting in particular as another copolymerizable monomer used as needed of said (3), Although it can select suitably according to the objective, For example, in Unexamined-Japanese-Patent No. 2005-258431, [0165]-[0174] The compound described, etc. are mentioned.

As a synthesis method of the vinyl monomer which has a urethane group or a urea group as the said functional group, addition reaction of an isocyanato group, a hydroxyl group, or an amino group is mentioned, for example, One monomer and hydroxyl group which have an isocyanato group specifically, are mentioned. The addition reaction of the compound containing, or the compound which has one primary or secondary amino group, the monomer which has a hydroxyl group, or the addition reaction of the monomer which has a primary or secondary amino group, and monoisocyanato is mentioned.

As a monomer which has the said isocyanato group, the compound described in [0176]-[0180] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.

As said monoisocyanate, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As a monomer which has the said hydroxyl group, the compound described in [0182]-[0192] of Unexamined-Japanese-Patent No. 2005-258431 is mentioned, for example.

As a compound containing one said hydroxyl group, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As a monomer which has the said primary or secondary amino group, vinylbenzylamine etc. are mentioned, for example.

As a compound containing one said primary or secondary amino group, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

By vinyl (co) polymerizing these, the (co) polymer containing an acidic group, an acid anhydride group, and if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. is obtained. The said vinyl (co) polymer can be prepared by copolymerizing the corresponding monomer, respectively by a well-known method according to a conventional method. For example, it can prepare by the method of Unexamined-Japanese-Patent No. 2005-258431.

The (co) polymer obtained in this way has the reactivity with at least one of the acidic groups in these copolymers and, if necessary, hydroxyl groups, amino groups, isocyanate groups, glycidyl groups and acid halide groups. It is obtained by polymer-reacting the compound which has a functional group and a (meth) acryloyl group.

As a compound which has the functional group and (meth) acryloyl group which are reactive with at least 1 sort (s) among the acidic group in the (co) polymer of said (4), or the functional group which can be used for polymer reaction, the compound etc. which were mentioned in (2) mentioned above are mentioned. It is available.

Examples of the combination of functional groups in the case of performing these polymer reactions include, for example, a combination of a copolymer having an acid group (carboxyl group and the like) and a vinyl monomer having an epoxy group, a combination of a copolymer having an amino group and a vinyl monomer having an epoxy group, Combination of copolymer having amino group and vinyl monomer having isocyanate group, Combination of copolymer having hydroxyl group and vinyl monomer having isocyanate group, Combination of copolymer having hydroxyl group and vinyl monomer having acid halide group, Copolymer having amino group and active Combination of vinyl monomers having halide groups, copolymers of acid anhydride groups and vinyl monomers having hydroxyl groups, combinations of copolymers having isocyanate groups and vinyl monomers having amino groups, combinations of copolymers having isocyanate groups and vinyl monomers having hydroxyl groups Active harley The combination of such a vinyl monomer having an amino group and a copolymer having a group are exemplified. In addition, these combinations may use 2 or more types together.

<Maleamic Acid Copolymer>

The maleic amide copolymer is a copolymer obtained by reacting at least one primary amine compound with an anhydride group of a maleic anhydride copolymer. The copolymer is preferably a maleamic acid copolymer comprising at least a maleamic acid unit B having a maleic acid half amide structure represented by the following structural formula (VII) and a unit A not having the maleic acid half amide structure.

The unit A may be one kind or two or more kinds. For example, when said unit B is 1 type, when the said unit A is 1 type, the said maleamic acid type copolymer means a binary copolymer, and when said unit A is 2 types, the said maleamic acid type is Copolymer means tertiary copolymer.

As said unit A, the combination of the aryl group which may have a substituent and the vinyl monomer (c) whose glass transition temperature (Tg) of the homopolymer of the said vinyl monomer is less than 80 degreeC is mentioned preferably.

However, in said structural formula (VII), R <^3> and R < ⁴ > represents either a hydrogen atom and a lower alkyl group. x and y represent the mole fraction of a repeating unit, for example, when the said unit A is 1 type, x is 85-50 mol% and y is 15-50 mol%.

Examples of R ^{1 in} the structural formula (VI) include (-COOR ¹⁰ ), (-CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (-OCOR ¹³ ), (-OR ¹⁴ ), (-COR ¹⁵ Substituents such as Here, said R <^10> -R <^15> represents either the hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.

As said R <^10> -R <^15> , methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like are listed.

As a specific example of said R <^1> , For example, benzene derivatives, such as phenyl, (alpha)-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2, 4- dimethylphenyl; n-propyloxycarbonyl, n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyl Oxycarbonyl and the like.

As said R <^2> , the alkyl group, aryl group, aralkyl group etc. which may have a substituent are mentioned. These may have a cyclic structure or a branched structure. Specific examples of R ² include benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, α-methylbenzyl 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2 -(4-chlorophenyl) ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) ethyl, 4-fluoro-α, α Dimethyl phenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, Methyl, ethyl, propyl, i-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl , 2-ethoxyethyl, 3- The ethoxypropyl, 2-ethoxypropyl-butoxyethyl, 2-cyclohexyl-oxyethyl, 3-, and 3-propoxy propyl, 3-isopropoxy-propylamine are exemplified.

The binder is a copolymer of (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, wherein the copolymer comprises a vinyl monomer having a glass transition temperature (Tg) of the homopolymer of the vinyl monomer of less than 80 ° C. It is preferable that it is a copolymer obtained by making a primary amine compound react with an anhydride group. In the copolymer which consists of said (a) component and said (b) component, although the photosensitive layer of the high surface hardness mentioned later can be obtained, it may become difficult to ensure lamination property. Moreover, although lamination property can be ensured in the copolymer which consists of said (a) component and said (c) component, securing of the said surface hardness may become difficult.

-(b) Aromatic Vinyl Monomers--

There is no restriction | limiting in particular as said aromatic vinyl monomer, Although it can select suitably according to the objective, Since the surface hardness of the photosensitive layer formed using the photosensitive composition of this invention can be made high, the glass transition temperature of a homopolymer ( The compound whose Tg) is 80 degreeC or more is preferable, and the compound which is 100 degreeC or more is more preferable.

As a specific example of the said aromatic vinyl monomer, For example, styrene (Tg = 100 degreeC of homopolymer), (alpha) -methylstyrene (Tg = 168 degreeC of homopolymer), 2-methylstyrene (Tg = 136 degreeC of homopolymer), Styrene derivatives, such as 3-methylstyrene (Tg of homopolymer = 97 degreeC), 4-methylstyrene (Tg of homopolymer Tg = 93 degreeC), and 2, 4- dimethyl styrene (Tg of homopolymer (112 degreeC)) are preferable. Listed. These may be used individually by 1 type and may use 2 or more types together.

-(c) vinyl monomers--

As for the said vinyl monomer, the glass transition temperature (Tg) of the homopolymer of the said vinyl monomer needs to be less than 80 degreeC, 40 degrees C or less is preferable, and 0 degrees C or less is more preferable.

As said vinyl monomer, n-propyl acrylate (Tg = -37 degreeC of a homopolymer), n-butyl acrylate (Tg = -54 degreeC of a homopolymer), pentyl acrylate, or hexyl acrylate (homopolymer, for example) Tg = -57 ° C.), n-butyl methacrylate (Tg = -24 ° C. of homopolymer), n-hexyl methacrylate (Tg = -5 ° C. of homopolymer), and the like. These may be used individually by 1 type and may use 2 or more types together.

Primary amine compound

As said primary amine compound, for example, benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1- Hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3- Phenylpropylamine, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 4-bromophenethylamine, 2- ( 2-chlorophenyl) ethylamine, 2- (3-chlorophenyl) ethylamine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl ) Ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethylphenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine , 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methyla , Ethylamine, propylamine, 1-propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylaniline, Anicidine, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclo Hexyloxyethylamine, 3-ethoxypropyl amine, 3-propoxypropylamine, 3-isopropoxypropylamine and the like. Among these, benzylamine and phenethylamine are particularly preferable.

The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.

As reaction amount of the said primary amine compound, it is necessary that it is 0.1-1.2 equivalent with respect to the said anhydride group, and 0.1-1.0 equivalent is preferable. When the said reaction amount exceeds 1.2 equivalent, when 1 or more types of said primary amine compounds are reacted, solubility may deteriorate remarkably.

15-50 mol% is preferable, as for content in the said binder of (a) maleic anhydride, 20-45 mol% is more preferable, 20-40 mol% is especially preferable. If the content is less than 15 mol%, alkali developability cannot be imparted. If the content exceeds 50 mol%, alkali resistance deteriorates, and the synthesis of the copolymer becomes difficult, and a normal permanent pattern can be formed. There may be no. In this case, the content in the binder of the vinyl monomer in which the glass transition temperature (Tg) of the (b) aromatic vinyl monomer and (c) homopolymer in this case is less than 80 ° C is 20 to 60 mol% and 15 to 15, respectively. 40 mol% is preferable. When the said content satisfies the said numerical range, both surface hardness and lamination property can be aimed at.

3,000-500,000 are preferable and, as for the molecular weight of the said maleamic acid type copolymer, 8,000-150,000 are more preferable. When the said molecular weight is less than 3,000, after hardening of the photosensitive layer mentioned later, film quality may become weak and surface hardness may deteriorate, and when it exceeds 500,000, the fluidity at the time of lamination | stacking of the said photosensitive composition will become low, and ensuring appropriate lamination property May become difficult, and developability may deteriorate.

<Other Binders>

As said binder, you may use other binder together. As said other binder, the polyamide (imide) resin of Unexamined-Japanese-Patent No. 11-288087, the polyimide precursor of Unexamined-Japanese-Patent No. 11-282155, etc. can be used. These may be used individually by 1 type and may mix and use 2 or more types.

As molecular weight of binders, such as the said polyamide (imide) or polyimide precursor, 3,000-500,000 are preferable and 5,000-100,000 are more preferable. When the said molecular weight is less than 3,000, the tackiness of the surface of a photosensitive layer may become strong, and after hardening of the photosensitive layer mentioned later, a film quality may become weak or surface hardness may deteriorate, and when it exceeds 500,000, Developability may deteriorate.

5-70 mass% is preferable, and, as for solid content in the photosensitive composition solid content of the said binder, 10-50 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the tackiness of the surface of the photosensitive layer may deteriorate. When the content exceeds 70% by mass, the exposure sensitivity may decrease. have.

[(B) Polymerizable Compound]

There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has at least 1 addition polymerization group in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is preferable, For example, (meth) acryl At least 1 sort (s) chosen from the monomer which has a group is mentioned preferably.

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 a) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylolpropane triacrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedioldi (meth) acrylate, trimethylolpropane Tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin, bisphenol (Meth) acrylate after addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols such as Urethane acrylates described in each publication such as yttrate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates, methacrylates, etc., such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

5-50 mass% is preferable, and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. When the solid content is less than 5% by mass, problems may occur such as deterioration of developability and a decrease in exposure sensitivity, and when it exceeds 50% by mass, the adhesiveness of the photosensitive layer may be too strong, which is not preferable.

