KR20080103061A - Photosensitive composition, photosensitive film, photosensitive layered product, method of forming permanent pattern, and printed wiring board - Google Patents

Abstract

A photosensitive composition which is free from edge fusion, is excellent in tackiness and long-term performance stability, can be easily formed into a film, and can be efficiently formed into a highly precise permanent pattern (protective film, interlayer dielectric, solder resist pattern, etc.); a photosensitive film; a photosensitive layered product; a method of forming a permanent pattern from the photosensitive layered product; and a printed wiring board having a permanent pattern formed by the permanent-pattern formation method. The photosensitive composition comprises a binder, a polymerizable compound, a photopolymerization initiator, an elastomer, and a thermal crosslinking agent, wherein the binder comprises a polymer having an acid group and an ethylenically unsaturated bond in a side chain.

Description

PHOTOSENSITIVE COMPOSITION, PHOTOSENSITIVE FILM, PHOTOSENSITIVE LAYERED PRODUCT, METHOD OF FORMING PERMANENT PATTERN, AND PRINTED WIRING BOARD}

The present invention is free of edge fusion (cross-sectional fusion), has excellent tackiness and performance stability over time, facilitates film formation, and provides high-definition permanent patterns (protective film, interlayer insulating film, solder resist pattern, etc.). It relates to a photosensitive composition which can be formed efficiently, a photosensitive film, a photosensitive laminate, a permanent pattern forming method using the photosensitive laminate, and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.

Conventionally, in forming permanent patterns, such as a soldering resist pattern, the photosensitive film which formed the photosensitive layer by apply | coating and drying a photosensitive composition on a support body is used. As a manufacturing method of the said permanent pattern, the laminated body is formed by laminating | stacking the said photosensitive film on base materials, such as a copper clad laminated board in which the said permanent pattern is formed, for example, and exposing to the said photosensitive layer in the said laminated body, After the exposure, the photosensitive layer is developed to form a pattern, and then the permanent pattern is formed by performing a curing treatment or the like.

In the above-mentioned permanent pattern, in the solder resist of the board | substrate use which has flexibility, such as a package board | substrate and a flexible board | substrate, it is required to relieve a stress in order to prevent a crack. Moreover, in recent years, the said board | substrate and the components used for this are also downsized, and when a liquid resist type photosensitive composition is used, it is difficult to apply | coat smoothly from application and drying on a board | substrate, and film formation of the photosensitive composition is carried out. Requests are increasing.

Here, for the purpose of stress relaxation, for example, a photocurable resin containing an acid-modified vinyl group-containing epoxy resin (A), an elastomer (B), a photopolymerization initiator (C), a diluent (D), and a curing agent (E) as essential components. A composition is proposed (refer patent document 1).

However, when the acid-modified vinyl group-containing epoxy resin of the above-mentioned proposal is used as a binder, edge fusion (cross-section fusion) occurs especially when a pattern formation material on a film is constructed, or the performance stability under tack and time is poor. Filming was difficult because of the problem.

Therefore, there is no edge fusion (cross-sectional fusion), and excellent tackiness and performance stability over time facilitate film formation, and can efficiently form high-definition permanent patterns (protective film, interlayer insulating film, solder resist pattern, etc.). The photosensitive film, the photosensitive laminated body, the permanent pattern forming method using the said photosensitive laminated body, and the printed circuit board in which a permanent pattern is formed by the said permanent pattern forming method are not yet provided, and improvement development is further required. The current state.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-240930

This invention is made | formed in view of such a present situation, and makes it a subject to solve all the said problems in the past, and to achieve the following objectives. That is, the present invention is free of edge fusion (cross-sectional fusion), and has excellent performance stability under tackiness and time-lapse, which facilitates film formation, and efficiently forms high-definition permanent patterns (protective film, interlayer insulating film, solder resist pattern, etc.). It aims at providing the photosensitive composition which can be formed, the photosensitive film and the photosensitive laminated body which used this, the permanent pattern formation method using the said photosensitive laminated body, and the printed circuit board with which a permanent pattern is formed by the said permanent pattern formation method.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnestly examining by the present inventors, the binder contains a polymeric compound, a photoinitiator, an elastomer, and a thermal crosslinking agent, and the said binder has the high molecular compound which has an acidic group and ethylenically unsaturated bond in a side chain. It was found that the photosensitive composition contained had no edge fusion (cross-sectional fusion), was excellent in tackiness and performance stability over time, was easily filmed, and was able to efficiently form a high-definition permanent pattern.

This invention is based on the said knowledge of this inventor, As a means for solving the said subject, it is as follows. In other words,

It is a photosensitive composition containing a <1> binder, a polymeric compound, a photoinitiator, an elastomer, and a thermal crosslinking agent, and the said binder contains the high molecular compound which has an acidic group and ethylenically unsaturated bond in a side chain.

<2> Photosensitive composition as described in said <1> containing the high molecular compound which has an aromatic group and ethylenically unsaturated bond which may contain an acidic group and a heterocyclic ring in a side chain.

<3> High molecular compound is the photosensitive composition as described in said <1> or <2> containing 0.5-3.0 meq / g of ethylenically unsaturated bonds.

The acidic group of a <4> high molecular compound is a carboxyl group, The content of the said carboxyl group in the said high molecular compound is 1.0-4.0 meq / g, The photosensitive composition in any one of said <1> to <3>.

It is a photosensitive composition in any one of said <1> to <4> whose mass mean molecular weight of a <5> high molecular compound is 10,000 or more and less than 100,000.

<6> high molecular compound is the photosensitive composition in any one of said <1> to <5> containing 20 mol% or more of structural units represented by following structural formula (I).

[However, in the structural formula (I), R ₁ , R _2, and R ₃ represent a hydrogen atom or a monovalent organic group. L may represent an organic group and may be absent. Ar represents an aromatic group.]

<7> elastomer is the photosensitive composition in any one of said <1> to <6> which shows either swelling property or solubility with respect to alkaline aqueous solution.

<8> The elastomer according to any one of <1> to <7>, wherein the elastomer is at least one selected from styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. The pattern formation method described.

<9> elastomer is a pattern formation method in any one of said <1> to <8> which is at least 1 sort (s) chosen from butadiene-styrene type elastomer and butadiene-acrylic acid ester type elastomer.

Content of a <10> elastomer is a pattern formation method in any one of said <1> to <9> which is 2-50 mass parts with respect to 100 mass parts of binders.

&Lt; 11 > The photopolymerization initiator contains at least one selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metallocenes, and acylphosphine oxide compounds. It is a photosensitive composition in any one of said <1> to <10>.

<12> photoinitiator is the photosensitive composition in any one of said <1> to <11> containing an oxime derivative.

The <13> polymerizable compound is the photosensitive composition in any one of <1>-<12> containing the compound which has one or more of ethylenically unsaturated bonds.

<14> polymerizable compounds are the photosensitive compositions in any one of said <1> to <13> containing at least 1 sort (s) chosen from the monomer which has a (meth) acryl group.

The <15> thermal crosslinking agent is the photosensitive composition in any one of said <1> to <14> which is alkali-insoluble.

The <16> thermal crosslinking agent is the photosensitive composition as described in said <15> 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, a polyisocyanate compound, and a melamine derivative.

<17> Photosensitive composition contains a sensitizer and the said sensitizer is the photosensitive composition in any one of said <1> to <16> which is a heterocyclic ring-type ketone.

It is a photosensitive film which has a <18> support body and the photosensitive layer which consists of a photosensitive composition in any one of said <1> to <17> on the said support body.

<19> support body contains a synthetic resin, and is a transparent photosensitive film as described in said <18>.

The <20> support body is a photosensitive film as described in said <18> or <19> which is a long picture.

It is a <21> long shape and is the photosensitive film in any one of said <18> to <20> formed by winding in a roll shape.

It is the photosensitive film in any one of said <18> to <21> which has a protective film on the photosensitive layer in a <22> photosensitive film.

It is a photosensitive laminated body which has a photosensitive layer which consists of a photosensitive composition in any one of said <1> to <17> on a <23> base body.

<24> photosensitive layer is a photosensitive laminated body as described in said <23> formed with the photosensitive film in any one of said <18> to <22>.

It is a photosensitive laminated body in any one of said <23> to <24> whose thickness of a <25> photosensitive layer is 1-100 micrometers.

<26> The photosensitive layer in the photosensitive laminated body in any one of said <23>-<25> is provided,

At least the light irradiation means which can irradiate light, and the light modulation means which modulates the light from the said light irradiation means, and exposes the photosensitive layer in the said photosensitive film is a pattern forming apparatus characterized by the above-mentioned. In the pattern formation apparatus as described in said <26>, the said light irradiation means irradiates light toward the said light modulation means. The light modulation means modulates the light received from the light irradiation means. Light modulated by the light modulating means is exposed to the photosensitive layer. For example, after developing the said photosensitive layer, a high-definition pattern will be formed.

And having a pattern signal generating means for generating a control signal based on the pattern information formed by the light modulating means, and modulating the light irradiated from the light irradiation means in accordance with the control signal generated by the pattern signal generating means. It is a pattern forming apparatus as described in said <26>. In the pattern forming apparatus according to the above <27>, the light modulating means has the pattern signal generating means, so that the light irradiated from the light irradiating means is modulated in accordance with the control signal generated by the pattern signal generating means.

<27> The light modulating means has n drawing parts, and the control part can control according to pattern information to form any less than n of the drawing parts arranged continuously among the n drawing parts. It is a pattern forming apparatus as described in>. In the pattern forming apparatus according to the above <28>, light from the light irradiation means is controlled by controlling any less than n seedling portions continuously arranged among the n seedling portions in the light modulating means according to the pattern information. Modulated at high speed.

<29> light modulation means is a pattern formation apparatus in any one of said <26> to <28> which is a spatial light modulation element.

The <30> spatial light modulator is a pattern forming apparatus as described in said <29> which is a digital micro mirror device (DMD).

<31> drawing parts are the pattern forming apparatuses in any one of said <28> to <30> which is a micro mirror.

<32> light irradiation means is a pattern forming apparatus in any one of said <26> to <31> which can synthesize | combine two or more lights, and can irradiate. In the pattern formation apparatus as described in said <32>, the said light irradiation means can irradiate | combine two or more lights, and exposure is performed by exposure light with a deep depth of focus. As a result, exposure to the said photosensitive layer is performed very highly. For example, when the photosensitive layer is developed after that, a very fine pattern is formed.

<33> Any one of the above <26> to <32>, 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 to the multi-mode optical fiber; It is a pattern forming apparatus of description. In the pattern forming apparatus described in the above <33>, the light irradiation means is irradiated with the laser light irradiated from the plurality of lasers, respectively, by the collective optical system and can be coupled to the multi-mode optical fiber, so that the depth of exposure is deep. It is performed with exposure light. As a result, exposure to the said photosensitive layer is performed very highly. For example, when the photosensitive layer is developed after that, a very fine pattern is formed.

<34> It is a permanent pattern formation method characterized by exposing to the photosensitive layer in the photosensitive laminated body in any one of said <23> to <25>.