[(C) Photopolymerization Initiator]

As said photoinitiator, there is no restriction | limiting in particular as long as it has the ability to start superposition | polymerization of the said polymeric compound, Although it can select suitably from well-known photoinitiators, For example, what has photosensitivity with respect to visible light from an ultraviolet range is preferable. And an activator that causes some action with the photoexcited sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer.

In addition, the photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 in the range of about 300 to 800 nm (more preferably, 330 to 500 nm).

As said photoinitiator, a halogenated hydrocarbon derivative (for example, having a triazine skeleton, an oxadiazole skeleton, etc.), phosphine oxide, hexa aryl biimidazole, an oxime derivative, an organic peroxide, a thio compound , Ketone compounds, aromatic onium salts, metallocenes and the like.

As a halogenated hydrocarbon compound which has the said triazine skeleton, Wakabayashi et al., Bull. Chem. Soc. Compounds described in Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in JP-A-53-133428, compounds described in JP 3337024, FCSchaefer and the like. 0rg. Chem; 29, 1527 (1964), a compound of JP-A-62-58241, a compound of JP-A-5-281728, a compound of JP-A-5-34920, United States And the compounds described in patent 4212976.

Wakabayashi et al., Bull. Chem. Soc. As a compound of Japan, 42, 2924 (1969), the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As a compound of the said British patent 1388492 specification, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As a compound of the said Unexamined-Japanese-Patent No. 53-133428, the compound etc. which were described in Unexamined-Japanese-Patent No. 2005-258431, etc. are mentioned, for example.

As a compound of the said German patent 3337024 specification, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

J. 0rg. Chem. By F. C. Schaefer et al .; As a compound of 29, 1527 (1964), the compound etc. which were described in Unexamined-Japanese-Patent No. 2005-258431 are mentioned, for example.

As a compound of the said Unexamined-Japanese-Patent No. 62-58241, the compound etc. which were described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As a compound of the said Unexamined-Japanese-Patent No. 5-281728, the compound etc. which were described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As said compound of Unexamined-Japanese-Patent No. 5-34920, the compound etc. which were described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As a compound described in the said US patent 4212976, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As said phosphine oxide, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As said hexaaryl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (o-fluorine, for example) Rophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5 , 5'-tetra (3-methoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-methoxyphenyl) biimidazole , 2,2'-bis (4-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2- Methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-trifluoromethylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, And the compounds described in WO00 / 52529.

The biimidazoles are, for example, Bull. Chem. Soc. Japan, 33, 565 (1960) and J. Org. It can be synthesize | combined easily by the method disclosed by Chem, 36 (16) 2262 (1971).

Examples of the oxime derivatives preferably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) Iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. are mentioned.

As said organic peroxide, 3,3 ', 4,4'- tetra (t-butylperoxycarbonyl) benzophenone etc. are mentioned, for example.

As said thio compound, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy cyoxanthone, 2-benzoylmethylene-3-methyl naphthothiazoline And the like.

As said ketone compound, the compound etc. which are described, for example in Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

As said aromatic onium salt, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, a triphenyl sulfonium tetrafluoro borate, a triphenyl sulfonium hexafluoro phosphonate, tetra, for example. Phenylphosphonium-hexafluorophosphate and the like.

Examples of the metallocenes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl Titanium, η ⁵ -5-cyclopentadienyl- η ⁶ -cumenyl-an (1 +)-hexafluorophosphate (1-), and the like.

Moreover, as a photoinitiator of that excepting the above, polyhalogen compounds, such as N-phenylglycine (for example, carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), amines (for example, 4-dimethyl) Ethyl aminobenzoate, 4-dimethylaminobenzoic acid n-butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimideethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl, pentamethylene ester of 3-dimethylaminobenzoic acid, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethyl Aminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenyl Amine, N-methyl-N-phenylbenzylamine, 4-bromine-N, N-dimeth Aniline, tridodecylamine, crystal violet lactone, leuco crystal violet, etc.), Japanese Patent Laid-Open No. 53-133428, Japanese Patent Laid-Open No. 57-1819, Japanese Patent Laid-Open No. 57-6096, and US Patent No. 3615455 The compound described in the above is mentioned.

Moreover, in addition to the said photoinitiator, it is possible to add a sensitizer in order to adjust the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer mentioned later.

The said sensitizer can be suitably selected with visible light, an ultraviolet light, a visible light laser, etc. as light irradiation means mentioned later.

The sensitizer is excited by an active energy ray, and interacts with other substances (e.g., radical generators, acid generators, etc.) (e.g., energy transfer, electron transfer, etc.) It is possible to generate useful groups such as these.

In addition, these compounds not only improve the sensitivity of the photosensitive layer, but also have a function as a photopolymerization initiator that initiates polymerization of the monomers by photo-excitation.

There is no restriction | limiting in particular as said sensitizer, Although it can select suitably from well-known sensitizers, For example, well-known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (e.g. indocarbocyanine, thiacarbocyanine, oxacarbocyanine), melocyanines (e.g. melo Cyanine, carbomelocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acrylflavin), anthra Quinones (for example, anthraquinone), squariases (for example, squalarium), etc. are mentioned.

As said sensitizer, a heterocyclic ring-type compound is further preferably listed. The heterocyclic ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. As said heterocyclic ring-type compound, a heterocyclic ring-type ketone compound, a quinoline compound, an acridine compound is mentioned, for example.

Specific examples of the heterocyclic ring-type ketone compound include acridons such as acridon, chloro acridon, N-methyl acridon, N-butyl acridon and N-butyl-chloro acredon. compound; 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'-carbonyl bis (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-dipropoxycoumarin, 7-benzo Triazole-2-ylcoumarin, 7-diethylamino-4-methylcoumarin, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japanese Patent Laid-Open No. 2002-363206, Japanese Patent Laid-Open Coumarins such as coumarin compounds described in 2002-363207, Japanese Patent Laid-Open No. 2002-363208, Japanese Patent Laid-Open No. 2002-363209 and the like; And the like.

Specific examples of the quinoline compound include quinoline, 9-hydroxy-1,2-dihydroxyquinolin-2-one, 9-ethoxy-1,2-dihydrquinolin-2-one and 9- Dibutylamino-1,2-dihydroquinolin-2-one, 8-hydroxyquinoline, 8-mercaptoquinoline, quinoline-2-carboxylic acid and the like.

Specific examples of the acridine compound include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, acridine orange, chloroflavin, acrylflavin and the like. This is listed. It is more preferable to contain a nitrogen element in a ring among these heterocyclic compounds. As what contains a nitrogen element in the said ring, the said acridine compound, the coumarin compound substituted by the amino group, an acridon compound, etc. are mentioned preferably. Among these, the said acridon, the coumarin substituted by the amino group, 9-phenylacridine, etc. are more preferable, and the said acridon is especially preferable.

As a combination of the said photoinitiator and the said sensitizer, the electron transfer type | system | group starter described in Unexamined-Japanese-Patent No. 2001-305734 [(1) electron donation type initiator and sensitizing dye, (2) electron accepting type initiator and a sensitizing dye, for example. , (3) electron donating type initiator, sensitizing dye, and electron accepting type initiator (three-way initiator)].

As content of the said sensitizer, 0.05-30 mass% is preferable with respect to the all components in the said photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% is especially preferable. When the said content is less than 0.05 mass%, the sensitivity to an active energy ray falls, an exposure process may take time, productivity may fall, and when it exceeds 30 mass%, it will increase and decrease from the said photosensitive layer at the time of storage. There is a case where I settle.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

As a particularly preferable example of the photopolymerization initiator, in the following exposure, a halogenated hydrocarbon compound having an phosphine oxide, the α-aminoalkyl ketone, and the triazine skeleton and an amine compound capable of responding to a laser beam having a wavelength of 405 nm are combined. Complex photoinitiators, hexaaryl biimidazole compounds, hexaaryl biimidazole compounds, heterocyclic compounds, and metallocenes.

Moreover, even if it uses together a chain transfer agent (for example, a mercapto compound, more specifically 2-mercapto benzimidazole, 2-mercapto benzoxazole, 2-mercaptobenzoxazole, etc.) with these initiators, good.

As content in the said photosensitive composition of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

[(D) At least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3)]

The compounds represented by the following general formulas (1) to (3) do not cause a reaction at low temperature or normal temperature, and have a function as a thermal crosslinking agent which initiates a crosslinking reaction by heating. By incorporating the compound into the photosensitive composition of the present invention, the photosensitive composition does not react at low or normal temperature, and excellent storage stability can be achieved, and at the time of heat treatment, it exhibits a rapid reaction at the heat treatment temperature and cures. Hardened | cured material excellent in surface hardness, alkali resistance, etc. is obtained.

However, P in the said General formula (1), (2), and (3) represents either an oxygen atom, a carbonyl group, an amide group, a urethane group, alkylene, and arylene. Q represents any of a boron atom, a nitrogen atom, alkylene, and arylene. W represents naphthalene having a bond with two X moieties. A ^{1 to} A ⁵ represent any one of a single bond, alkylene and arylene, and X ^{1 to} X ⁶ represent any one of -OCONH-, -NHCOO-, -NHCO-, and -CONH-. R ¹ to R ⁶ represent any one of a hydrogen atom, a halogen atom, an alkyl group and an aryl group.

In the general formulas (1) to (3), the alkylene of P is unsubstituted alkylene; At least one of an aryl group, an alkenyl group, and a hydroxyl group, and the substituent containing alkylene substituted by at least any one of an alkoxy group, a cyano group, and a halogen atom are shown.

As said unsubstituted alkylene, you may have a branch, you may have a double bond and a triple bond, It is preferable that total carbon number is 1-20, and 1-8 are especially preferable. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, cyclohexylene and the like.

As an aryl substituent in the said substituent containing alkylene, it is preferable that it is 6-30 total carbons, 6-15 are especially preferable, As a substituent, for example, a phenyl group, a naphthyl group, anthracenyl group, a methoxyphenyl group, a chlorophenyl group And the like.

As an alkenyl substituent in the said substituent containing alkylene, 2-10 total carbons are preferable, 2-6 are especially preferable, As a substituent, an ethynyl group, a propenyl group, butyryl group etc. are mentioned, for example.

As an alkoxy substituent in the said substituent containing alkylene, you may have a branch, 1-10 total carbons are preferable, 1-5 are especially preferable, As a substituent, a methoxy group, an ethoxy group, a propyloxy group, 2 -Methylpropyloxy group, butoxy group, etc. are mentioned.

As such a substituent containing alkylene, you may have a branch, you may have a double bond and a triple bond, 2-40 carbon atoms are preferable, and 2-25 are especially preferable. Examples of such substituted-containing alkylene include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group and the like.

Examples of the arylene group P is as defined and arylene, which is described later A ¹ ~A ^5.

In the general formulas (1) to (3), as the alkylene of Q, the unsubstituted alkylene may be cited, and as the unsubstituted alkylene may have a branch, and may have a double bond or a triple bond. The total carbon number is preferably 2 to 30. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, cyclohexylene and the like.