<35> exposure is a permanent pattern formation method as described in said <34> performed using the laser beam of 350-415 nm wavelength.

It is a permanent pattern formation method as described in said <34> or <35> performed in an image shape based on the pattern information formed by <36> exposure.

<37> The exposure has light irradiation means and n number of light-receiving portions (n is two or more natural numbers) arranged to receive and emit light from the light irradiation means, wherein the drawing elements are arranged in accordance with pattern information. An exposure head having light modulating means capable of controlling the part, using an exposure head arranged such that a column direction of the drawing part has a predetermined set inclination angle θ with respect to a scanning direction of the exposure head,

About the said exposure head, by the use drawing part designation means, the said drawing part used for exposure among N (where N is a natural number of 2 or more) among the available drawing parts,

The drawing head control means controls the drawing head so that only the drawing part designated by the drawing head designation means is involved in the exposure by the drawing part control means.

It is a permanent pattern formation method in any one of said <34> to <36> performed by making the said exposure head move relatively to a scanning direction with respect to the said photosensitive layer. In the permanent pattern formation method as described in said <37>, the said drawing material used for exposure among N (except N is natural number of 2 or more) among the said drawing parts which can be used with the use drawing part designation means with respect to the said exposure head. Further, the drawing section control means controls the drawing section so that only the drawing section designated by the use drawing section designation means participates in exposure. The exposure is performed by moving the exposure head relative to the photosensitive layer in the scanning direction, whereby the unevenness of the resolution of the pattern formed on the exposed surface of the photosensitive layer due to the shift of the installation position or installation angle of the exposure head. However, the concentration variation is even. As a result, the exposure to the photosensitive layer is performed with high detail, and then the photosensitive layer is developed, whereby a fine pattern is formed.

The exposure is performed by a plurality of exposure heads, and the use drawing part designation means is the head among the drawing parts involved in the exposure of the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. It is a permanent pattern formation method as described in said <37> which designates the said drawing part used in order to implement N-exposure in interconnection area | region. In the method for forming a permanent pattern according to the above <38>, exposure is performed by a plurality of exposure heads so that the use drawing part designation means is used for exposure of the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The head on the to-be-exposed surface of the said photosensitive layer by the shift | offset | difference of the installation position and the installation angle of the said exposure head is designated by designating the said drawing part used in order to implement | achieve N-weight exposure in the said head-to-head connection area | region among the drawing parts concerned. The nonuniformity of the resolution and the nonuniformity of the concentration of the pattern formed in the liver connection area are even. As a result, exposure to the photosensitive layer is performed with high precision. For example, a high-definition pattern is formed by developing the said photosensitive layer after that.

Exposure is carried out by a plurality of exposure heads, and among the drawing parts involved in the exposure other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads, the head It is a permanent pattern formation method as described in said <38> which designates the said drawing part used in order to implement | achieve N-exposure in area | regions other than an interconnection area | region. In the method for forming a permanent pattern according to the above <39>, exposure is performed by a plurality of exposure heads so that the use drawing part designation means is an exposure other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of the exposure heads. The drawing part used for realizing N-weight exposure other than the said head-to-head connection area | region among the drawing part which concerns on is specified, and on the to-be-exposed surface of the said photosensitive layer by the shift | offset | difference of the installation position or installation angle of the said exposure head. Non-uniformity of the resolution of the pattern and variation of the density formed other than the connection area between the heads are even. As a result, exposure to the photosensitive layer is performed with high precision. For example, a high-definition pattern is formed by developing the said photosensitive layer after that.

The set inclination angle θ is orthogonal to the scanning direction of the exposure head in a state in which N of the number of exposures N, the number s in the column direction of the drawing part, the interval p in the column direction of the drawing part, and the exposure head are inclined. with respect to the column direction of the pitch δ graves unit in the direction, of the following formula, with respect to the _ideal θ that satisfies the _ideal spsinθ ≥Nδ, from the <37> is set to satisfy a relationship of _ideal θ≥θ <39> It is a permanent pattern formation method in any one of them.

<41> The method of forming a permanent pattern according to any one of <37> to <40>, wherein N of exposure is a natural number of 3 or more. In the permanent pattern formation method as described in said <41>, multiple drawing is performed because N of exposure of N is a natural number of 3 or more. As a result, the effect of replenishment makes it possible to more accurately and evenly uneven the density of the resolution of the pattern formed on the exposed surface of the photosensitive layer due to the deviation of the installation position and the installation angle of the exposure head.

<42> use cemetery designation means

Light point position detection means which is generated by a drawing unit and detects a light point position as a drawing unit constituting an exposure area on the to-be-exposed surface on the to-be-exposed surface;

Drawing part selecting means which selects the drawing part used for realizing N-exposure based on the detection result by the said light spot position detection means.

It is a permanent pattern formation method in any one of said <37> to <41> provided with.

<43> use seedling part designation means is a permanent pattern formation method in any one of said <37> to <42> which designates the use drawing part used in order to implement N exposure.

An actual inclination angle θ 'formed between the column direction of the light spot on the exposed surface and the scanning direction of the exposure head based on the at least two light spot positions detected by the light spot position detecting means. ), And the drawing part selecting means selects the drawing part to be used so as to absorb an error between the actual tilt angle θ 'and the set tilt angle θ. The permanent pattern forming method according to the above <42> or <43>. .

An average value, a median value, a maximum value of a plurality of actual inclination angles formed by the column direction of the light spot on the exposed surface and the scanning direction of the exposure head in a state in which the actual inclination angle [theta] 'is inclined; It is a permanent pattern formation method as described in said <44> which is any one of a minimum value.

Based on the actual inclination angle [theta] ', the drawing part selecting means derives a natural number T close to t that satisfies the relationship of ttan [theta]' = N (where N represents N of the number of exposures among N), The permanent column according to any one of <42> to <45>, wherein the drawing section in the first row of the drawing section arranged in the m rows (where m represents a natural number of two or more) is selected as the use drawing section. Pattern formation method.

The drawing part selecting means derives a natural number T close to t based on the actual inclination angle θ 'and satisfies the relationship of ttan θ' = N (where N represents N of the number of exposures in N), m the line (where m represents a natural number of 2 or more), and specifies the cemetery part from the (t + 1) th line to the m line part arranged in the cemetery part as the unused cemetery part and uses the cemetery part except the unused cemetery part It is a permanent pattern formation method in any one of said <42> to <46> selected as a part.

<48> in the region in which the drawing unit selecting means includes at least an overlapping exposure area on the exposed surface formed by the plurality of rows of the drawing units,

(1) Means for selecting the use drawing part so that the total area of the area | region which becomes overexposure and the area | region which become underexposure with respect to ideal N medium exposure is minimum,

(2) a means for selecting the use drawing section so that the number of drawing units in the area overexposed and the number of drawing units in the area underexposed is the same with respect to the ideal N-exposure;

(3) Means for selecting the use drawing part so that the area of the area which becomes overexposure becomes minimum and the area which becomes underexposure does not generate | occur | produce with respect to ideal N medium exposure, and

(4) With respect to the ideal N-exposure, the area of the area which becomes underexposure becomes minimum, and the above-mentioned <42> to <47, which is one of means for selecting the use drawing part so that the area that becomes overexposure does not occur. It is a permanent pattern formation method in any one of>.

In the head-to-head connection area which is an overlapping exposure area on the to-be-exposed surface formed by a plurality of exposure heads,

(1) With respect to the ideal N-exposure, an unused drawing part is specified from the drawing part involved in the exposure of the connection area between the heads so that the total area of the over-exposure area and the under-exposure area is minimum. Means for selecting the drawing section except the drawing section as the use drawing section,

(2) With respect to the ideal N-exposure, the unused drawing part is specified from the drawing part involved in the exposure of the head-to-head connection area so that the drawing unit number in the overexposure area and the underexposure area are the same. Means for selecting the drawing part except the unused drawing part as the using drawing part,

(3) With respect to the ideal N-exposure, the unused drawing part is identified from the drawing part involved in the exposure of the head-to-head connection area so that the area of the overexposure area is minimized and the area underexposure is not generated. Means for selecting the drawing part except the unused drawing part as the using drawing part, and

(4) With respect to the ideal N-exposure, the unused drawing part is identified from the drawing part involved in the exposure of the head-to-head connection area so that the area of the underexposure area is minimized and the area that becomes overexposure is not generated. Means for selecting the drawing part except the unused drawing part as the using drawing part.

It is any one of said <42> to <48> which is a permanent pattern formation method.

<50> unused drawing parts are the permanent pattern formation methods as described in said <49> specified by line unit.

In order to designate the use drawing part in the use drawing part designation means, only the said drawing part which comprises the drawing part row for every (N-1) columns is used with respect to N of N exposures among the available drawing parts. It is a permanent pattern formation method in any one of said <37> to <50> which performs reference exposure. In the permanent pattern formation method as described in said <51>, in order to designate a use drawing part in use drawing part designation means, the drawing part for every (N-1) rows with respect to N of exposure among N among the available drawing parts. A reference exposure is performed using only the drawing part constituting the column, and a simple pattern of approximately single drawing is obtained. As a result, the drawing part in the connection area between the heads is easily designated.

In order to designate the use drawing part in the use drawing part designation means, using only the said drawing part which comprises the drawing part row every 1 / N row with respect to N of exposure of N among the available drawing parts, It is a permanent pattern formation method in any one of said <37> to <50> which performs reference exposure. In the permanent pattern formation method as described in said <52>, in order to designate a drawing material part in use drawing part designation means, the drawing part column every 1 / N rows with respect to N of exposure among N among the available drawing parts. A reference exposure is performed using only the drawing portion constituting the structure, thereby obtaining a simple pattern of approximately single drawing. As a result, the drawing part in the connection area between the heads is easily designated.

<53> The permanent pattern according to any one of <37> to <52>, wherein the drawing element specifying means has a slit and a photodetector as the light spot position detecting means and a computing device connected to the photodetector as the drawing element selecting means. Formation method.

<54> is a permanent pattern formation method in any one of said <37> to <53> whose N of exposure N is a natural number of 3 or more and 7 or less.

Further comprising a pattern signal generating means for generating a control signal based on the pattern information formed by the light modulating means, and modulating the light irradiated from the light irradiation means according to the control signal generated by the pattern signal generating means. It is a permanent pattern formation method as described in any one of said <37> to <54> which is made. In the permanent pattern forming method described in the above <55>, the light modulating means has the pattern signal generating means, so that the light irradiated from the light irradiating means is modulated in accordance with the control signal generated by the pattern signal generating means. .

<56> light modulation means is a permanent pattern formation method in any one of said <37> to <55> which is a spatial light modulation element.

<57> spatial light modulation element is a permanent pattern formation method as described in said <56> which is a digital micro mirror device (DMD).

<58> drawing parts are the permanent pattern formation methods in any one of said <37> to <57> which is a micromirror.

The above <37> to <58> having conversion means for converting the pattern information so that the dimension of the predetermined portion of the pattern indicated by the pattern information matches the dimension of the corresponding portion that can be realized by the designated use drawing part. It is a permanent pattern formation method in any one of them.

<60> light irradiation means is a permanent pattern formation method in any one of said <37> to <59> which can synthesize | combine two or more lights, and is irradiated. In the permanent pattern formation method as described in said <60>, exposure is performed by exposure light with a deep depth of focus because the said light irradiation means can synthesize | combine two or more lights, and can irradiate. As a result, exposure to the said photosensitive film is performed very highly. For example, when the photosensitive layer is developed after that, a very fine pattern is formed.

<61> Any one of <37> to <60>, 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 to the multi-mode optical fiber; It is a permanent pattern formation method of description. In the method for forming a permanent pattern according to the above <61>, the exposure depth of focus is achieved by the light irradiation means being able to focus the laser light irradiated from the plurality of lasers onto the multi-mode optical fiber by collecting the laser light. It is performed with deep exposure light. As a result, exposure to the said photosensitive film is performed very highly. For example, when the photosensitive layer is developed after that, a very fine pattern is formed.

After <62> exposure is performed, it is a permanent pattern formation method in any one of said <34> to <61> which performs image development of a photosensitive layer. In the permanent pattern formation method as described in said <62>, after the said exposure is performed, a fine pattern is formed by developing the said photosensitive layer.

It is a permanent pattern formation method as described in said <62> which forms a permanent pattern after <63> image development is performed.

<64> It is a permanent pattern formed by the pattern formation method in any one of said <34> to <63>. Since the permanent pattern described in the above <64> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and is highly detailed, and has high density to a multilayer wiring board, a buildup wiring board, or the like of a semiconductor or a component. Useful for mounting.

It is a pattern as described in said <64> which is at least any one of a <65> protective film, an interlayer insulation film, and a soldering resist pattern. Since the permanent pattern described in the above <65> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring is protected from external shock, warpage, etc. by the insulation, heat resistance, and the like of the film.

<66> A printed circuit board comprising a permanent pattern formed by the permanent pattern forming method according to any one of <34> to <63>.

(Effects of the Invention)

According to the present invention, the problem in the prior art can be solved, there is no edge fusion (cross-section fusion), and excellent tackiness and performance stability over time are easy to form a film, and a high-definition permanent pattern (protective film, interlayer insulation film) And a photosensitive composition capable of efficiently forming a solder resist pattern), a photosensitive film and a photosensitive laminate using the same, a permanent pattern forming method using the photosensitive laminate, and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method. Can be provided.

1 is a perspective view showing an appearance of an example of a pattern forming apparatus.

2 is a perspective view showing an example of a scanner configuration of a pattern forming apparatus.

3A is a plan view showing an exposed-completed area formed on the exposed surface of the photosensitive layer.

3B is a plan view showing the arrangement of the exposure areas by the respective exposure heads.

4 is a perspective view showing an example of a schematic configuration of an exposure head.

5A is a top view illustrating an example of a detailed configuration of an exposure head.

5B is a side view illustrating an example of a detailed configuration of an exposure head.

6 is a partially enlarged view illustrating an example of a DMD of the pattern forming apparatus of FIG. 1.

7A is a perspective view for explaining the operation of the DMD.

7B is a perspective view for explaining the operation of the DMD.

FIG. 8 is an explanatory diagram showing an example of nonuniformity occurring in a pattern on the exposed surface when there is an installation angle error and pattern deformation of the exposure head.

9 is a top view showing the positional relationship between an exposure area by one DMD and a corresponding slit.

10 is a top view for explaining a method of measuring the position of a light spot on an exposed surface using a slit.

FIG. 11 is an explanatory diagram showing a state in which the unevenness occurring in the pattern on the exposed surface is improved as a result of using only the selected micromirrors for exposure.

It is explanatory drawing which showed the example of the nonuniformity which arises in the pattern on a to-be-exposed surface, when there exists a shift of a relative position between adjacent exposure heads.

Fig. 13 is a top view showing the positional relationship between the exposure area by two adjacent exposure heads and the corresponding slit.

It is a top view for demonstrating the method of measuring the position of the light spot on a to-be-exposed surface using a slit.

FIG. 15 is an explanatory diagram showing a state in which only the use pixel selected in the example of FIG. 12 actually moves and the nonuniformity generated in the pattern on the exposed surface is improved.

FIG. 16 is an explanatory diagram showing an example of nonuniformity generated in a pattern on the exposed surface when there is a shift in relative position and an installation angle error between adjacent exposure heads. FIG.

17 is an explanatory diagram showing exposure using only the use drawing part selected in the example of FIG. 16.

18A is an explanatory diagram showing an example of magnification deformation.

18B is an explanatory diagram showing an example of beam diameter modification.

19A is an explanatory diagram showing a first example of reference exposure using a single exposure head.

19B is an explanatory diagram showing a first example of the reference exposure using the single exposure head.

20 is an explanatory diagram showing a first example of a reference exposure using a plurality of exposure heads.

21A is an explanatory diagram showing a second example of the reference exposure using the single exposure head.

21B is an explanatory diagram showing a second example of the reference exposure using the single exposure head.

22 is an explanatory diagram illustrating a second example of the reference exposure using the plurality of exposure heads.

(Photosensitive composition)

It contains a binder, a polymeric compound, a photoinitiator, an elastomer, and a thermal crosslinking agent, and contains other components as needed.

[bookbinder]

As said binder, the high molecular compound which contains an acidic group and ethylenically unsaturated bond in a side chain is used. As said acidic group, although a carboxyl group, a phosphoric acid group, a sulfonic acid group etc. are mentioned, for example, a carboxyl group is preferable from the point of a raw material acquisition.

As said binder, the compound which is insoluble in water and swells or melt | dissolves by alkaline aqueous solution is preferable.

Moreover, as said binder, at least 1 polymerizable double bond in a molecule | numerator, for example, acrylic groups, such as a (meth) acrylate group or a (meth) acrylamide group, vinyl ester of carboxylic acid, a vinyl ether, an allyl ether, etc. Various polymerizable double bonds of can be used. More specifically, glycidyl esters of unsaturated fatty acids such as cyclic ether group-containing polymerizable compounds, for example, glycidyl acrylate, glycidyl methacrylate, cinnamic acid, in an acrylic resin containing a carboxyl group as an acidic group And compounds obtained by adding an epoxy group-containing polymerizable compound such as an alicyclic epoxy group (for example, an epoxy group such as cyclohexene oxide in the same molecule) and a compound having a (meth) acryloyl group. Moreover, the compound obtained by adding polymeric compounds containing isocyanate groups, such as isocyanate ethyl (meth) acrylate, to the acrylic resin containing an acidic group and a hydroxyl group, hydroxyalkyl (meth) acrylate, etc. to the acrylic resin containing anhydride groups, etc. Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group. Moreover, the compound etc. which are obtained by copolymerizing cyclic ether group containing polymeric compounds, such as glycidyl methacrylate, and vinyl monomers, such as (meth) acryloylalkyl ester, and adding (meth) acrylic acid to the side chain epoxy group are also mentioned. .

Examples thereof include Japanese Patent Laid-Open No. 2763775, Japanese Patent Laid-Open No. 3-172301, Japanese Patent Laid-Open No. 2000-232264, and the like.

Among these, the binder is a cyclic ether group (for example, an epoxy group, a group having an oxetane group in a partial structure) containing a polymerizable compound added to a part of the acidic group of the polymer compound, and a part of the cyclic ether group of the polymer compound Or a polymer compound selected from any of those in which a carboxyl group-containing polymerizable compound is added to all of them. At this time, the addition reaction of the compound having an acidic group and a cyclic ether group is preferably carried out in the presence of a catalyst, and in particular, the catalyst is preferably selected from an acidic compound and a neutral compound.

Among them, from the viewpoint of developing stability over time of the photosensitive composition, the binder is preferably an aromatic group which may contain a carboxyl group and a heterocycle in the side chain and a high molecular compound containing an ethylenically unsaturated bond in the side chain.

Aromatic group which may contain hetero ring

As an aromatic group which may contain the said heterocyclic ring (Hereinafter, it may only refer to an "aromatic group.") For example, a benzene ring, the thing which two to three benzene rings formed condensed ring, the benzene ring, and 5-membered unsaturated The ring formed the condensed ring, etc. are mentioned.

Specific examples of the aromatic group include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, pyrazole ring group and isoxa Sol ring group, isothiazole ring group, indazole ring group, benzoisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, Pyridine ring group, quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, asyrizine ring group, phenanthryl ring group, carbazole ring group, purine ring group, The pyran ring group, the piperidine ring group, the piperazine ring group, the indole ring group, the indoligin ring group, the chromen ring group, the cinnoline ring group, the acridine ring group, the phenothiazine ring group, the tetrazole ring group, the triazine ring group, etc. are mentioned. In these, a hydrocarbon aromatic group is preferable and a phenyl group and a naphthyl group are more preferable.

The aromatic group may have a substituent, and examples of the substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group, respectively. Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group etc. which may have a substituent are mentioned.

As said alkyl group, a C1-C20 linear alkyl group, a branched alkyl group, a cyclic alkyl group etc. are mentioned, for example.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl and octadecyl groups , Ecosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhex The actual group, cyclohexyl group, cyclopentyl group, 2-norbornyl group, etc. are mentioned. Among these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are preferable.

As a substituent which the said alkyl group may have, the group which consists of monovalent nonmetallic atom groups except a hydrogen atom is mentioned, for example. As such a substituent, for example, a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercap group, alkylthio group, arylthio group, alkyldithio group, aryl Dithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N -Alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl Sulfoxy group, aryl sulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'- Aryl ureido group, N ', N'- diaryl ureido group, N'-alkyl-N'- aryl ureido group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl Dido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N -Aryl ureido group, N ', N'- diaryl-N-alkyl ureido group, N', N'- diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkyl ureido group , N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group , N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, Arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated base group (Referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N- Diaryl sulfinamoyl group, N-alkyl-N-aryl sulfinamoyl group, sulfamoyl group, N-alkyl sulfamoyl group, N, N-dialkyl sulfamoyl group, N-aryl sulfamoyl group, N, N-dia Rylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂ ) and its conjugated base group (referred to as phosphonate group), dialkyl phosphono group (-PO ₃ (alkyl) ₂ ) (hereinafter "alkyl" means an alkyl group), diaryl phosphono group (-PO ₃ (aryl) ₂ ) (hereinafter "aryl" means an aryl group), alkylaryl phosphono group ( -PO ₃ (alkyl) (aryl), monoalkylphosphono group (-PO ₃ (alkyl)) and its conjugated base group (referred to as alkylphosphonate group), monoarylphosphono group (-PO ₃ H (aryl)) and its conjugated base group (referred to as arylphosphonate group), and phosphonooxy group (- OPO ₃ H ₂ ) and its conjugated base group (referred to as phosphonateoxy group), dialkyl phosphonooxy group (-OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (-OPO ₃ (aryl ₂ ), alkylarylphosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (alkylphosphonateoxy group) .), Monoarylphosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base (referred to as arylphosphonateoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, hetero Ventilation, silyl groups and the like.

Specific examples of the alkyl group in these substituents include the alkyl group described above.