As the arylene and Q is as defined and arylene, which is described later A ¹ ~A ^5.

In said general formula (1)-(3), the coupling | bonding site | part with the X part of said W is 1, 2 position, 1, 3 position, 1, 5 position, 1, 6 position, 1, 7 position, 1, 8 It is a position, 2, 3 position, 2, 4 position, 2, 5 position, 2, 7 position, and W may be substituted by any of an alkyl group, an aryl group, an alkoxy group, and a halogen atom.

In the general formulas (1) to (3), the arylene of A ^{1 to} A ⁵ is a substituent substituted with at least one of a benzene ring and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, a cyano group, and a halogen atom. Containing arylene is shown.

As an alkyl group in the said substituent containing arylene, you may have a branch, you may have a double bond, and a triple bond, 1-20 pieces are preferable, and, as for total carbon number, 1-10 pieces are especially preferable. Examples of such alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, butyryl group, cyclohexyl group and cyclohexenyl group.

The aryl substituent in the substituent-containing arylene is preferably 6 to 30 carbon atoms, particularly preferably 6 to 15 carbon atoms. Examples of the substituent include a phenyl group, naphthyl group, anthracenyl group, methoxyphenyl group, chlorophenyl group, and the like. This is listed.

As an alkyl group in the said substituent containing arylene, you may have a branch, you may have a double bond, and a triple bond, 1-20 pieces are preferable, and, as for total carbon number, 1-10 pieces are especially preferable. Examples of such alkyl groups include methyl, ethyl, ethynyl, propyl, isopropyl, butyl, s-butyl, t-butyl, butyryl, cyclohexyl and cyclohexenyl groups.

As an alkenyl substituent in a substituent containing arylene, 2-10 total carbons are preferable, 2-6 are especially preferable, For example, an ethynyl group, a propenyl group, butyryl group etc. are mentioned as said substituent.

As an alkoxy substituent in a substituent containing arylene, it may have a branch, 1-10 total carbons are preferable, 1-5 are especially preferable, As a substituent, a methoxy group, an ethoxy group, a propyloxy group, 2- Methylpropyloxy group, butoxy group, etc. are mentioned.

Such substituent-containing arylene may have a branch, may have a double bond, or a triple bond, 2-40 total carbon atoms are preferable, and 2-25 are especially preferable.

As such substituent-containing arylene, for example, methylphenyl ring, dimethylphenyl ring, dibutylphenyl ring, methoxyphenyl ring, cyclohexylphenyl ring, biphenyl structure, dichlorophenyl ring, tribromophenyl ring, chlorocyanophenyl Rings and the like.

In addition, the alkylene of said A <^1> -A <^5> is synonymous with the alkylene of said P.

In said general formula (1)-(3), said X <^1> -X <^6> represents either -OCONH-, -NHCOO-, -NHCO-, and -CONH- as mentioned above.

In the general formulas (1) to (3), the alkyl group of R ¹ to R ⁶ is an unsubstituted alkyl group; At least one of an aryl group, an alkenyl group and a hydroxyl group, and at least one of an alkoxy group, cyano group and a halogen atom, and at least any one of an oxygen atom, a sulfur atom, a carbonyl group, an amide group, a urethane group and a urea group The substituent containing alkyl group which may have either of the divalent groups of one and an ester group is shown.

As said unsubstituted alkyl group, you may have a branch, you may have a double bond, and a triple bond, 1-20 pieces are preferable, and 1-10 pieces are especially preferable. Examples of such alkyl groups include methyl, ethyl, ethynyl, propyl, isopropyl, butyl, s-butyl, t-butyl, butyryl, cyclohexyl and cyclohexenyl groups.

As an aryl substituent in the said substituent containing alkyl group, the thing of 6-30 total carbons is preferable, 6-15 are especially preferable, As said substituent, a phenyl group, a naphthyl group, anthracenyl group, a methoxyphenyl group, chloro phenyl group, etc. are mentioned, for example. This is listed.

As an alkenyl substituent in the said substituent containing alkyl group, 2-10 total carbons are preferable, 2-6 are especially preferable, As said substituent, an ethynyl group, a propenyl group, butyryl group etc. are mentioned, for example.

As an alkoxy substituent in the said substituent containing alkyl group, you may have a branch, 1-10 total carbons are preferable, 1-5 are especially preferable, As a substituent, a methoxy group, an ethoxy group, a propyloxy group, 2 -Methylpropyloxy group, butoxy group, etc. are mentioned.

Such a substituent-containing alkyl group may have a branch, and may have a double bond and a triple bond, 2-40 carbon atoms are preferable, and 2-25 are especially preferable. Examples of such substituent-containing alkyl group include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group and the like.

Specific examples of the compound represented by the general formula (1) include compounds represented by the following structural formulas (1) to (10), but are not limited to these compounds.

Among the compounds represented by the structural formulas (1) to (10), the compounds represented by the structural formulas (1), (2), (4) to (7) and (9) are particularly preferable.

The compounds represented by the general formulas (1) to (3) are compounds having two or more oxirane rings in one molecule having a substituent in the oxirane ring moiety, and it is ¹ H- that these compounds are contained in the photosensitive composition. The NMR spectrum can be measured and identified.

[Combination of thermal crosslinking agent]

In addition to the compounds represented by General Formulas (1) to (3) which function as the heat crosslinking agent, other conventionally known heat crosslinking agents may be further used in combination.

There is no restriction | limiting in particular as said other thermal crosslinking agent, According to the objective, in order to improve the film strength after hardening of the photosensitive layer formed using the said photosensitive composition, in the range which does not adversely affect 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.

As an epoxy compound which has at least two oxirane groups in the said 1 molecule, For example, a bixylenol type or a biphenol type epoxy resin ("YX4000 Japan epoxy resin company make", etc.), these mixtures, an isocyanurate skeleton etc. are mentioned. Heterocyclic cyclic epoxy resin ("TEPIC; Nissan Chemical Co., Ltd.", "Araldite PT810; Chiba Specialty Chemicals Co., Ltd."), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, Hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolak) Epoxy resin, etc.), allyl group-containing bisphenol A epoxy resin, tris phenol methane epoxy resin, diphenyl dimethanol epoxy G, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; Dainippon Ink and Chemicals", etc.), glycidylamine type epoxy resin (diaminodiphenylmethane type) Epoxy resin, diglycidyl aniline, triglycidylaminophenol, etc., glycidyl ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, Hydantoin type epoxy resin, alicyclic epoxy resin (3, 4- epoxycyclohexyl methyl-3 ', 4'- epoxycyclohexane carboxylate, bis (3, 4- epoxy cyclohexyl) Methyl) adipate, dicyclopentadiene diepoxide, `` GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industry, '' etc.), imide alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A Novolak epoxy resin, te Laphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercial item Examples include "ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemicals Co., Ltd. &quot;), a polyphenol compound obtained by addition reaction of a phenol compound and diolefin compounds such as divinylbenzene and dicyclopentadiene, and a reaction product of epichlorohydrin, 4-vinylcyclohexene Epoxidized ring-opening polymer of -1-oxide with peracetic acid or the like, epoxy resin having linear phosphorus containing structure, epoxy resin having cyclic phosphorus containing structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal Epoxy resin, azo phenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer type epoxy resin ("CP-50S, CP-50M; Japanese fats and oils production ", etc., the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, bis (glycidyl oxyphenyl) fluorene type Although a foxy resin, bis (glycidyl oxyphenyl) adamantane type epoxy resin, etc. are mentioned, It is not limited to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether and 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) Methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate Or a compound having an oxetane group, a novolak resin, a poly (p-hydroxy styrene), a cardo-type bisphenol, a kalisarene, a calix resorcinarene, in addition to polyfunctional oxetanes such as these oligomers or copolymers, Ether compounds, such as resin which has hydroxyl groups, such as a silsesquioxane, are mentioned, In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

In addition, in order to promote thermosetting of the epoxy compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N Amine compounds such as, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzyl ammonium chloride; Block isocyanate compounds such as dimethylamine; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2- Imidazole derivative bicyclic amidine compounds such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and salts thereof; Phosphorus compounds such as triphenylphosphine; Guanamine compounds, such as melamine, guanamine, acetoguanamine and benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S- S-triazine derivatives, such as a triazine isocyanuric acid adduct and a 2, 4- diamino-6-methacryloyloxyethyl-S-triazine and an isocyanuric acid adduct; Etc. can be used. These may be used individually by 1 type and may use 2 or more types together. In addition, as long as it can accelerate | stimulate reaction of the hardening catalyst of the said epoxy compound, the said oxetane compound, or these, and a carboxyl group, there is no restriction | limiting in particular, You may use the compound which can promote the thermosetting of that excepting the above.

As content of solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the compound which can promote thermosetting of these and a carboxylic acid, it is 0.01-15 mass% normally.

As the thermal crosslinking agent, a polyisocyanate compound described in Japanese Patent Application Laid-Open No. 5-9407 can be used, and the polyisocyanate compound is derived from an aliphatic, cyclic aliphatic or aromatic group-substituted aliphatic compound containing at least two isocyanate groups. You may be. Specifically, difunctional isocyanate (for example, a mixture of 1,3-phenylenediisocyanate and 1,4-phenylenediisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1, 4-xylylene diisocyanate, bis (4-isocyanatephenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate and Polyfunctional alcohols such as trimethylolpropane, pentaerythritol and glycerin; An adduct of an alkylene oxide adduct of the polyfunctional alcohol and the difunctional isocyanate; Cyclic trimers and biuret bodies such as hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate and derivatives thereof; Norbornane diisocyanate; And the like.

Moreover, you may use the compound obtained by making a blocking agent react with the isocyanate group of the said polyisocyanate and its derivative (s) for the purpose of improving the storage property of the photosensitive composition of this invention and the photosensitive film mentioned later.

As said isocyanate group blocking agent, alcohols (for example, isopropanol, tert-butanol, etc.), lactams (for example, (epsilon) -caprolactam, etc.), phenols (for example, phenol, cresol, p-tert- butylphenol , p-sec-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (for example, 3-hydroxypyridine, 8-hydroxyquinoline, etc.) And active methylene compounds (e.g., dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetooxime, cyclohexanone oxime, etc.). In addition, the compound etc. which have any one of at least 1 polymerizable double bond and at least 1 block isocyanate group in the molecule | numerator of Unexamined-Japanese-Patent No. 6-295060 can be used.

In addition, a melamine derivative may be used as the thermal crosslinking agent. Examples of the melamine derivatives include methylolmelamine, alkylated methylolmelamine (compounds obtained by etherification of methylol with methyl, ethyl, butyl, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated methylol melamine is preferred, and hexamethylated methylol melamine is particularly preferable because of its good storage stability, and the effect of improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

Moreover, as other heat crosslinking agents, aldehyde condensation products other than melamine, resin precursors, etc. can be used. Specifically, N, N'- dimethylol urea, N, N'- dimethylol malonamide, N, N'- dimethylol succinimide, 1, 3-N, N'- dimethylol terephthalamide, 2, 4,6-trimethylolphenol, 2,6-dimethylol-4-methylolanisole, 1,3-dimethylol-4,6-diisopropylbenzene, and the like. Instead of these methylol compounds, corresponding ethyl or butyl ethers or esters of acetic acid or propionic acid may be used.

As solid content in the photosensitive composition solid content of the compound represented by the said General formula (1)-(3), and other heat crosslinking agent, 1-50 mass% is preferable, and 3-30 mass% is more preferable. When the said content is less than 1 mass%, reaction at the time of heat processing may fall, the improvement of the film strength of a cured film may not be planable, and when it exceeds 50 mass%, developability, the fall of exposure sensitivity, and hardening The film hardness of the film may be lowered in some cases.

Thermosetting accelerator

In order to promote thermosetting of the epoxy acrylate compound in the binder, a conventionally known thermosetting accelerator can be blended. As said thermosetting accelerator, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl- Amine compounds such as N, N-dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzyl ammonium chloride; Block isocyanate compounds blocked with dimethylamine or the like; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2- Imidazole derivative bicyclic amidine compounds such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and salts thereof; Phosphorus compounds such as triphenylphosphine; Guanamine compounds, such as melamine, guanamine, acetoguanamine and benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S- S-triazine derivatives, such as a triazine isocyanuric acid adduct and a 2, 4- diamino-6-methacryloyl oxyethyl-S-triazine and an isocyanuric acid adduct; Etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

The thermosetting accelerator is not particularly limited as long as it can promote thermosetting of the epoxy acrylate compound, and a compound capable of promoting thermosetting other than the above may be used.

It is preferable that solid content in the said photosensitive composition solid content of the said thermosetting accelerator is 0.01-15 mass%.

[Other Ingredients]

As said other components, a thermal polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye), a sieving pigment, etc. are mentioned, for example, Adhesion promoter to a surface of a base material, and other preparations (for example, electroconductive particle) , Fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, and the like. By containing these components suitably, properties, such as stability, a photographic property, film | membrane property, etc. of the target photosensitive composition or photosensitive film, can be adjusted.

Thermal polymerization inhibitor

The thermal polymerization inhibitor may be added in order to prevent thermal polymerization or polymerization with time of the polymerizable compound.

Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydride. Roxy benzophenone, first copper chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl-6 t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic xylates reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and A1 And chelates with.

As content of the said thermal polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. When the said content is less than 0.001 mass%, stability at the time of storage may fall, and when it exceeds 5 mass%, the sensitivity with respect to an active energy ray may fall.

-Pigmentation 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 (CI42595), Oramine (CI41000), Fat black HB (CI26150), Mono light, Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Host star red ESB (CI pigment violet 19), permanent ruby FBH (CI pigment red 11), pastel pink B spura (CI pigment red 81) monastral first blue (CI pig) Blue 15), monolight first black B (CI pigment black 1), carbon, CI pigment red 97, CI pigment red 122, CI Pigment Red 149, C.I. Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Green 36, CI Pigment blue 15: 1, CI pigment blue 15: 4, CI pigment blue 15: 6, CI pigment blue 22, CI Pigment blue 60, C.I. pigment blue 64, and the like. These may be used individually by 1 type and may use 2 or more types together.

Solid content content in the said photosensitive composition solid content of the said coloring pigment can be determined in consideration of exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, and it changes with kinds of the said coloring pigment, but is generally 0.01-10 Mass% is preferable and 0.05-5 mass% is more preferable.

Constitution Pigment

If necessary, inorganic pigments and organic fine particles are added to the photosensitive composition for the purpose of improving the surface hardness of the permanent pattern, or suppressing the coefficient of linear expansion low, or reducing the dielectric constant and dielectric loss tangent of the cured film itself. can do.

There is no restriction | limiting in particular as said inorganic pigment, It can select from a well-known thing suitably, For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, fine powder silicon oxide, vapor phase silica, amorphous silica, crystalline silica, melting Silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like.

Less than 10 micrometers is preferable and, as for the average particle diameter of the said inorganic pigment, 3 micrometers or less are more preferable. When the said average particle diameter is 10 micrometers or more, resolution may deteriorate by optical confusion.

There is no restriction | limiting in particular as said organic microparticles | fine-particles, According to the objective, it can select suitably, For example, a melamine resin, benzoguanamine resin, crosslinked polystyrene resin, etc. are mentioned. Moreover, the spherical porous fine particles which consist of silica of about 1-5 micrometers of average particle diameters, oil absorption amount of about 100-200m <^2> / g, crosslinking resin, etc. can be used.

As for the addition amount of the said extender pigment, 5-60 mass% is preferable. If the addition amount is less than 5% by mass, the coefficient of linear expansion may not be sufficiently lowered. If the amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, the film quality of the cured film becomes weak and permanent. When wiring is formed using a pattern, the function as a protective film of wiring may be impaired.

Adhesion Promoter

In order to improve the adhesiveness between each layer, or the adhesiveness of a photosensitive layer and a base material, what is called a well-known so called adhesion promoter can be used for each layer.

As said adhesion promoter, the adhesion promoter described in Unexamined-Japanese-Patent No. 5-11439, Unexamined-Japanese-Patent No. 5-341532, Unexamined-Japanese-Patent No. 6-43638, etc. is mentioned preferably, for example. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-tria Sol-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione and 2-mercapto-5-methylthio -Thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to the all components in the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1 mass%-5 mass% are especially preferable.

The photosensitive composition of the present invention can be image-formed by UV exposure, has low surface tack, good lamination and handling properties, does not cause a reaction at room temperature at the time of storage, is excellent in storage stability, and develops with high sensitivity. It shows excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation after development. For this reason, protective films of printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, color filters and aggregates, rib members, spacers, partitions, display members, such as partition walls, holograms, micromachines, and proofs. It can be widely used for permanent pattern formation, such as these, and can especially use for the photosensitive film of this invention, a permanent pattern, and its formation method.

(Photosensitive film)

The photosensitive film of the present invention comprises at least a support and a photosensitive layer, preferably a protective film, and, if necessary, includes other layers such as a cushion layer, an oxygen barrier layer (PC layer), and the like. It is done by

There is no restriction | limiting in particular as a form of the said photosensitive film, According to the objective, it can select suitably, For example, on the said support body, the form which contains the said photosensitive layer and the said protective film film in this order, on the said support body, The form which comprises the said PC layer, the said photosensitive layer, and the said protective film in this order, the form which includes the said cushion layer, the said PC layer, the said photosensitive layer, and the said protective film in this order on the said support body, etc. are enumerated. do. The photosensitive layer may be a single layer or a plurality of layers.

[Photosensitive layer]

The photosensitive layer is formed by the photosensitive composition of the present invention.

There is no restriction | limiting in particular as a location formed in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it is laminated | stacked on the said support body.

The photosensitive layer is modulated with light from the light irradiation means by the light modulating means having n drawing portions that receive and emit light from the light irradiation means in the exposure step to be described later. It is preferable to be exposed to light through a microlens array in which a microlens having an aspherical surface capable of correcting aberration due to deformation of the exit face of? Is arranged.

When exposing and developing the said photosensitive layer, the minimum energy of the light used for the said exposure which does not change the thickness of the part which exposes the said photosensitive layer after the said exposure and image development is 0.1-100 (mJ / cm <^2> ). It is preferable that it is and it is more preferable that it is 1-80mJ / cm <^2> . If the minimum energy of light used for the exposure is less than 0.1mJ / cm ^2, and if the machining margin is narrowed, if it exceeds 100mJ / cm ^2, it is not preferable since a long tact time.

Here, "the minimum energy of the light used for the said exposure which does not change the thickness of the part which exposes the said photosensitive layer after the said exposure and image development" is what is called image development sensitivity, for example, when the said photosensitive layer is exposed, It can obtain | require from the graph (sensitivity curve) which shows the relationship between the energy amount (exposure amount) of the light used for the said exposure, and the thickness of the said hardened layer produced | generated by the said developing process continued to the said exposure.

The thickness of the cured layer increases as the exposure amount increases, and then becomes constant while being substantially equal to the thickness of the photosensitive layer before the exposure. The said developing sensitivity is a value calculated | required by reading the minimum exposure amount when the thickness of the said hardened 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.

There is no restriction | limiting in particular as a measuring method of the thickness of the said hardened layer and the said photosensitive layer before the exposure, Although it can select suitably according to the objective, A film thickness measuring apparatus and a surface roughness measuring instrument (for example, Surfcom 1400D (Tokyo Precision) The method of measurement using the company make) is mentioned.

There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 3-100 micrometers is preferable and 5-70 micrometers is more preferable.

As a formation method of the said photosensitive layer, the method of laminating | stacking by preparing the photosensitive composition solution by dissolving, emulsifying, or disperse | distributing the said photosensitive composition of this invention in water or a solvent on the said support body, apply | coating the said solution directly, and enumerating are listed do.

There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol ; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 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 hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethylformamide, dimethylacetamide, dimethylsulfooxide, sulfolane and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, you may add a well-known surfactant.

There is no restriction | limiting in particular as said coating method, According to the objective, it can select suitably, For example, apply | coating directly to the said support body using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method is listed.

As said drying conditions, although it changes also with each component, a kind of solvent, a use ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60-110 degreeC.

[Support]

There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, it is preferable that the said photosensitive layer is peelable, and that light transmittance is favorable, and that surface smoothness is more preferable.

The support is made of synthetic resin and is preferably transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) Acrylic 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 a low ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is especially preferable. These may be used individually by 1 type and may use 2 or more types together.

Moreover, as said support body, it is described, for example in Unexamined-Japanese-Patent No. 4-208940, Unexamined-Japanese-Patent No. 5-80503, Unexamined-Japanese-Patent No. 5-173320, Unexamined-Japanese-Patent No. 5-72724, etc., for example. Supports can be used.

There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

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

[Protective film]

The protective film has a function of preventing and protecting contamination or damage of the photosensitive layer.

There is no restriction | limiting in particular as a location formed in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, it is normally formed on the said photosensitive layer.

As said protective film, what is used for the said support | support, for example, the silicone paper, polyethylene, the paper laminated with polypropylene, a polyolefin or a polytetrafluoroethylene sheet, etc. are mentioned, Among these, a polyethylene film and a polypropylene film are preferable. Do.

There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.

When using the said protective film, it is preferable that the adhesive force A of the said photosensitive layer and said support body, and the adhesive force B of the said photosensitive layer and protective film are the relationship of adhesive force A> adhesive force B.

As a combination (support / protective film) of the said support body and a protective film, it is polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, for example. And the like. In addition, by surface-treating at least any one of a support body and a protective film, the relationship of the adhesive force mentioned above can be satisfied. The surface treatment of the support may be carried out in order to increase the adhesion with the photosensitive layer, and for example, application of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma Irradiation treatment, laser beam irradiation treatment, and the like.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.

When the said static friction coefficient is less than 0.3, it is too slippery, and when it makes into a roll shape, winding shift may generate | occur | produce, and when it exceeds 1.4, it may become difficult to wind up to a favorable roll shape.