Specific examples of the aryl group in the substituent include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloro methylphenyl group, hydroxyphenyl group, methoxyphenyl group, Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, Phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatephenyl group, phosphonophenyl group, phosphonatephenyl group, etc. are mentioned.

Specific examples of the alkenyl group in the substituent include vinyl group, 1-propenyl group, 1-butenyl group, cinnammyl group, 2-chloro-1-ethenyl group and the like.

Specific examples of the alkynyl group in the substituent include an ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of R ⁰¹ in the acyl group (R ⁰¹ CO-) in the above-mentioned substituents are exemplified an alkyl group such as a hydrogen atom, the above-described aryl group.

Among these substituents, halogen atom (-F, -Br, -Cl, -I), alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, acyl jade Period, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N -Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsul Pamoyl group, N-aryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosph Phonate groups, monoaryl phosphono groups, aryl phosphonate groups, phosphonooxy groups, phosphonateoxy groups, aryl groups, alkenyl groups and the like are preferable.

Moreover, as a heterocyclic group in the said substituent, a pyridyl group, a piperidinyl group, etc. are mentioned, for example, As a silyl group in the said substituent, a trimethylsilyl group etc. are mentioned.

On the other hand, examples of the alkylene group in the alkyl group include those in which any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above is removed to form a divalent organic residue, for example, carbon. Preferred are linear alkylene groups having 1 to 12 atoms, branched alkylene groups having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

As a preferable specific example of the substituted alkyl group obtained by combining such a substituent and an alkylene group, a chloromethyl group, a bromomethyl group, 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, isopropoxymethyl group, butoxymethyl group, s-butoxy Butyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetramethylpiperidinylmethyl group, trimethylsilylmethyl group, Methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group , N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxyka Carbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N- Methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonate butyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoyl Propyl group, N-methyl-N- (phosphonophenyl) sulfamoyl octyl group, phosphono butyl group, phosphonate hexyl group, diethyl phosphono butyl group, diphenyl phosphono propyl group, methyl phosphono butyl group, methyl Phosphonate butyl group, tolyl phosphonohexyl group, tolyl phosphonate hexyl group, phosphonooxypropyl group, phosphonate oxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1- Phenylethyl group, p-methylbenzyl group, cinnamil group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenyl Tyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. are mentioned.

Examples of the aryl group include a benzene ring, two to three benzene rings forming a condensed ring, a benzene ring and a five-membered unsaturated ring forming a condensed ring, and the like.

As a specific example of the said aryl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, etc. are mentioned, for example. In these, a phenyl group and a naphthyl group are preferable.

The alkyl group may have a substituent, and as an aryl group (hereinafter sometimes referred to as a "substituted aryl group") having such a substituent, for example, hydrogen is used as a substituent on the cyclic carbon atom of the aryl group described above. Enumerated having a group consisting of monovalent nonmetallic atom groups other than atoms.

As a substituent which the said aryl group is good, what was shown as the substituent which the above-mentioned alkyl group, substituted alkyl group, and the said alkyl group may have is preferable, for example.

Preferable specific examples of the substituted aryl group include a biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, and Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclo Hexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbon Barmoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfope Carbamoylphenyl group, sulfophenyl group, sulfonatephenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (force Phonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatephenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatephenyl group, tolylphosphonophenyl group, tolylphosphonatephenyl group, Allylphenyl group, 1-propenyl methylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, etc. are mentioned. .

Examples of the alkenyl group (-C (R ⁰² ) = C (R ⁰³ ) (R ⁰⁴ )) and alkynyl group (-C≡C (R ⁰⁵ )) include R ⁰² , R ⁰³ , R ⁰⁴ , and R ^The group which ⁰⁵ consists of monovalent nonmetallic atom groups is mentioned.

As said R <^02> , R <^03> , R <^04> , R <^05> , a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, etc. are mentioned, for example. As these specific examples, what was shown as the above-mentioned example can be enumerated. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, or a cyclic alkyl group is preferable.

Preferable specific examples of the alkenyl group and alkynyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group and 2- Methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenylethy Nilyl groups and the like.

As said heterocyclic group, the pyridyl group etc. which were illustrated as a substituent of a substituted alkyl group are mentioned, for example.

Examples of the oxy group (R ⁰⁶ O-) include those in which R ⁰⁶ is a group consisting of monovalent nonmetallic atomic groups in which hydrogen atoms are removed.

As such an oxy group, an alkoxy group, an aryloxy group, acyloxy group, carbamoyloxy group, N-alkyl carbamoyloxy group, N-aryl carbamoyloxy group, N, N-dialkyl carbamoyloxy group is mentioned, for example. , N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy group, phosphonooxy group, phosphonateoxy group and the like are preferable.

As the alkyl group and the aryl group in these, the thing shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group can be mentioned. Moreover, as an acyl group (R ⁰⁷ CO-) in an acyloxy group, the thing of the alkyl group, substituted alkyl group, aryl group, and substituted aryl group which R ⁰⁷ listed by the previous example is mentioned. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an aryl sulfoxy group are more preferable.

Specific examples of preferred oxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group, phenethyloxy group, carboxy Ethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholi Noethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, Ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyloxy group, naphthyloxy group, phenylsulfonyloxy group, phosphonooxy group, phosphonateoxy group, etc. are mentioned.

Examples of the amino group (R ⁰⁸ NH-, (R ⁰⁹ ) (R ⁰¹⁰ ) N-) which may include an amide group include those in which R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ consist of a monovalent nonmetallic atomic group in which hydrogen atoms are removed. do. In addition, R ⁰⁹ and R ¹⁰ may be bonded to each other to form a ring.

Examples of the amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkyl acylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'- dialkyl ureido group, N'-aryl ureido group, N', N'- diaryl ureido group, N'-alkyl- N'-aryl ureido group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl ureido group, N ', N'-dialkyl- N-alkylureido group, N'-alkyl-N'-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N'-arylureido group, N '-Aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group , N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonyl Mino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, etc. are mentioned. Listed. Examples of the alkyl group and the aryl group in these include those described as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group described above. Further, R ⁰⁷ of the acyl amino group, N- alkyl acyl amino group, N- aryl acyl amino group of the acyl group (R ⁰⁷ CO-) in the same as described above. Among these, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, and acylamino group are more preferable.

Specific examples of the preferred amino group include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

Examples of the sulfonyl group (R ⁰¹¹ -SO _2- ) include a group in which R ⁰¹¹ is a monovalent nonmetallic atom group.

As such a sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, etc. are preferable, for example. Examples of the alkyl group and the aryl group in these include those described as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group described above.

Specific examples of the sulfonyl group include butylsulfonyl group, phenylsulfonyl group, chlorophenylsulfonyl group and the like.

The sulfonate group (-SO ₃ -) means a conjugated base anion group of a sulfo (-SO ₃ H) as described above, and generally is preferably used as well as the counter cation.

As such counter cations, generally known ones can be appropriately selected and used, for example, oniums (eg, ammonium, sulfonium, phosphonium, iodonium, azinium, etc.), metal ions ( For example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ and the like) are listed.

Examples of the carbonyl group (R ⁰¹³ -CO-) include those in which R ⁰¹³ is composed of a monovalent nonmetallic atom group.

Examples of such carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkyl carbamoyl, N-arylcarbamoyl, N, N- diarylcarbamoyl group, N-alkyl-N'-arylcarbamoyl group, etc. are mentioned. Examples of the alkyl group and the aryl group in these include those described as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group described above.

As the carbonyl group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group are preferable, and More preferred are a wheat group, an acyl group, an alkoxycarbonyl group, and an aryloxy carbonyl group.

Specific examples of the carbonyl group include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenyl etenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N-methylcarbamoyl group, N-phenyl carbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group, etc. are mentioned preferably.

Examples of the sulfinyl group (R ⁰¹⁴ -SO-) include groups in which R ⁰¹⁴ is a monovalent nonmetallic atom group.

Examples of such sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N-dia The aryl sulfinamoyl group, N-alkyl-N-aryl sulfinamoyl group, etc. are mentioned. Examples of the alkyl group and the aryl group in these include those described as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group described above. Among these, alkylsulfinyl groups and arylsulfinyl groups are preferable.

Specific examples of the substituted sulfinyl group include hexyl sulfinyl group, benzyl sulfinyl group, tolyl sulfinyl group and the like.

The said phosphono group means that one or two of the hydroxyl groups on a phosphono group are substituted by the other organic oxo group, For example, the above-mentioned dialkyl phosphono group, the diaryl phosphono group, the alkylaryl phosphono group, and mono An alkyl phosphono group, a monoaryl phosphono group, etc. are preferable. In these, a dialkyl phosphono group and a diaryl phosphono group are more preferable.

As a more preferable specific example of the said phosphono group, a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, etc. are mentioned.

As described above, the phosphonate group (-PO ₃ H _2- , -PO ₃ H-) is derived from an acid first dissociation or an acid second dissociation of a phosphono group (-PO ₃ H ₂ ). It means a conjugated base anion group. It is usually preferred to use it with counter cations. As such counter cations, generally known ones can be appropriately selected, for example, various oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.), metal ions (Na ⁺ , K). ⁺ , Ca ²⁺ , Zn ²⁺ and the like).

The phosphonate group may be a conjugated base anion of a hydroxyl group substituted with one organic oxo group in the phosphono group. Examples of the phosphonate group include the monoalkyl phosphono group (-PO ₃ H (alkyl)) and the monoaryl phosphono group described above. The conjugated base of (-PO ₃ H (aryl)) is listed.

The said aromatic group can manufacture 1 or more types of radically polymerizable compounds containing an aromatic group, and 1 or more types of other radically polymerizable compounds as a copolymerization component as needed by a normal radical polymerization method.

As said radical polymerization method, suspension polymerization method, solution polymerization method, etc. are generally mentioned, for example.

As a radically polymerizable compound containing the said aromatic group, the compound represented by structural formula (A) and the compound represented by structural formula (B) are preferable, for example.

However, in said structural formula (A), R <_1> , R <_2> and R <_3> represent a hydrogen atom or monovalent organic group. L may represent an organic group and may be absent. Ar represents an aromatic group which may contain a heterocycle.

However, in said structural formula (B), R <_1> , R <_2> and R <_3> and Ar show the same meaning as the said structural formula (A).

As said L organic group, it is a polyvalent organic group which consists of a nonmetallic atom, for example, 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 And those consisting of from 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms.

More specifically, as said organic group of L, what is comprised by combining the following structural units, polyvalent naphthalene, polyvalent anthracene, etc. can be mentioned.

The linking group of L may have a substituent, and as the substituent, the aforementioned halogen atom, hydroxyl group, carboxyl group, sulfonate group, nitro group, cyano group, amide group, amino group, alkyl group, alkenyl group, alkynyl group, aryl group , Substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonate group, silyl group, heterocyclic group.

In the compound represented by the said structural formula (A), and the compound represented by the structural formula (B), structural formula (A) is preferable at the point of a sensitivity. Moreover, it is preferable from the point of stability that it has a coupling group in the said structural formula (A), and, as said organic group of L, a C1-C4 alkylene group is preferable at the point of the removable (developability) of a non-image part.