It is preferable that the said photosensitive film is wound by the cylindrical core, for example, is wound up in the shape of a roll in the shape of a long picture, and is stored. There is no restriction | limiting in particular as length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. Moreover, you may slit process so that a user may use it, and you may make the elongate body of the range of 100-1,000m into roll shape. Moreover, in this case, it is preferable to wind up so that the said support body may become outermost. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. In storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the edge surface from the viewpoint of protecting the edge surface and preventing edge fusion. It is preferable to use.

You may surface-treat the said protective film in order to adjust the adhesiveness of the said protective film and the said photosensitive layer. The said surface treatment forms the undercoat layer which consists of polymers, such as a polyorganosiloxane, a fluorinated polyolefin, polyfluoroethylene, polyvinyl alcohol, on the surface of the said protective film, for example. The undercoat can be formed by applying the polymer coating liquid to the surface of the protective film and then drying at 30 to 150 ° C (in particular, 50 to 120 ° C) for 1 to 30 minutes.

Moreover, in addition to the said photosensitive layer, the said support body, and the said protective film, you may have layers, such as a cushion layer, an oxygen barrier layer (PC layer), a peeling layer, an adhesive layer, a light absorption layer, and a surface protective layer.

The cushion layer is a layer which does not have tackiness at normal temperature and melts and flows when laminated under vacuum and heating conditions.

The said PC layer is a film of about 0.5-5 micrometers normally formed using polyvinyl alcohol as a main component.

The photosensitive film of the present invention has small surface tack, good lamination and handling properties, excellent storage stability, high sensitivity and developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, and the like after development. It comprises a photosensitive layer in which the photosensitive composition is laminated. For this reason, it can be widely used for forming permanent patterns, such as a printed wiring board, a color filter, aggregate, a rib material, a spacer, a partition, a display member, a hologram, a micromachine, a proof, etc., The permanent pattern of this invention, and its formation method It can be used preferably.

In particular, in the photosensitive film of the present invention, since the thickness of the film is uniform, lamination to the substrate is performed more precisely at the time of forming the permanent pattern.

(Permanent pattern and permanent pattern formation method)

The permanent pattern of this invention is obtained by the permanent pattern formation method of this invention.

The permanent pattern formation method of this invention is a 1st aspect, apply | coats the photosensitive composition of this invention to the surface of a base material, and after drying and forming a photosensitive layer, it exposes, develops, and heats.

Moreover, the permanent pattern formation method of this invention is a 2nd aspect, after laminating | stacking the photosensitive film of this invention on the surface of a base material under at least one of heating and pressurization, it exposes, develops, and heats.

Hereinafter, the detail of the permanent pattern of this invention becomes clear through description of the permanent pattern formation method of this invention.

[materials]

There is no restriction | limiting in particular as said base material, From a well-known material, it can select suitably from the thing with high surface smoothness to the surface with an unevenness, A plate-shaped base material (substrate) is preferable, Specifically, well-known printed wiring board formation Substrates for use (e.g. copper clad laminates), glass plates (e.g., soda glass plates, etc.), synthetic resin films, papers, metal plates and the like are listed. Among these, printed wiring board forming substrates are preferred, and multilayer wiring boards are preferred. It is particularly preferable that the printed wiring board forming substrate is complete with wiring in that high density mounting of a semiconductor or the like into a buildup wiring board or the like becomes possible.

The said base material is a laminated body by which the photosensitive layer by the said photosensitive composition is formed on the said base material as said 1st form, or laminated | stacked by laminating | stacking so that the photosensitive layer in the said photosensitive film may overlap as said 2nd aspect. A sieve can be formed and used. That is, the exposed area which is mentioned later with respect to the said photosensitive layer in the said laminated body can be hardened | cured, and a permanent pattern can be formed by the phenomenon mentioned later.

Laminate

There is no restriction | limiting in particular as a formation method of the said 1st aspect, Although it can select suitably according to the objective, It is preferable to laminate | stack the photosensitive layer formed by apply | coating and drying the said photosensitive composition on the said base material.

There is no restriction | limiting in particular as said coating and drying method, According to the objective, it can select suitably, For example, the method similar to the coating and drying of the said photosensitive composition solution performed when forming the photosensitive layer in the said photosensitive film. The method of apply | coating the said photosensitive composition solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. is mentioned, for example.

There is no restriction | limiting in particular as a formation method of the said 2nd aspect, Although it can select suitably according to the objective, It is preferable to laminate | stack the said photosensitive film on the said base material, performing at least any one of heating and pressurization. Moreover, when the said photosensitive film has the said protective film, it is preferable to peel off the said protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.

There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.

There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

There is no restriction | limiting in particular as an apparatus which performs at least any of the said heating and pressurization, According to the objective, it can select suitably, For example, a heat press and a heat roll laminator (for example, Daesung Laminator Co., VP-II) , Vacuum laminators (eg, MKLP, MVLP 500) and the like are suitable.

Exposure process

The exposure step is a step of exposing the photosensitive layer.

As long as it is a material which has a photosensitive layer as an object of the said exposure, there is no restriction | limiting in particular and it can select suitably according to the objective, For example, with respect to the said laminated body in which the said photosensitive composition or the said photosensitive film is formed on a base material, It is preferable to be done.

There is no restriction | limiting in particular as exposure to the said laminated body, According to the objective, it can select suitably, For example, you may expose the said photosensitive layer through the said support body, a cushion layer, and a PC layer, and after peeling the said support body, After exposing the said photosensitive layer through a cushion layer and a PC layer, after peeling the said support body and a cushion layer, you may expose the said photosensitive layer through the said PC layer, after peeling the said support body, a cushion layer, and a PC layer You may expose the said photosensitive layer.

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

There is no restriction | limiting in particular as said digital exposure, Although it can select suitably according to the objective, For example, to generate a control signal based on the pattern formation information to form, and to perform it using the light modulated according to the said control signal desirable.

There is no restriction | limiting in particular as said means of digital exposure, According to the objective, it can select suitably, For example, the light which modulates the light irradiated from the said light irradiation means based on pattern information to form, Modulation means and the like.

<Optical Modulation Means>

There is no restriction | limiting in particular as long as it can modulate light as said optical modulation means, Although it can select suitably according to the objective, For example, it is preferable to have n drawing parts.

There is no restriction | limiting in particular as an optical modulation means which has the said n drawing parts, Although it can select suitably according to the objective, For example, a spatial light modulation element is preferable.

Examples of the spatial light modulator include digital micro mirror devices (DMD), MEMS (Micro Electro Mechanical Systems) type spatial light modulators (SLM; Special Light Modulator), and modulated transmitted light by electro-optic effects. Optical element (PLZT element), liquid crystal light shutter (FLC), etc. are mentioned, DMD is mentioned preferably among these.

It is also preferable that the light modulating means has a pattern signal generating means for generating a control signal based on the pattern information to be formed. In this case, the light modulating means modulates light according to the control signal generated by the pattern signal generating means.

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 preferably.

As a specific example of the said optical modulation means, the means etc. which are described in [0016]-[0047] of Unexamined-Japanese-Patent No. 2005-258431 are mentioned.

Light irradiation means

There is no restriction | limiting in particular as said light irradiation means, According to the objective, it can select suitably, For example, (super) high pressure mercury, xenon, etc., carbon arcs, halogen lamps, copiers, fluorescent tubes, LED, a semiconductor, etc. Known light sources, such as a laser, or the means which can irradiate by combining 2 or more lights are mentioned, Among these, the means which can irradiate by combining 2 or more lights are preferable.

As the light irradiated from the light irradiation means, for example, when light irradiation is carried out through a support, electromagnetic waves that transmit the support and activate the photopolymerization initiator and the sensitizer used, visible light from the ultraviolet ray, electron beam, X A line, a laser beam, etc. are enumerated, Among these, a laser beam is preferable and the laser beam which synthesize | combined two or more lights (henceforth "mold wave laser beam") is more preferable. Moreover, even when light irradiation is performed after peeling a support body, the same light can be used.

As said ultraviolet-ray wavelength of visible light, 300-1500 nm is preferable, 320-800 nm is more preferable, 330 nm-650 nm are especially preferable.

As a wavelength of the said laser beam, 200-1,500 nm is preferable, 300-800 nm is more preferable, 330 nm-500 nm are still more preferable, 395 nm-415 nm are especially preferable.

As means capable of irradiating the haptic laser light, for example, a means having a plurality of lasers, a multi-mode optical fiber, and a collective optical system for receiving the laser light irradiated from the plurality of lasers and coupling the multi-mode optical fiber to the multi-mode optical fiber is preferable.

As a means (fiber array light source) which can irradiate the said haptic laser, the means described in Paragraph No. [0130]-[0177] of Unexamined-Japanese-Patent No. 2005-316431, etc. are mentioned, for example.

<Microlens Array>

The exposure is preferably performed through the microlens array and may be performed through an aperture array, an imaging optical system, or the like.

There is no restriction | limiting in particular as said microlens array, Although it can select suitably according to the objective, For example, what arrange | positioned the microlens which has an aspherical surface which can correct the aberration by the deformation of the exit surface in the said drawing part is preferable. do.

There is no restriction | limiting in particular as said aspherical surface, Although it can select suitably according to the objective, For example, a toric surface is preferable.

Further, as the microlens array, the aperture array, and the imaging optical system, for example, paragraph numbers [0051] to [0063], paragraph numbers [0065] of [Patent No. 2005-258431], and [ The means described in 0070]-[0073], paragraph numbers [0083]-[0088], etc. are mentioned.

<Other optical system>

In the permanent pattern formation method of this invention, you may use together with the other optical system suitably selected from well-known optical systems, For example, the light quantity distribution correction optical system which consists of one combination lens, etc. are mentioned.

Specific examples of the light amount distribution correcting optical system include means described in, for example, paragraphs [0090] to [0105] of JP-A-2005-258431.

[Developing process]

The said developing process is a process of exposing the said photosensitive layer by the said exposure process, hardening the exposed area | region of the said photosensitive layer, and developing by removing a non-hardened area | region, and forming a permanent pattern.

There is no restriction | limiting in particular as a removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method of removing using a developing solution, etc. are mentioned.

There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, the hydroxide of alkali metal or alkaline-earth metal, or the carbonate, hydrogencarbonate, aqueous ammonia, the quaternary ammonium salt, etc. are mentioned preferably. Among these, an aqueous sodium carbonate solution is particularly preferable.

The developing solution may be a surfactant, an antifoaming agent, an organic base (eg, benzyl amine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.), In order to promote development, you may use together with an organic solvent (for example, alcohol, ketones, ester, ether, amide, lactone, etc.). The developer may be an aqueous developer in which water or an alkali aqueous solution and an organic solvent are mixed, or may be an organic solvent alone.

Curing Treatment Process

The permanent pattern formation method of this invention also contains a heat processing as a hardening process process, and also includes a whole surface exposure process as needed.

The said hardening process process is a process of performing hardening process with respect to the photosensitive layer in the permanent pattern formed after the said image development process is performed.