The compound represented by the said structural formula (A) becomes a compound containing the structural unit of the following structural formula (I). In addition, the compound represented by the said structural formula (B) becomes a compound containing the structural unit of the following structural formula (II). Among these, the structural unit of structural formula (I) is preferable at the point of storage stability.

However, in Formulas (I) and (II), R ₁ , R ₂ and R ₃ , and Ar have the same meanings as those of Formulas (A) and (B).

In the structural formulas (I) and (II), it is preferable that R ₁ and R ₂ are hydrogen atoms and R ₃ is a methyl group in view of the removable (developability) of the non-image portion.

In addition, L of the said structural formula (I) is preferable at the point of the removable (developability) of a C1-C4 alkylene group of a non-burn part.

Although there is no restriction | limiting in particular as a compound represented by said structural formula (A) or a compound represented by structural formula (B), For example, the following exemplary compounds (1)-(30) are mentioned.

Among the exemplary compounds (1) to (30), (5), (6), (11), (14), and (28) are preferred, and among these, (5) and (6) are storage stability and development. It is more preferable at the point of sex.

Although content in the said binder of the aromatic group which may contain the said heterocycle does not have a restriction | limiting in particular, When the total structural unit of a high molecular compound is 100 mol%, the structural unit represented by said structural formula (I) is 20 mol% or more. It is preferable to contain, and it is more preferable to contain 30-45 mol%. When the said content is less than 20 mol%, storage stability may become low, and when it exceeds 45 mol%, developability may fall.

Ethylenically unsaturated bonds

There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, what is represented by following structural formula (III)-(V) is preferable.

However, of the structural formula (III) ~ (V), R 1 ~R 11 represents a monovalent organic group independently. X and Y each independently represent an oxygen atom, a sulfur atom, or -NR ₄ . Z represents an oxygen atom, a sulfur atom, -NR ₄ , or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

In said structural formula (III), R <_{1> is} respectively independently a hydrogen atom, the alkyl group which may have a substituent, etc. are preferable, respectively, and since a hydrogen atom and a methyl group have high radical reactivity, it is more preferable.

As said R <_2> and R <_{3>, they} are respectively independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxy carbonyl group, a sulfo group, a nitro group, a cyano group, the alkyl group which may have a substituent, the aryl group which may have a substituent, An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent Etc. are listed, and the hydrogen atom, the carboxyl group, the alkoxycarbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are more preferable because they have high radical reactivity.

As said R <_4> , the alkyl group etc. which may have a substituent are preferable, for example, and since a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group have high radical reactivity, it is more preferable.

Here, as the substituent which can be introduced, for example, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, halogen atom, amino group, alkylamino group, arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, Nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group, etc. are mentioned.

In the structural formula (IV), as R ₄ to R _8, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent , An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkyl amino group which may have a substituent, an aryl amino group which may have a substituent, an alkyl sulfonyl group which may have a substituent And an arylsulfonyl group which may have a substituent are preferable, and a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.

As said substituent which can be introduce | transduced, the thing enumerated in the said Formula (III) is illustrated.

In the above structural formula (V), R ₉ is preferably, for example, a hydrogen atom, an alkyl group which may have a substituent, and more preferable, because the hydrogen atom and the methyl group have high radical reactivity.

As said R <_10> , R <_11> , they respectively independently have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxy carbonyl group, a sulfo group, a nitro group, a cyano group, the alkyl group which may have a substituent, and a substituent, for example. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent A preferable arylsulfonyl group is preferable, and a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable because they have high radical reactivity.

Here, as said substituent which can be introduced, what was listed in Structural formula (III) is illustrated.

Z is an oxygen atom, a sulfur atom, -NR _13- , or a phenylene group which may have a substituent. R <_13> represents the alkyl group etc. which may have a substituent, and since a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group have high radical reactivity, it is preferable.

Among the side chain ethylenically unsaturated bonds represented by the above structural formulas (III) to (V), those of the structural formula (III) have a high polymerization reactivity, and thus the sensitivity is more preferable.

Although content in the said high molecular compound of the said ethylenically unsaturated bond does not have a restriction | limiting in particular, 0.5-3.0 meq / g is preferable, 1.0-3.0 meq / g is more preferable, 1.5-28 meq / g is especially preferable. When the said content is less than 0.5 meq / g, since there is little hardening reaction amount, it may become a reduction degree, and when more than 3.0 meq / g, storage stability may deteriorate.

Here, the said content (meq / g) can measure iodine by titration, for example.

Although there is no restriction | limiting in particular as a method of introduce | transducing the ethylenically unsaturated bond represented by said structural formula (III) into a side chain, For example, it is obtained by addition-reacting the high molecular compound containing a carboxyl group in a side chain, and the compound which has ethylenically unsaturated bond and an epoxy group Can be.

The high molecular compound which contains a carboxyl group in the said side chain, for example, manufactures 1 or more types of radically polymerizable compounds containing a carboxyl group, and 1 or more types of other radically polymerizable compounds as a copolymerization component as needed by a normal radical polymerization method. As said radical polymerization method, suspension polymerization method, solution polymerization method, etc. are mentioned, for example.

Although it will not restrict | limit especially if it has these as a compound which has the said ethylenically unsaturated bond and an epoxy group, For example, the compound represented by the following structural formula (VI) and the compound represented by (VII) are preferable. It is especially preferable to use the compound represented by structural formula (VI) from the point of high sensitivity.

However, in said structural formula (VI), R <_1> represents a hydrogen atom or a methyl group. L ₁ represents an organic group.

However, in said structural formula (VII), R <_2> represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4-7 membered aliphatic hydrocarbon group.

Among the compounds represented by the above formula (VI) and the compound represented by the formula (VII), the compound represented by the formula (VI) is preferable, and in the above formula (VI), L ₁ is a C 1-4 alkylene group It is more preferable.

There is no restriction | limiting in particular as a compound represented by said structural formula (VI) or a compound represented by structural formula (VII), For example, the following exemplary compounds (31)-(40) are mentioned.

As a radically polymerizable compound containing the said carboxyl group, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxy styrene, etc. are mentioned, for example, Acrylic acid, methacrylic acid is especially preferable. And the like.

Examples of the introduction reaction into the side chain include quaternary ammonium salts such as tertiary amines such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride and tetraethylammonium chloride, pyridine and triphenylphosphate. It can carry out by making a fin etc. catalyze and reacting for several hours to several hours at 50-150 degreeC reaction temperature in an organic solvent.

Although there is no restriction | limiting in particular as a structural unit which has an ethylenically unsaturated bond in the said side chain, For example, what is represented by the structure represented by following structural formula (i), the structure represented by structural formula (ii), and a mixture thereof is preferable. .

However, in said structural formula (i) and (ii), Ra-Rc represents a hydrogen atom or monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group which may have a linking group.

20 mol% or more is preferable, as for content in the high molecular compound of the structure represented by the said structural formula (i)-the structure represented by structural formula (ii), 20-50 mol% is more preferable, 25-45 mol% is especially preferable. . When the said content is less than 20 mol%, since there is little hardening reaction amount, it may become a reduction degree, and when more than 50 mol%, storage stability may deteriorate.

Carboxyl group

In the high molecular compound of this invention, in order to improve various performances, such as a non-image part removal property, you may have a carboxyl group.

The said carboxyl group can be provided to the said high molecular compound by copolymerizing the radically polymerizable compound which has an acidic group.

As an acid group which has such radically polymerizable, carboxylic acid, sulfonic acid, a phosphoric acid group, etc. are mentioned, for example, A carboxylic acid is especially preferable.

There is no restriction | limiting in particular as a radically polymerizable compound which has the said carboxyl group, According to the objective, it can select suitably, For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxy styrene Etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxy styrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

Content in the binder of the said carboxyl group is 1.0-4.0 meq / g, and 1.5-3.0 meq / g is preferable. Developability may become inadequate when the said content is less than 1.0 meq / g, and when it exceeds 4.0 meq / g, it may become easy to receive the image intensity damage by alkaline-water image development.

It is preferable to further copolymerize another radically polymerizable compound in addition to the above-mentioned radically polymerizable compound for the purpose of improving various performances, such as image intensity | strength, of the high molecular compound of this invention.

As a radically polymerizable compound of that excepting the above, the radically polymerizable compound chosen from acrylic acid ester, methacrylic acid ester, styrene, etc. are mentioned, for example.

Specific examples include acrylic acid esters such as alkyl acrylates, methacrylates such as aryl acrylates and alkyl methacrylates, styrenes such as aryl methacrylates, styrenes and alkyl styrenes, alkoxy styrenes and halogen styrenes. do.

As said acrylic ester, the thing of 1-20 carbon atoms of an alkyl group is preferable, For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, Chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

As said aryl acrylate, phenyl acrylate etc. are mentioned, for example.

As said methacrylic acid ester, the thing of 1-20 carbon atoms of an alkyl group is preferable, For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl 3-hydroxypropyl methacrylate, trimethylol propane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, and the like.

As said aryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc. are mentioned, for example.

As the styrene, for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoro Romethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene and the like.

As said alkoxy styrene, methoxy styrene, 4-methoxy-3-methylstyrene, dimethoxy styrene, etc. are mentioned, for example.

As said halogen styrene, for example, chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromine styrene, dibrom styrene, iodine styrene, fluoro styrene, trifluoro styrene, 2-bromo- 4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc. are mentioned.

These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

There is no restriction | limiting in particular as a solvent used when synthesize | combining the high molecular compound of this invention, According to the objective, it can select suitably, For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol , Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N , N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These may be used individually by 1 type and may mix and use 2 or more types.

10, OO or more are preferable and, as for the molecular weight of the high molecular compound of this invention, 10,000-50,000 are more preferable. When the said mass average molecular weight is less than 10,000, cured film strength may run short, and when it exceeds 50,000, developability will fall.

In addition, the high molecular compound of this invention may contain the unreacted monomer. In this case, 15 mass% or less of content in the said high molecular compound of the said monomer is preferable.

The high molecular compound which concerns on this invention may be used individually by 1 type, and may mix and use 2 or more types. Moreover, you may mix and use other high molecular compounds. In this case, 50 mass% or less is preferable and, as for content in the high molecular compound of the said invention of the high molecular compound of that excepting the above, 30 mass% or less is more preferable.

5-80 mass% is preferable, and, as for solid content in the said photosensitive composition of the said binder, 10-70 mass% is more preferable.

[Elastomer]

The elastomer has a modulus of elasticity of 1 to 100 MPa by dynamic viscoelasticity measurement in a temperature range of 200 to 220 deg. C in which the cured shrinkage and flexibility of the cured film are modified and the temperature at the time of reflow is improved by using the polymer in combination with the binder. It can be reduced, and has the function of improving the shear adhesion with the sealing material. That is, by adding a flexible elastomer, the stress of the cured film can be alleviated, and the cured coating film can be modified. If the elastic modulus is less than 1 MPa, the mechanical strength is lowered, and if it exceeds 100 MPa, the shear adhesion is lowered.

There is no restriction | limiting in particular as said elastomer, According to the objective, it can select suitably, For example, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer are mentioned, These elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. In addition, there is no restriction | limiting in particular as a property of the said elastomer, According to the objective, it can select suitably, For example, it is preferable that it is alkali-soluble or swelling in terms of the production efficiency of a developing process.

There is no restriction | limiting in particular as said styrene-type elastomer, According to the objective, it can select suitably, For example, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene- ethylene- butylene-styrene block copolymer Polymers, styrene-ethylene-propylene-styrene block copolymers are listed. In addition to styrene which is a component constituting the styrenic elastomer, styrene derivatives such as α-methyl styrene, 3-methyl styrene, 4-propyl styrene and 4-cyclohexyl styrene can be used. Specifically, Tuprene, Solprene T, Asaprene T, Toughtec (above, manufactured by Asahi Kasei Industries), Elastomer AR (made by Aaron Mars), Clayton G, Overlyflex (made by Shell Japan) , JSR-TR, TSR-SIS, Dynaron, XSK-Series XFR-Series (above, manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Electrochemical Industry Co., Ltd.), Quintech (manufactured by Japan Xeon), TPE -SB series (manufactured by Sumitomo Chemical Industry Co., Ltd.), Rabaron (manufactured by Mitsubishi Chemical Co., Ltd.), Septon, Hibra (above, made by Kuraray), Sumprex (manufactured by Sumitomo Bake Light Co., Ltd.), Leosto Mercury, actiner (manufactured by Riken Vinyl Industries Co., Ltd.), VANDEX series (manufactured by Dic Bayer Polymer), Hytrel series (manufactured by Toray DuPont), and the like.

There is no restriction | limiting in particular as said olefin elastomer, According to the objective, it can select suitably, For example, C2-C20 alpha olefin, such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl- pentene And ethylene-propylene copolymers (EPR), ethylene-propylene-diene copolymers (EPDM) and the like, and further include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, Non-conjugated dienes and α-olefin copolymers having 2 to 20 carbon atoms such as methylene norbornene, ethylene norbornene, butadiene and isoprene are listed. Also listed are carboxy-modified NBRs obtained by copolymerizing methacrylic acid with butadiene-acrylonitrile copolymers. Specific examples include ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer rubber, and the like. In addition, specifically, a mirror stormer (made by Mitsui Petrochemical), EXACT (made by Exxon Chemical), ENGAGE (made by Dow Cal), hydrogenated styrene-butadiene rubber "DYNABON HSBR" (made by Nippon Synthetic Rubber Co., Ltd.), butadiene Acrylonitrile copolymer “NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.) or “XER series” of sock end carboxyl group-modified butadiene-acrylonitrile copolymer having a crosslinking point (manufactured by Nippon Synthetic Rubber Co., Ltd.), etc. This is listed.

There is no restriction | limiting in particular as said urethane-type elastomer, According to the objective, it can select suitably, For example, it consists of the hard segment which consists of low molecular glycol and diisocyanate, and the structural unit of the soft segment which consists of high molecular (long-chain) diol and diisocyanate, , Polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene · 1,4-butylene adipate), polycaprolactone, poly (1, 6-hexylene carbonate), poly (1, 6- hexylene neopentylene adipate), etc. are mentioned. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. In addition to ethylene glycol, short-chain diols, such as propylene glycol, 1, 4- butanediol, and bisphenol A, can be used, The number average molecular weight of short-chain diol is 48-500 is preferable. Specific examples of the urethane elastomer include PANDEX T-2185, T-2983N (manufactured by Japan Nippon Ink), silactron E790 and the like.

There is no restriction | limiting in particular as said polyester-type elastomer, According to the objective, it can select suitably, For example, what is obtained by polycondensing a dicarboxylic acid or its derivative (s) and a diol compound or its derivative (s) is mentioned. As a specific example of dicarboxylic acid, Aromatic dicarboxylic acid, such as telephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and aromatic dicarboxylic acid in which the hydrogen atom of these aromatic nucleus was substituted by methyl group, ethyl group, phenyl group, etc., Aliphatic dicarboxylic acids, such as a C2-C20 aliphatic dicarboxylic acid, such as adipic acid, a sebacic acid, and a dodecane dicarboxylic acid, and cyclohexane dicarboxylic acid, etc. are mentioned. These compounds may be used alone or in combination of two or more. Specific examples of the diol compound include aliphatic diols and alicyclic compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol Diols or dihydric phenols represented by the following structural formulas are listed.

In the above structural formula, Y represents any one of 1 to 10 carbon atoms alkylene group, 4 to 8 carbon atoms cycloalkylene group, -O-, -S-, and -SO _2- , or benzene Direct bonds between the rings are shown. R ¹ and R ² represent a halogen or an alkyl group having 1 to 12 carbon atoms. 1 and m represent the integer of 0-4, p is 0 or 1.

Specific examples of the polyester elastomer include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, resorcin and the like. These compounds may be used alone or in combination of two or more.

In addition, as the polyester-based elastomer, a multi-component having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example polytetramethylene glycol) portion as a soft segment component Block copolymers may also be used.

As said multi-block copolymer, the thing of various grades is mentioned by the difference of the kind, ratio, and molecular weight of a hard segment and a soft segment. Specific examples include Hytrel (manufactured by Dupont Toray Co., Ltd.), Perpren (manufactured by Dongyang Spinning Co., Ltd.), Espell (manufactured by Hitachi Chemicals, Inc.), and the like.

There is no restriction | limiting in particular as said polyamide-type elastomer, According to the objective, it can select suitably, For example, the polyether block amide type and polyether ester which used polyamide on hard, and polyether or polyester on soft. Polyamide-6, 11, 12, etc. are used as a polyamide, and polyoxyethylene, polyoxypropylene, polytetramethylene glycol, etc. are used as a polyamide. Specifically, UBE polyamide elastomer (manufactured by Ubeheungsan Co., Ltd.), diamide (manufactured by Daicel Hurus Co., Ltd.), PEBAX (manufactured by Toray Corporation), Glylon ELY (manufactured by MS Japan), Nopamix (manufactured by Mitsubishi Chemical Corporation), Gleelax (manufactured by Japan Nippon Inks Co., Ltd.), and the like are listed.

There is no restriction | limiting in particular as said acrylic elastomer, According to the objective, it can select suitably, For example, an acrylate, a butyl acrylate, a methoxy ethyl acrylate, an ethoxy ethyl acrylate, etc. are used as a main component, Moreover, glycidyl methacrylate, allyl glycidyl ether, etc. are used as a crosslinking point monomer. Moreover, acrylonitrile and ethylene can also be copolymerized. Specifically, an acrylonitrile- butyl acrylate copolymer, an acrylonitrile- butyl acrylate- ethyl acrylate copolymer, an acrylonitrile- butyl acrylate- glycidyl methacrylate copolymer, etc. are mentioned.

There is no restriction | limiting in particular as said silicone elastomer, According to the objective, it can select suitably, For example, organo polysiloxane is made into the main component, and it is divided into polydimethylsiloxane type, polymethylphenylsiloxane, and polydiphenylsiloxane type. Some may have been modified with a vinyl group, an alkoxy group or the like. As a specific example, KE series (made by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), etc. are mentioned.

In addition to the thermoplastic elastomer described above, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin is, for example, some or all epoxy groups of the above-described bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolak type epoxy resin or cresol novolak type epoxy resin. It is obtained by modifying into a sock end carboxylic acid modified butadiene-acrylonitrile rubber, terminal amino modified silicone rubber, or the like. Among these elastomers, in terms of shear adhesion, Espel (Hitachi Chemical Co., Ltd., Espel 1612, 1620), which is a sock-end carboxyl group-modified butadiene-acrylonitrile copolymer and a polyester-based elastomer having a hydroxyl group, is preferable. .

There is no restriction | limiting in particular in content of the said elastomer, According to the objective, it can select suitably, For example, 2-50 mass parts is preferable with respect to 100 mass parts of binders, and 4-20 mass parts is more preferable. If it is less than 2 mass parts, the elasticity modulus in the high temperature area | region of a cured film will not fall, and when it exceeds 50 mass parts, an unexposed part will tend not to elute with a developing solution.

[Polymerizable Compound]

There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, For example, the compound which has one or more ethylenically unsaturated bond is preferable.

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

There is no restriction | limiting in particular as a compound which has one or more of said ethylenically unsaturated bonds, Although it can select suitably according to the objective, For example, at least 1 sort (s) chosen from the monomer which has a (meth) acryl 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, (Meth) acrylate after addition reaction of ethylene oxide and a propylene oxide to polyfunctional alcohols, such as bisphenol Urethane acrylates described in each publication such as yttized, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Polyester acrylates described in each publication such as 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 these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

5-50 mass% is preferable, and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. When the solid content is less than 5% by mass, problems such as deterioration of developability and a decrease in exposure sensitivity may occur. When the solid content is more than 50% by mass, the adhesiveness of the photosensitive layer may be too strong.

[Photopolymerization Initiator]

There is no restriction | limiting in particular as said photoinitiator 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, It may be an activator which generates a certain radical with a photoexcited sensitizer and generates an active radical, or may be an initiator for initiating cationic polymerization depending on the type of monomer.

The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 in a range of about 300 to 800 nm in wavelength. As for the said wavelength, 330-500 nm is more preferable.

As said photoinitiator, a halogenated hydrocarbon derivative (for example, having a triazine skeleton, having an oxadiazole skeleton, etc.), hexaaryl biimidazole, an oxime derivative, an organic peroxide, a thio compound, a ketone The compound, aromatic onium salt, metallocenes, etc. are mentioned. Among these, halogenated hydrocarbons, oxime derivatives, ketone compounds, and hexaarylbiimidazole-based compounds having a triazine skeleton are preferable from the viewpoints of the sensitivity, the storage properties of the photosensitive layer, and the adhesion between the photosensitive layer and the substrate for forming a printed wiring board. .

Specifically, the compound etc. which are described in [0288]-[0309] of Unexamined-Japanese-Patent No. 2005-258431 are mentioned, for example.

As a more preferable example of the said photoinitiator, in the exposure mentioned later, wavelength can respond to a 405 nm laser beam, A phosphine oxide, (alpha)-aminoalkyl ketone, the halogenated hydrocarbon compound which has the said triazine skeleton, and the amine as a sensitizer mentioned later The complex photoinitiator which combined the compound, the said oxime derivative, the said hexaaryl biimidazole compound, titanocene, etc. are mentioned.

Moreover, what combined alpha-amino alkyl ketones and aromatic ketone compounds, such as thioxanthone, as a sensitizer is also preferable.

In particular, an oxime derivative is preferable from a high sensitivity.

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

[Thermal cross-link]

There is no restriction | limiting in particular as said 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. It is preferable that the said thermal crosslinking agent is alkali-insoluble from a viewpoint of plating tolerance.