Heating treatment

The said heat processing is performed in order to achieve sufficient improvement of the film hardness by the thermal crosslinking effect of the compound represented by the said General Formula (1)-(3) contained in the photosensitive composition of this invention. As said heat processing, whole surface heat processing may be sufficient, heat processing may be performed in a pattern form, and the whole surface heat processing is especially preferable.

As a method of whole surface heat processing, the method of heating the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development process is mentioned. By whole surface heating, the crosslinking reaction of the compound represented by the said General formula (1)-(3) is accelerated | stimulated, and the film strength of the surface of the said permanent pattern becomes high.

As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the said heating temperature is less than 120 degreeC, the crosslinking reactivity of resin in the photosensitive composition by the compound represented by the said General formula (1)-(3) falls, and the improvement of the film strength by heat processing may not be obtained. When it exceeds 250 degreeC, decomposition | disassembly of resin in the said photosensitive composition generate | occur | produces, film quality may be weak, and it may become soft.

As heating time in the said whole surface heating, 10 to 120 minutes are preferable, and 15 to 60 minutes are more preferable.

There is no restriction | limiting in particular as an apparatus which performs said whole surface heating, According to the objective, it can select suitably from a well-known apparatus, For example, a dry oven, a hotplate, an IR heater, etc. are mentioned.

Full surface exposure treatment

As a method of the said front surface exposure process, the method of exposing the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development process is mentioned, for example. By said whole surface exposure, hardening of resin in the photosensitive composition which forms the said photosensitive layer is accelerated | stimulated, and the surface of the said permanent pattern is hardened.

There is no restriction | limiting in particular as an apparatus which performs said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned preferably.

Moreover, when the said base material is a printed wiring board, such as a multilayer wiring board, the permanent pattern of this invention can be formed on the said printed wiring board, and can be soldered as follows.

That is, by the said developing process, the hardened layer which is the said permanent pattern is formed, and a metal layer is exposed on the surface of the said printed wiring board. After plating with gold on the site | part of the metal layer exposed to the surface of the said printed wiring board, soldering is performed. And a semiconductor, a component, etc. are mounted in the soldered part. At this time, the permanent pattern by the said hardened layer functions as a protective film or an insulating film (interlayer insulation film), and the impact from the outside and the conduction of the electrodes of these neighbors are prevented.

In the permanent pattern formation method of this invention, it is preferable to form at least any one of a protective film, an interlayer insulation film, and a soldering resist pattern. 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 or bending from the outside. In particular, in the case of the interlayer insulating film, for example, a multilayer wiring board It is useful for high-density mounting of semiconductor components to build-up wiring boards and the like.

Since the pattern formation method of the present invention can form a pattern at high speed, it can be widely used for formation of various patterns, and especially can be used for formation of a wiring pattern.

Moreover, the permanent pattern formed by the permanent pattern formation method of this invention has the outstanding surface hardness, insulation, heat resistance, etc., and can be used suitably as a protective film, an interlayer insulation film, and a soldering resist pattern.

(Example)

Hereinafter, although the Example of this invention is described, this invention is not limited to a following example at all.

(Example 1)

Preparation of Photosensitive Composition

The photosensitive composition was prepared based on the following composition. Moreover, methyl ethyl ketone was used as a dispersion solvent, and 55 mass% of solid content concentration was prepared. Dispersion was carried out using a bead mill, and it was confirmed that the obtained dispersion was free of aggregation by a particle gauge.

[Composition of Photosensitive Composition Solution]

33.4 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30)

40.0 parts by mass of a binder represented by the following structural formula (46)

15.7 parts by mass of the compound (thermal crosslinking agent) represented by the above structural formula (1)

Dipentaerythritol hexaacrylate 16.0 parts by mass

IRGACURE 819 (Chiba Specialty Chemicals) 5.8 parts by mass

0.056 parts by mass of hydroquinone monomethyl ether

0.77 parts by mass of dicyandiamide

2MAOK ^{* 1} 0.47 parts by mass

* 1: 2MAOK is an isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine represented by the following structural formula (47): (Manufactured by Shikoku Kasei Kogyo Co., Ltd.).

Synthesis of Compound Represented by Structural Formula (1)

In addition, the compound represented by the said Formula (1) was synthesize | combined as follows.

50 mass parts of 4-hydroxybenzyl alcohol and 83.7 mass parts of epichlorohydrin were put into the reaction kiln, and it heated at 80 degreeC. 31.6 mass parts of 48% sodium hydroxide aqueous solution was dripped at the reaction kiln over 3 hours. The reaction was then carried out for 3 hours. After cooling, the mixture was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/7), and 59 mass parts (yield 84%) of 1st intermediate products were obtained.

Next, 4.84 mass parts of m-xylylene diisocyanate, 10 mass parts of said 1st intermediate products, and 14 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 90 degreeC. 0.02 mass part of stannock (made by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 2 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off and recrystallized from ethyl acetate to obtain 12.5 parts by mass of a white solid (yield 84%).

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.67 (t, 2H), 7.28-7.08 (m, 8H), 6.88 (d, 4H), 4.28 (d, 2H), 4.12 (q, 8H), 3.79 (q, 2H), 2.85 -2.77 (m, 8H), 2.70 (q, 2H).

In addition, content in the photosensitive composition of the compound represented by the said Formula (1) is 14 mass%.

Production of Photosensitive Film

The obtained photosensitive composition was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 µm as the support, and dried to form a photosensitive layer having a thickness of 30 µm. A polypropylene film having a thickness of µm was laminated with a laminate to prepare a photosensitive film.

Formation of permanent patterns

--Preparation of Laminates--

Next, as the base material, a chemical polishing treatment was performed on the surface of the copper-clad laminate (no through hole, 12 µm thick) for wiring formation to prepare. On the said copper clad laminated board, it laminates using a vacuum laminator (Nichigo Motor Co., Ltd. make, VP130), peeling the protective film in the said photosensitive film so that the photosensitive layer of the said photosensitive film may contact the said copper clad laminated board. The laminated body by which the said copper clad laminated board, the said photosensitive layer, and the said polyethylene terephthalate film (support) were laminated | stacked in this order was prepared.

The crimping conditions were 40 seconds of the time of vacuum processing, 70 degreeC of crimping temperature, 0.2MPa of crimping pressure, and 10 second of pressurization time.

<Evaluation of Tajik>

The tackiness of the surface of the photosensitive layer in the laminated body obtained as mentioned above was evaluated based on the following criteria. When the protective film in the photosensitive film of the said Example 1 was peeled off, there was no strong tackiness on the surface of the said photosensitive layer, and peeling itself could also be easily performed. The results are shown in Table 3.

[Evaluation standard]

(Circle): Strong tackiness was not confirmed on the surface of the photosensitive layer.

(Triangle | delta): Weak weakness was confirmed to the surface of the photosensitive layer.

X: Strong tackiness was confirmed on the surface of the photosensitive layer.

Exposure Process

The photosensitive layer in the prepared laminate is irradiated with a laser light of 405 nm from a polyethylene terephthalate film (support) side so as to obtain a pattern in which holes having different diameters are formed, and then exposed, thereby exposing the photosensitive layer. The area of part of the layer was cured.

Development Process

After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled from the laminate, and a 1% by mass aqueous solution of soda carbonate was used as an alkali developer to the entire surface of the photosensitive layer on the copper clad laminate, and the spray pressure was 0.2 MPa. The shower development was carried out at 30 ° C. for 60 seconds, and the uncured area was dissolved and removed. Thereafter, the mixture was washed with water and dried to form a permanent pattern.

--Hardening Process--

The whole surface of the laminated body in which the said permanent pattern was formed was heat-processed at 160 degreeC for 60 minutes, the surface of the permanent pattern was hardened, and the film strength was raised. When the permanent pattern was visually observed, no bubble was observed on the surface of the permanent pattern.

Exposure sensitivity, resolution, exposure speed, and storage stability were evaluated about the produced photosensitive film, and pencil hardness and dielectric properties were evaluated about the formed permanent pattern. The results are shown in Table 3.

<Exposure Sensitivity>

In the obtained permanent pattern, the thickness of the hardened region of the remaining photosensitive layer was measured. Next, the relationship between the irradiation amount of laser light and the thickness of the cured layer is plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the thickness of the cured region on the wiring became 15 µm, and the amount of light energy when the surface of the cured region was a glossy surface was used as the amount of light energy required for curing the photosensitive layer.

As a result, the amount of light energy required to cure the photosensitive layer was 30 mJ / cm ² .

<Resolution>

The surface of the obtained printed wiring board of the permanent pattern formation completed was observed with an optical microscope, the minimum hole diameter without a residual film was measured and this was made into the resolution. The smaller the numerical value, the better. As a result, the resolution was 70 µm.

<Exposure Speed>

Using a 405 nm laser exposure apparatus, the speed of moving the exposure light and the photosensitive layer relative to each other was changed to determine the speed at which the permanent pattern was formed. Exposure was performed from the polyethylene terephthalate film (support) side with respect to the photosensitive layer in the prepared laminated body. In addition, the faster the setting speed, the more efficient the permanent pattern formation becomes possible. Moreover, the said 405 nm laser exposure apparatus had the light modulation means which consists of said DMD, and the exposure speed was 13 mm / sec.

<Storage stability>

The developing time of the unexposed film | membrane was measured after 3 days of forced aging of the photosensitive film produced above at 40 degreeC.

<Pencil hardness>

After the gold plating was performed on the printed wiring board of the permanent pattern formation completed according to a conventional method, water soluble flux treatment was performed. Subsequently, it was immersed three times in the solder bath set to 260 degreeC over 5 second, and the flux was removed by water washing. And about the permanent pattern after the said flux removal, pencil hardness was measured based on JISK-5400.

As a result, the pencil hardness was 5H. Moreover, when visual observation was performed, peeling, swelling, and discoloration of the cured film in the said permanent pattern were not confirmed.

<Measurement of dielectric properties>

The dielectric properties of the cured film having a film thickness of 500 µm were measured at 25 ° C using an LCR meter manufactured by Azident Technology Co., Ltd. and a 4291A type solid electrode. As a result, the dielectric constant at 1 GHz was 3.3 and the dielectric tangent was 0.013.

(Example 2)

The photosensitive composition was prepared based on the following composition, the photosensitive film and the laminated body were prepared by the method similar to Example 1, and the permanent pattern was formed.

In addition, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 were evaluated for tackiness, exposure sensitivity, resolution, exposure speed, and storage stability. Evaluation was performed. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mJ / cm ² . Other results are shown in Table 3.