Examples of the epoxy compound having at least two oxysilane groups in the above molecule include bixylenol type or biphenol type epoxy resins (manufactured by YX4000 Japan Epoxy Resin Co., Ltd.) or mixtures thereof, isocyanurate skeletons and the like. Heterocyclic epoxy resin ("TEPIC", Ilsan Chemical Industry Co., Ltd., "Araldite PT810; Chiba Specialty Chemicals", etc.), 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 type) Epoxy resins), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyl dimethanol type epoxy resin, Phenolic biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; Dai Nippon Ink Chemical Co., Ltd. product", 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) , Dimeric acid diglycidyl ester) hydantoin type epoxy resin, alicyclic epoxy resin (3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxy) Cyclohexylmethyl) adipate, dicyclopentadiene diepoxide, `` GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industry, '' etc.), imide alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, Bisphenol A novolac epoxy resin, tetra Neilol 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, a commercial item as "ESN -190, ESN-360, manufactured by Shinil Iron Chemical Co., Ltd., `` HP-4032, EXA-4750, EXA-4700; The reaction product of the polyphenol compound and epichlorohydrin obtained by addition reaction of a phenol compound and diolefin compounds, such as divinylbenzene and dicyclopentadiene, 4-vinylcyclo Epoxidized ring-opening polymer of hexene-1-oxide with pernitric 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, azophenyl type liquid crystal epoxy resin, azomethinephenyl 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 Nippon Oil Holding Co., Ltd. "etc.), copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, bis (glycidyl oxyphenyl) fluorene type epoxy water And bis (glycidyl oxyphenyl) adamantane, but open the like tanhyeong epoxy resin is not limited to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

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

In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl substituted glycidyl group, or at least one epoxy group may be a β-alkyl substituted glycidyl group. good.

There is no restriction | limiting in particular as said (beta) -alkyl substituted glycidyl group, According to the objective, it can select suitably, For example, (beta) -methyl glycidyl group, (beta)-ethyl glycidyl group, (beta) -propyl glycidyl group, (beta)- The butylglycidyl group etc. are enumerated, and among these, the (beta) -methylglycidyl group is preferable from a viewpoint of improving the storage stability of the said photosensitive resin composition, and a viewpoint of the ease of synthesis.

As an epoxy compound containing the epoxy group which has an alkyl group in the said (beta) position, the epoxy compound derived from a polyhydric phenol compound and (beta) -alkyl epihalohydrin, for example is preferable.

There is no restriction | limiting in particular as said (beta) -alkyl epihalohydrin, According to the objective, it can select suitably, For example, (beta) -methyl epichlorohydrin, (beta) -methyl epibromohydrin, (beta) -methyl epifluorohydrin Β-methyl epihalohydrin, such as drone; β-ethyl epihalohydrin such as β-ethyl epichlorohydrin, β-ethyl epibromohydrin and β-ethyl epifluorohydrin; β-propyl epihalohydrin such as β-propyl epichlorohydrin, β-propyl epibromohydrin and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin and β-butyl epifluorohydrin; And the like. Among these, (beta) -methyl epihalohydrin is preferable from a viewpoint of the reactivity with the said polyhydric phenol, and fluidity | liquidity.

There is no restriction | limiting in particular if it is a compound containing two or more aromatic hydroxyl groups in 1 molecule as said polyhydric phenol compound, According to the objective, it can select suitably, For example, bisphenol compounds, such as bisphenol A, bisphenol F, bisphenol S, Non-phenol compounds such as biphenol, biphenol and tetramethyl biphenol, naphthol compounds such as dihydroxynaphthalene and vinaptol, phenol novolak resins such as phenol-formaldehyde polycondensate, cresol-formaldehyde polycondensate and the like Bisphenol compounds, such as a C1-C10 dialkyl substituted phenol-formaldehyde polycondensate, such as ten monoalkyl substituted phenol-formaldehyde polycondensates, xylenol-formaldehyde polycondensate, and a bisphenol A-formaldehyde polycondensate- Formaldehyde polycondensates, co-condensates of phenol and monoalkyl substituted phenols having 1 to 10 carbon atoms, formaldehyde, phenolic compounds and di Heavy addition products of vinylbenzene, etc. are mentioned. Among these, the said bisphenol compound is preferable, for example, when selecting for the purpose of improving fluidity | liquidity and storage stability.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include, for example, di-β-alkylglycidyl ether of bisphenol A, di-β-alkylglycidyl ether of bisphenol F and di-β of bisphenol S. Di-β-alkylglycidyl ethers of bisphenol compounds such as -alkylglycidyl ether; Di-β-alkylglycidyl ethers of biphenol compounds such as di-β-alkylglycidyl ether of biphenol and di-β-alkylglycidyl ether of tetramethylbiphenol; Β-alkylglycidyl ethers of naphthol compounds such as di-β-alkylglycidyl ether of dihydroxynaphthalene and di-β-alkylglycidyl ether of vinaphthol; Poly-β-alkylglycidyl ethers of phenol-formaldehyde polycondensates; Poly-β-alkyl glycidyl ethers of 1 to 10 carbon-based monoalkyl substituted phenol-formaldehyde polycondensates such as poly-β-alkylglycidyl ether of cresol-formaldehyde polycondensate; Poly-β-alkyl glycidyl ethers of 1 to 10 carbon atoms dialkyl substituted phenol-formaldehyde polycondensates such as poly-β-alkylglycidyl ethers of xylenol-formaldehyde polycondensates; Poly-β-alkylglycidyl ethers of bisphenol compound-formaldehyde polycondensates such as poly-β-alkylglycidyl ethers of bisphenol A-formaldehyde polycondensates; Poly-β-alkylglycidyl ethers of polyaddition products of phenol compounds and divinylbenzene; And the like.

Among these, (beta) -alkylglycidyl ether derived from the bisphenol compound represented by the following structural formula (iii), and the polymer obtained from this, epichlorohydrin, etc., and the phenolic compound-formaldehyde polycondensation represented by the following structural formula (iv) Preference is given to poly-β-alkyl glycidyl ethers of the combination.

However, in said structural formula (iii), 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 (iv) R represents either a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, R "represents any one of hydrogen atom and CH _3, n is an integer of 0 to 20.

The epoxy compound containing the epoxy group which has an alkyl group in these (beta) positions may be used individually by 1 type, and may use 2 or more types together. Moreover, it is also possible to use together the epoxy compound which has the epoxy compound which has an at least two oxirane group in 1 molecule, and the epoxy group which has an alkyl group in (beta) position.

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) methylmethacrylate, (3-ethyl-3-oxetanyl) methylmethacrylate or In addition to polyfunctional oxetanes such as these oligomers or copolymers, compounds having an oxetane group, novolak resins, poly (p-hydroxy styrene), cardo-type bisphenols, calix arenes, calyx resorcinrenes, and seals Some ether compounds, such as resin which has hydroxyl groups, such as a sesquioxane, are mentioned, In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate, etc. are mentioned.

Moreover, in order to promote the thermosetting of the said epoxy compound and the said oxetane compound, an amine compound (for example, dicyandiamide, benzyl dimethylamine, 4- (dimethylamino) -N, N- dimethylbenzylamine , 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc., quaternary ammonium salt compounds (e.g. triethylbenzylammonium chloride, etc.), block isocyanate compounds (e.g. For example, dimethylamine etc., an imidazole derivative bicyclic amidine compound, and its salt (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl imida) Sol, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. ), Phosphorus compounds (e.g. triphenylphosphine), guanamine compounds (e.g. melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine induction (E.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6- Diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc. can be used. These may be used individually by 1 type and may use 2 or more types together. Moreover, as long as it can accelerate | stimulate reaction of the said hardening catalyst of the said epoxy resin 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 thermosetting other than the above.

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 carboxylic acid 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 isocyanates (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-isoisanatephenyl) 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 such as hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate and derivatives thereof; 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.

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, alkylacetate acetate oxime, acetoxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one block isocyanate group in the molecule of JP-A-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 preferred 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.

In addition, in order to promote thermosetting of the thermal crosslinking agent, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzyl amine, 4-meth). Methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzyl ammonium chloride, etc.), block isocyanate compounds (for example, Dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2 -Phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus Compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4- Diamino-6-meth Tacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc. can be used. These may be used individually by 1 type and may use 2 or more types together. The curing catalyst of the thermal crosslinking agent or a compound capable of promoting the reaction between these and a carboxyl group is not particularly limited, and a compound capable of promoting thermosetting other than the above may be used.

As for solid content in the said photosensitive composition of the said thermal crosslinking agent and the compound which can promote thermosetting of these and a carboxylic acid, 0.01-15 mass% is preferable.

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

[Other Ingredients]

Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and adhesion promoters to the substrate surface and other auxiliary agents (e.g., For example, electroconductive particle, a filler, an antifoamer, a flame retardant, a leveling agent, a peeling promoter, antioxidant, a fragrance | flavor, a surface tension regulator, a chain transfer agent, etc.) may be used together.

By containing these components suitably, properties, such as stability, a photographic property, and film | membrane property, of the target photosensitive composition can be adjusted.

-Sensitizer-

It is possible to add a sensitizer to the said photoinitiator for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to a photosensitive layer.

The said sensitizer can be suitably selected with visible light, an ultraviolet-ray laser, 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 generator, acid generator, etc.) (e.g., energy transfer, electron transfer, etc.) It is possible to generate useful groups such as these.

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 supply type initiator and sensitizing dye, (2) electron accepting type initiator and a sensitizing dye, for example. , (3) electron supply type initiator, sensitizing dye, and electron accepting type initiator (three-way clock)].

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, erythrosin, rhodamine B, rose bengal), cyanines (e.g., indocarbocyanine, thiacarbocyanine, oxacarbocyanine), melocyanine (e.g., Melocyanine, carbomelocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acrylflavin, 9 -Phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, anthraquinones (e.g., anthraquinones), scaryliums (e.g., scalium), acri Porcines (eg, acridon, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (eg, 2 -Chloro-10-butylacridone, etc.), coumarins (for example, 3- (2-benzofloyl) -7-diethylaminocoumarin, 3- (2-benzofloyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylamino coumarin, 3- (4-dimethylaminobenzoyl) -7-di Ethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-meth Methoxycoumarin, 3- (2-floyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridyl Carbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japanese Patent Laid-Open 2002-363206, Japanese Patent Laid-Open 2002-363207 Coumarin compounds described in Japanese Patent Application Laid-Open No. 2002-363208, Japanese Patent Application Laid-Open No. 2002-363209, etc.), and thioxanthone compound ( Thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propyloxy thioxanthone, Quantacure QTX, etc.), and the like Preferred are amine compounds substituted with any of bright compounds (cyclic compounds) and at least two aromatic hydrocarbon rings and aromatic heterocycles.

Among the above-mentioned condensed compounds, heterocyclic condensed ketone compounds (acridone compounds, thioxanthone compounds, coumarin compounds, etc.), and acridine compounds are more preferable. Among the heterocyclic ring-type ketone compounds, an acridon compound and a thioxanthone compound are particularly preferable.