[Composition of Photosensitive Composition Solution]

Barium sulfate 33.4 parts by mass

Addition reaction product of styrene / maleic anhydride / butyl acrylate copolymer (molar ratio 40/32/28) and benzyl amine (1.0 equivalent to the anhydride group of the copolymer) ^{* 2} 40.0 parts by mass

15.7 parts by mass of the compound (thermal crosslinking agent) represented by the above structural formula (1)

Dipentaerythritol hexaacrylate 16.0 parts by mass

IRGACURE 819 (Chiba Specialty Chemicals) 5.8 parts by mass

0.056 parts by mass of hydroquinone monomethyl ether

0.77 parts by mass of dicyandiamide

2MAOK 0.47 parts by mass

* 2: a maleamic acid copolymer having unit A and unit B represented by the following structural formula (VII). The unit A is composed of a structural unit of two, and R ¹ is phenyl in one of the structural units of which, R ¹ in the other constituent unit is butyloxycarbonyl, R ³ and R ⁴ are hydrogen atoms to be. R ² in the unit B is benzyl. The mole fraction x of the repeating unit in the said unit A is 40 mol% with respect to the structural unit of said 1, 28 mol% with respect to the structural unit other than the above, and the mole fraction y of the repeating unit in the said unit B is 32 mol%. In addition, the reaction amount of the benzyl amine to the anhydride group of the styrene / maleic anhydride / butyl acrylate copolymer is 1.0 equivalent.

The glass transition temperature (Tg) of the homopolymer of butylacrylate which is the said vinyl monomer is -54 degreeC.

Content in the photosensitive composition of the epoxy resin compound represented by the said Structural formula (1) in Example 2 is 14 mass%.

(Example 3)

In Example 1, the addition amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 0.8 parts by mass, and the content in the photosensitive composition of the epoxy resin compound represented by the structural formula (1) is 0.8 mass% (1 mass) A photosensitive composition was prepared in the same manner as in Example 1 except that the composition was less than%), a photosensitive film and a laminate were prepared in the same manner as in Example 1, and a permanent pattern was formed.

Moreover, about the photosensitive film manufactured by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mJ / cm ² . Other results are shown in Table 3.

(Example 4)

In Example 1, the addition amount of the epoxy resin compound represented by the structural formula (1) in the photosensitive composition is 100 parts by mass, and the content in the photosensitive composition of the epoxy resin compound represented by the structural formula (1) is 51% by mass (50 masses). A photosensitive composition was prepared in the same manner as in Example 1 except that the concentration was greater than%), a photosensitive film and a laminate were prepared in the same manner as in Example 1, and a permanent pattern was formed.

Moreover, about the photosensitive film manufactured above by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mJ / cm ² . Other results are shown in Table 3.

(Examples 5 to 13)

In Example 1, the method similar to Example 1 except having changed the compound represented by the said Formula (1) in the photosensitive composition into the compound represented by the said Formula (2)-(10) shown in Table 3 is carried out. The photosensitive composition was prepared, the photosensitive film and the laminated body were prepared by the method similar to Example 1, and the permanent pattern was formed.

Moreover, about the photosensitive film manufactured by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. As a result, in Examples 5 to 13, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mJ / cm ² . Other results of each example are shown in Table 3.

In addition, the compound (thermal crosslinking agent) represented by said structural formula (2)-(10) was synthesize | combined as follows.

Synthesis of Compound Represented by Structural Formula (2)

10.9 mass parts of the 1st intermediate products obtained in the said Example 1, 4.71 mass parts of hexamethylene diisocyanate, and 14 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 90 degreeC. 0.02 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 2 hours. After cooling, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized from ethyl acetate to obtain 13.2 parts by mass of a white solid (yield 85%).

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.13 (d, 4H), 6.86 (d, 4H), 4.69 (br, 2H), 4.25-4.17 (m, 6H), 3.94 (q, 2H), 3.37-3.33 (m, 2H) , 3.14 (d, 4H), 2.75 (q, 2H), 1.47 (m, 4H), and 1.31 (m, 4H).

Synthesis of Compound Represented by Structural Formula (3)

20 mass parts of tolylene diisocyanate, 21.8 mass parts of 3-methyl-3 butene-1-ols, and 80 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 6 hours. After cooling, the solvent was distilled off from the reaction product and purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 7/3) to obtain 32 parts by mass of the intermediate product (yield 80%).

Next, 28 mass parts of said intermediate products, 250 mass parts of ethyl acetate, 68 mass parts of sodium hydrogencarbonate, 200 mass parts of water, and 98 mass parts of acetone were put into the reaction kiln. The aqueous solution which melt | dissolved OXONE115 mass part in 400 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated in saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 6/4), and obtained 19.5 mass parts (yield 64%) of oily substances.

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.79 (s, 1H), 7.22 (d, 1H), 7.09 (d, 1H), 6.68 (s, 1H), 6.41 (s, 1H), 4.37-4.02 (m, 4H), 2.63 (d, 4H), 2.20 (s, 3H), 2.03-1.86 (m, 4H), and 1.39 (s, 6H).

Synthesis of Compound Represented by Structural Formula (4)

7.56 parts by mass of the first intermediate product obtained in Example 1, 4.87 parts by mass of methylenebisphenylisocyanate and 12 parts by mass of ethyl acetate were placed in a reaction kettle, and heated at 90 ° C. 0.02 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 2 hours. After allowing to cool, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 9.6 parts by mass (yield 77%) of a white solid.

The product was also identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 9.50 (s, 2H), 7.34 (d, 4H), 7.20 (d, 4H), 7.08 (d, 4H), 6.90 (d, 4H), 4.30-4.21 (m, 4H), 3.84 (q, 4H), 3.32 (s, 2H), 2.89-2.82 (m, 4H), 2.70 (t, 2H), and 2.50 (s, 4H).

Synthesis of Compound Represented by Structural Formula (5)

7.56 parts by mass of the first intermediate product obtained in Example 1, 5.66 parts by mass of 1,3-bis (1-isocyanate-1-methylethyl) benzene, and 15 parts by mass of ethyl acetate were placed in a reaction kiln, and heated at 90 ° C. 0.02 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 2 hours. After cooling, the mixture was extracted with 50 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and obtained 5.4 mass parts (yield 37%) of compounds.

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.47 (s, 2H), 7.29 (s, 4H), 7.12 (s, 2H), 6.86 (d, 4H), 5.06 (s, 2H), 4.22-4.16 (m, 6H), 3.94 (q, 2H), 3.34 (m, 2H), 2.92-2.74 (m, 4H), and 1.71 (s, 12H).

Synthesis of Compound Represented by Structural Formula (6)

20 mass parts of tolylene diisocyanate, 16.1 mass part of 2-methyl-2-propene-1-ols, and 80 mass parts of ethyl acetate were put into the reaction kettle, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 6 hours. After allowing to cool, the reaction solution was filtered. The solvent of the filtrate was distilled off and 21 mass parts (yield 60%) of intermediate products were obtained by recrystallization with the hexane / ethyl acetate = 1/1 solution.

Next, 20 parts by mass of the intermediate product, 200 parts by mass of ethyl acetate, 51 parts by mass of sodium bicarbonate, 200 parts by mass of water, and 73 parts by mass of acetone were placed in a reaction kiln. The aqueous solution which melt | dissolved 90 mass parts of OXONE in 400 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/7), and 15 mass parts (yield 68%) of white solids were obtained.

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.34-7.19 (m, 4H), 5.46 (s, 2H), 4.38 (d, 4H), 4.30 (d, 2H), 4.00 (d, 2H), 2.78 (d, 2H), 2.66 (d, 2H) and 1.38 (s, 6H).

Synthesis of Compound Represented by Structural Formula (7)

30 mass parts of 4-hydroxybenzyl alcohol, 37 mass parts of potassium carbonate, and 100 mass parts of dimethylacetamide were put into the reaction kiln, and it heated at 80 degreeC. 23.6 mass parts of 3-chloro-2-methyl-1-propenes were dripped at the said reaction kiln over 0.5 hour. The reaction was then carried out for 10 hours. After cooling, the reaction mass was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 34.5 mass parts (yield 89%) of 1st intermediate products were obtained.

Next, 30 mass parts of said 1st intermediate products, 200 mass parts of ethyl acetate, 71 mass parts of sodium hydrogencarbonate, 200 mass parts of water, and 103 mass parts of acetone were put into the reaction kiln. The aqueous solution which melt | dissolved 120 mass parts of OXONE in 500 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off and the residue was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5) to obtain 19.5 parts by mass (yield 60%) of the second intermediate product.

Finally, 5 parts by mass of m-xylylene diisocyanate, 10.6 parts by mass of the second intermediate product, and 50 parts by mass of ethyl acetate were placed in a reaction kiln and heated at 55 ° C. To the reaction kiln, 0.05 parts by mass of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added. The reaction was then carried out for 6 hours. After cooling, the reaction solution was filtered, the solvent of the filtrate was distilled off, and recrystallized with ethyl acetate to obtain 7 parts by mass of a white solid (yield 44%). The melting point of the white solid was 113-115 ° C.

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.32-7.11 (m, 8H), 6.84 (d, 4H), 4.97 (br, 2H), 4.35-4.25 (m, 8H), 3.99 (q, 4H), 2.87 (m, 6H) , 2.72 (d, 2H), 1.48 (s, 6H).

-Synthesis of epoxy resin compound represented by Structural Formula (8)-

30 mass parts of 4-hydroxybenzyl alcohol, 37 mass parts of potassium carbonate, and 100 mass parts of dimethylacetamide were put into the reaction kiln, and it heated at 80 degreeC. 23.6 mass parts of 3-chloro-2-methyl-1-propenes were dripped at the said reaction kiln over 0.5 hour. The reaction was then carried out for 10 hours. After cooling, the reaction mass was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 34.5 mass parts (yield 89%) of 1st intermediate products were obtained.

Next, 30 mass parts of said 1st intermediate products, 200 mass parts of ethyl acetate, 71 mass parts of sodium hydrogencarbonate, 200 mass parts of water, and 103 mass parts of acetone were put into the reaction kiln. The aqueous solution which melt | dissolved 120 mass parts of OXONE in 500 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 19.5 mass parts (yield 60%) of 2nd intermediate products were obtained.

Finally, 3.4 mass parts of tolylene diisocyanate, 7.7 mass parts of said 2nd intermediate products, and 40 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 6 hours. After cooling, the solvent of the said organic phase was distilled off and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 9.5 mass parts (yield 83%) of oily substances were obtained.

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.73 (s, 1H), 7.22 (d, 1H), 7.15 (d, 4H), 7.08 (d, 1H), 6.87 (d, 4H), 6.59 (s, 1H), 6.39 (s , 1H), 4.33 (t, 2H), 3.98 (q, 4H), 3.83 (t, 2H), 2.95-2.72 (m, 8H), 2.19 (s, 3H), 1.49 (s, 6H).

Synthesis of Compound Represented by Structural Formula (9)

20 mass parts of diphenylmethane diisocyanate, 11.8 mass parts of 2-methyl-2- propene-1-ols, and 60 mass parts of ethyl acetate were put into the reaction kettle, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. Then, it was reacted for 6 hours. After allowing to cool, the reaction solution was filtered. The solvent of the filtrate was distilled off and recrystallized from a hexane / ethyl acetate = 1/1 solution to obtain 19.5 parts by mass (yield 62%) of an intermediate product.

Next, 18 parts by mass of the intermediate product, 200 parts by mass of ethyl acetate, 40 parts by mass of hydrogen or sodium carbonate, 200 parts by mass of water, and 65 parts by mass of acetone were placed in a reaction kiln. The aqueous solution which melt | dissolved 80 mass parts of OXONE in 350 mass parts of water was dripped at the said reaction kiln over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/7), and 15.4 mass parts (yield 73%) of white solids were obtained.

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.30 (d, 4H), 7.12 (d, 4H), 6.76 (s, 2H), 4.37 (d, 2H), 4.07 (d, 2H), 3.91 (s, 2H), 2.83 (d , 2H), 2.71 (d, 2H) and 1.43 (s, 6H).

Synthesis of Epoxy Resin Compound Represented by Structural Formula (31)

20 mass parts of tolylene diisocyanate, 17 mass parts of 2-methyl-2-propene-1-ols, and 50 mass parts of ethyl acetate were put into the reaction kiln, and it heated at 55 degreeC. 0.05 mass part of stannock (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to the reaction kettle. The reaction was then carried out for 6 hours. After allowing to cool, the reaction solution was filtered. The solvent of the filtrate was distilled off and recrystallized with a hexane / ethyl acetate = 1/1 solution to obtain 20.5 parts by mass of an intermediate product (yield 56%).

Next, 20 parts by mass of the intermediate product, 150 parts by mass of ethyl acetate, 53 parts by mass of sodium bicarbonate, 150 parts by mass of water, and 77 parts by mass of acetone were placed in a reaction kiln. An aqueous solution in which 95 parts by mass of OXONE was dissolved in 400 parts by mass of water was added dropwise to the reaction kettle over 1 hour. The reaction was then carried out for 7 hours. 300 mass parts of 10% sodium thiosulfate aqueous solution was added to the said reaction kiln, it stirred for 1 hour, liquid-separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the said organic phase was distilled off, and it refine | purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5), and 11 mass parts (yield 50%) of oily substances were obtained.

In addition, the product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak in the spectrum is 7.82 (s, 1H), 7.21 (d, 1H), 7.10 (d, 1H), 6.74 (s, 1H), 6.51 (s, 1H), 4.36 (t, 2H), 4.05 (d , 2H), 2.82 (m, 2H), 2.76 (m, 2H), 2.21 (s, 3H), 1.43 (s, 6H).

(Example 14)

In Example 1, the acrylic resin (B1) which has 40.0 mass parts of binders represented by the said structural formula (46) in the photosensitive composition, and 20.0 mass parts of binders represented by the said structural formula (46), and the unsaturated group obtained by the synthesis example a shown below. Except having changed into 20 mass parts, the photosensitive composition was prepared by the method similar to Example 1, the photosensitive film and the laminated body were prepared by the method similar to Example 1, and the permanent pattern was formed.

In addition, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability was performed on the photosensitive film prepared in the same manner as in Example 1, and evaluation of pencil hardness and dielectric properties was performed on the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mJ / cm ² . Other results are shown in Table 3.

Synthesis Example a (Synthesis of Acrylic Resin (B1))-

A mixed solution consisting of 45.1 parts by mass of methyl methacrylate, 47.3 parts by mass of methacrylic acid, 1 part by mass of azoisovaleronitrile, and 215 parts by mass of propylene glycol monomethyl ether is placed in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere for 3 hours. Dropped. After dripping, it reacted for 4 hours and obtained acrylic resin (A1).

Next, 54.7 parts by mass of cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.), 0.2 parts by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine were added to the obtained acrylic resin (A1) solution while blowing air. It reacted at 80 degreeC for 8 hours, and obtained the acrylic resin (B1) solution (solid acid value; 111, Mw; 18,000, double bond equivalent 2.3mmol / g, propylene glycol monomethyl ether solution) which has an unsaturated group.

(Example 15)

In Example 1, acrylic resin (B2) which has 40.0 mass parts of binders represented by the said structural formula (46) in the photosensitive composition, and 20.0 mass parts of binders represented by the said structural formula (46), and the unsaturated group obtained by the synthesis example b shown below. Except having changed into 20 mass parts, the photosensitive composition was prepared like Example 1, the photosensitive film and the laminated body were prepared like Example 1, and the permanent pattern was formed.

In addition, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability was performed on the photosensitive film prepared in the same manner as in Example 1, and evaluation of pencil hardness and dielectric properties was performed on the formed permanent pattern. Done. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mJ / cm ² . Other results are shown in Table 3.

Synthesis Example b (synthesis of acrylic resin (B2))

A mixed solution consisting of 45.1 parts by mass of methyl methacrylate, 47.3 parts by mass of methacrylic acid, 1 part by mass of azoisovaleronitrile, and 215 parts by mass of propylene glycol monomethyl ether is placed in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere for 3 hours. Dropped. It reacted for 4 hours after dripping, and obtained acrylic resin (A2).

Next, 35.9 mass parts of glycidyl methacrylate, 0.2 mass part of hydroquinone monomethyl ether, and 1 mass part of triphenylphosphines are added to the obtained acrylic resin (A2) solution, and it is made to react at 80 degreeC for 8 hours, blowing air, And acrylic resin (B2) solution (solid acid value; 104, Mw; 20,000, double bond equivalent 2.0mmol / g, 37 mass% solution of propylene glycol monomethyl ether) which have an unsaturated group were obtained.

(Examples 16 to 19)

Examples 1, 5, 7, and 10, except that the exposure apparatus was replaced with the pattern forming apparatus described in paragraphs [0383] to [0393] of JP-A-2005-258431. In the same manner as in 1, the prepared photosensitive composition and the photosensitive film were evaluated for tackiness, exposure sensitivity, resolution, and exposure speed, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The exposure sensitivity in Examples 16-19 is 30 mJ / cm <^2> , the resolution is 70 micrometers, and an exposure speed is 7 mJ / cm <^2> . Table 3 shows the results of pencil hardness, dielectric properties, and storage stability.

(Comparative Example 1)

In Example 1, except having changed the compound represented by the said Structural formula (1) in the photosensitive composition into 2,2'-bis (4-glycidyl phenyl) propane, it carried out similarly to Example 1, and the photosensitive composition Was prepared, the photosensitive film and the laminated body were prepared like Example 1, and the permanent pattern was formed.

In addition, the tackiness, the exposure sensitivity, the resolution, the exposure speed, and the storage stability were evaluated for the photosensitive film prepared in the same manner as in Example 1, and the pencil hardness and dielectric properties were evaluated for the formed permanent pattern. . In Comparative Example 1 and Comparative Examples 2 and 3 thereafter, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mJ / cm ² . Other results are shown in Table 3.

(Comparative Example 2)

In Example 1, the photosensitive composition was manufactured by the method similar to Example 1 except having changed the compound represented by the said Structural formula (1) in the photosensitive composition to Epicoat YX4000 (made by Japan Epoxy Resin Co., Ltd., epoxy resin). In the same manner as in Example 1, a photosensitive film and a laminate were manufactured, and a permanent pattern was formed.

Moreover, about the photosensitive film manufactured above by the method similar to Example 1, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability is performed, and evaluation of pencil hardness and dielectric property is performed about the formed permanent pattern. Done. The results are shown in Table 3.

(Comparative Example 3)

In Example 1, the photosensitive composition was manufactured and performed similarly to Example 1 except having changed the compound represented by the said Structural formula (1) in the photosensitive composition into TEPIC (made by Nissan Chemical Corporation, epoxy resin). In the same manner as in Example 1, a photosensitive film and a laminate were prepared to form a permanent pattern.

In addition, evaluation of tackiness, exposure sensitivity, resolution, exposure speed, and storage stability was performed on the photosensitive film prepared in the same manner as in Example 1, and evaluation of pencil hardness and dielectric properties was performed on the formed permanent pattern. Done. The results are shown in Table 3.

From the result of Table 3, the photosensitive layer in the photosensitive film manufactured using the photosensitive composition of Examples 1-19 containing at least 1 sort (s) of compound chosen from the compound represented by General formula (1)-(3). Comparative example 1 which was excellent in silver tackiness, exposure sensitivity, and resolution, the surface hardness of the hardened layer and the dielectric property in the permanent pattern formed using the said photosensitive film was favorable, and used the conventionally well-known epoxy resin compound as a thermal crosslinking agent. It was confirmed that storage stability is very excellent compared with the photosensitive film of -3. In particular, it turned out that the photosensitive films of Examples 1-2 and 5-19 whose content in the photosensitive composition of the said compound are 0.01-15 mass% are excellent both in storage stability and dielectric properties.

In addition, in Examples 16 to 19 using the same photosensitive film as in Examples 1, 5, 7 and 10, since a pattern forming apparatus capable of high-speed modulation with a high brightness light source and optical system distortion correction by a toric lens was used, It was confirmed that the resolution and the exposure speed were excellent, and that a high-precision permanent pattern was formed.

The photosensitive composition of this invention and the photosensitive film using the said photosensitive composition contain the compound which does not produce reaction under normal temperature at the time of storage, starts a crosslinking reaction by heating, and obtains the favorable film hardness of a cured film, and is imaged by UV exposure. Formable, small surface tack, good lamination and handleability, excellent storage stability, high sensitivity, developability, excellent chemical resistance, surface hardness, heat resistance, dielectric properties after development Protective films of printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, and display members such as color filters, aggregates, ribs, spacers, partition walls, holograms, micromachines, and proofs. It can be used widely for permanent pattern formation, such as these.

In addition, the permanent pattern of the present invention is excellent in chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation. For this reason, protective films of printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, display members such as color filters, aggregates, ribs, spacers, partition walls, holograms, micromachines, proofs, and the like. It can be used preferably from the point which can be used widely for permanent pattern formation of the resin.

Claims (5)

(A) A polymer having at least one of at least one carboxyl group and ester group in one molecule, (B) polymerizable compound, (C) photopolymerization initiator, and (D) represented by the following general formulas (1) to (3) A photosensitive composition comprising at least one compound selected from losing compounds.

(However, in the general formulas (1), (2) and (3), P represents any one of an oxygen atom, a carbonyl group, an amide group, a urethane group, alkylene and arylene. Q represents a boron atom or a nitrogen atom. Represents any one of alkylene and arylene W represents naphthalene having a bond with two X moieties A ^{1 to} A ⁵ represent any one of a single bond, alkylene and arylene, and X ^{1 to} X ⁶ represents any one of -OCONH-, -NHCOO-, -NHCO-, and -CONH- R ¹ to R ⁶ represent any one of a hydrogen atom, a halogen atom, an alkyl group and an aryl group.) (D) Content of the 1 or more types of compound chosen from the compound represented by General formula (1)-(3) is 1-50 mass%, The photosensitive composition of Claim 1 characterized by the above-mentioned. It has a photosensitive layer formed by laminating | stacking the photosensitive composition of Claim 1 or 2 on a support body and the said support body, The photosensitive film characterized by the above-mentioned. The photosensitive composition of Claim 1 or 2 is apply | coated to the surface of a base material, and after drying and forming a photosensitive layer, it exposes, develops, and heats, The permanent pattern formation method characterized by the above-mentioned. The photosensitive film of Claim 3 is laminated | stacked on the surface of a base material in at least one of under heating and under pressure, and then exposes, develops, and heats, The permanent pattern formation method characterized by the above-mentioned.