The amine compound substituted with any one of the at least two aromatic hydrocarbon rings and the aromatic heterocycle is preferably a sensitizer having an absorption maximum with respect to light in the wavelength range of 330 to 450 nm. For example, a disubstituted amino benzophenone series A disubstituted amino-benzene compound having a heterocyclic group as a substituent on a carbon atom in the para position with respect to the compound and a benzene cyclic amino group, and a substituent containing a sulfonyl imino group in the carbon atom in the para position with respect to the benzene cyclic amino group. Di-substituted amino-benzene such as di-substituted amino-benzene compound having a compound, a di-substituted amino-benzene compound having a carbostyryl skeleton, and a compound having a structure in which at least two aromatic rings are bonded to a nitrogen atom. The compound which has as a structure is listed.

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

0.01-4 mass% is preferable with respect to the all components of the photosensitive composition, as for content of the said sensitizer, 0.02-2 mass% is more preferable, 0.05-1 mass% is especially preferable.

When the said content becomes less than 0.01 mass%, a sensitivity may fall, and when it exceeds 4 mass%, the shape of a pattern may deteriorate.

Thermal polymerization inhibitor

You may add the said thermal polymerization inhibitor in order to prevent thermal superposition | polymerization or time-lapse superposition | polymerization of the said polymeric compound in the said photosensitive layer.

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. Roxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl- 6-t-butyl phenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and A1 Chelates and the like.

As for content of the said thermal polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound of the said photosensitive layer, 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.

Plasticizer

The plasticizer may be added in order to control the film properties (flexibility) of the photosensitive layer.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, and diphenyl phthalate. Phthalic acid esters such as yate, diallyl phthalate and octyl capryl phthalate; Glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate and triethylene glycol dicaprylic acid ester; Phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate; Amides such as 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide and N-n-butylacetamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl azelate and dibutyl maleate; Glycols such as polyethylene glycol and polypropylene glycol, such as triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, and 4,5-diepoxycyclohexane-1,2-dicarboxylic acid dioctyl Listed.

0.1-50 mass% is preferable with respect to the all components of the said photosensitive layer, as for content of the said plasticizer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

-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 (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), Poster Bomb Red ESB (CI Pigment Violet 19) , Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Spooler (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black), Carbon CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI 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, CI Pigment Blue 64, and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, the dye suitably selected from well-known dye can be used as needed.

Solid 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, an inorganic pigment or organic fine particles may be added to the photosensitive composition for the purpose of improving the surface hardness of the permanent pattern, or reducing the coefficient of linear expansion or reducing the dielectric constant or dielectric tangent of the cured film itself. Can be.

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, Fused 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 100 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, crosslinked resin, etc. which are about 1-5 micrometers of average particle diameters, and the oil absorption amount of about 100-200m <^2> / g 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 reduced, and if it exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, the film quality of the cured film is subdued, and the permanent pattern In the case of forming the wiring by using the above, the function as a protective film of the wiring may be impaired.

--Adhesive Promoter--

In order to improve the adhesiveness between each layer of the photosensitive film containing the photosensitive layer formed using the photosensitive composition of this invention, or the adhesiveness of the said photosensitive film and gas, 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- Triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto -5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group containing benzotriazole, silane coupling agent, etc. are mentioned.

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

The photosensitive composition of the present invention is free of edge fusion (cross-sectional fusion), has excellent tackiness and performance stability over time, facilitates film formation, and can efficiently form high-definition permanent patterns. For this reason, it can be widely used for forming permanent patterns, such as a printed wiring board, a color filter, a corrugated material, a rib material, a spacer, a partition, a display member, a hologram, a micromachine, a proof, especially a permanent pattern formation of a printed circuit board. It can use suitably for the use.

(Photosensitive film)

As the photosensitive film of this invention, it is preferable to have a support body and the photosensitive layer which consists of the photosensitive composition of the said invention formed on the said support body at least, and to have other layers, such as a thermoplastic resin layer suitably as needed. The photosensitive layer is as described above.

<Photosensitive layer>

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

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 200 mJ / cm ^2. which is preferably, O.2~1OOmJ / cm ² is more preferable and, O.5~5OmJ / cm ² is that it is particularly preferred the more preferable, and, 1~3OmJ / cm ^2.

When the said minimum energy is less than 0.1mJ / cm <^2> , fog may generate | occur | produce in a process process, and when it exceeds 20mJ / cm < ² >, the time required for exposure may become long and a process speed may become slow. .

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 following the said exposure.

The thickness of the cured layer increases as the exposure amount increases and decreases, and then becomes substantially the same as and substantially constant with the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure amount when the thickness of the cured layer becomes substantially constant.

Here, when the thickness of the said hardened layer and the thickness of the said photosensitive layer before the said exposure are less than +/- 1micrometer, it is considered that the thickness of the said hardened layer does not change by exposure and image 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 said 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 (copper precision yarn) Production)) and the like.

Although the thickness of the said photosensitive layer does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, 4-30 micrometers is especially preferable.

<Support and protective film>

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. As said support body and protective film, it specifically describes in [0342]-[0348] of Unexamined-Japanese-Patent No. 2005-258431.

<Other layers>

There is no restriction | limiting in particular as another layer in the said photosensitive film, According to the objective, it can select suitably, For example, a cushion layer, an oxygen barrier layer (PC layer), a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer, etc. You may have a layer of. You may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have a protective film on the said photosensitive layer.

Cushion Floor

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

When the cushion layer is swellable or soluble with respect to the alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylic ester copolymer, a saponified product of styrene and a (meth) acrylic acid ester copolymer, and vinyltoluene ( Saponification of a meta) acrylic acid ester copolymer, poly (meth) acrylic acid ester, saponifications, such as (meth) acrylic acid ester copolymers, such as butyl (meth) acrylate and vinyl acetate, of (meth) acrylic acid ester and (meth) acrylic acid The copolymer, the copolymer of styrene, (meth) acrylic acid ester, and (meth) acrylic acid, etc. are mentioned.

There is no restriction | limiting in particular in the softening point (vicat) of a thermoplastic resin in this case, Although it can select suitably according to the objective, For example, 80 degrees C or less is preferable.

As the thermoplastic resin having the softening point of 80 ° C. or less, the above-mentioned thermoplastic resins and the above-mentioned plastic performance manual (Japanese Plastics Industry Federation, All Japan Plastic Molding Industry Association Editing, published by Industrial Society of Japan, issued October 25, 1968) It is enumerated that it is soluble in alkaline liquids among organic polymers having a softening point of about 80 ° C. or lower. In addition, even in an organic polymer material having a softening point of 80 ° C. or more, it is also possible to add various plasticizers compatible with the organic polymer material in the organic polymer material to lower the actual softening point to 80 ° C. or less.

In addition, when the cushion layer is swellable or soluble with respect to the alkaline liquid, there is no particular limitation as to the interlayer adhesion of the photosensitive film, and it can be appropriately selected according to the purpose, but for example, among the interlayer adhesion of each layer, It is preferable that the interlayer adhesion between the cushion layers is the smallest. By setting it as such an interlayer adhesive force, only the said support body is peeled from the said photosensitive film, and after exposing the said photosensitive layer through the said cushion layer, the said photosensitive layer can be developed using alkaline developing solution. Moreover, after exposing the said photosensitive layer leaving the said support body, only the said support body may be peeled from the said photosensitive film, and the said photosensitive layer may be developed using alkaline developing solution.

There is no restriction | limiting in particular as a adjusting method of the said interlayer adhesive force, According to the objective, it can select suitably, For example, the method of adding a well-known polymer, a supercooling substance, an adhesion | attachment improver, surfactant, a mold release agent, etc. to the said thermoplastic resin is listed. do.

There is no restriction | limiting in particular as said plasticizer, Although it can select suitably according to the objective, For example, polypropylene glycol, polyethyleneglycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, Alcohols and esters such as biphenyl diphenyl phosphate; Amides, such as toluene sulfonamide, etc. are mentioned.

When the cushion layer is insoluble in the alkaline liquid, examples of the thermoplastic resin include copolymers in which the main component is ethylene as an essential copolymer component.

There is no restriction | limiting in particular as a copolymer which uses the said ethylene as an essential copolymerization component, Although it can select suitably according to the objective, For example, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), etc. Listed.

When the cushion layer is insoluble in the alkaline liquid, there is no particular limitation as to the interlayer adhesion of the photosensitive film, and it can be appropriately selected according to the purpose. For example, the photosensitive layer and the cushion layer may be selected among the interlayer adhesion of each layer. It is preferable that the adhesive force of is the smallest. By setting it as such an interlayer adhesive force, after peeling the said support body and a cushion layer from the said photosensitive film, and exposing the said photosensitive layer, the said photosensitive layer can be developed using alkaline developing solution. Moreover, after exposing the said photosensitive layer leaving the said support body, you may peel off the said support body and the said cushion layer from the said photosensitive film, and develop the said photosensitive layer using an alkaline developing solution.

There is no restriction | limiting in particular as a adjusting method of the said interlayer adhesive force, According to the objective, it can select suitably, For example, the method of adding various polymers, a supercooling substance, an adhesion improving agent, surfactant, a mold release agent, etc. in the said thermoplastic resin, The method of adjusting the ethylene copolymerization ratio demonstrated to these etc. are mentioned.

There is no restriction | limiting in particular in the ethylene copolymer in the copolymer which makes the said ethylene an essential copolymer component, Although it can select suitably according to the objective, For example, 60-90 mass% is preferable, and 60-80 mass% is more It is preferable and 65-80 mass% is especially preferable.

When the copolymerization ratio of the said ethylene is less than 60 mass%, the interlayer adhesive force of the said cushion layer and the said photosensitive layer becomes high, and it may become difficult to peel at the interface of the said cushion layer and the said photosensitive layer, and it exceeds 90 mass% In this case, since the interlayer adhesion between the cushion layer and the photosensitive layer becomes too small, it is very easy to peel off between the cushion layer and the photosensitive layer, and the production of the photosensitive film including the cushion layer may be difficult. .

Although the thickness of the said cushion layer does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, 15-40 micrometers is especially preferable.

When the said thickness is less than 5 micrometers, the uneven | corrugated traceability to the unevenness | corrugation, a bubble, etc. in the surface of a base may fall, and a high-precision permanent pattern may not be formed, and when it exceeds 50 micrometers, dry load on manufacture Undesirable cases such as increase may occur.

Oxygen barrier layer (PC layer)

It is preferable that the said oxygen barrier layer is normally formed with polyvinyl alcohol as a main component, and it is preferable that it is a film about 0.5-5 micrometers in thickness.

[Method for Producing Photosensitive Film]

The said photosensitive film can be manufactured as follows, for example.

First, the material contained in the said photosensitive composition is melt | dissolved, emulsified, or disperse | distributed to water or a solvent, and the photosensitive resin composition solution for photosensitive films is prepared.

There is no restriction | limiting in particular as said solvent, 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, acetic acid-n-amyl, 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, dimethylene sulfoxide, 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.

Next, the said photosensitive resin composition solution is apply | coated on the said support body, it can be dried, a photosensitive layer can be formed, and a photosensitive film can be manufactured.

There is no restriction | limiting in particular as a coating method of the said photosensitive composition solution, Although it can select suitably according to the objective, For example, the spray method, the roll coating method, the rotation coating method, the slit coat method, the extrusion coating method, the curtain coating method Various coating methods, such as the die coat method, the gravure coat method, the wire bar coat method, the knife coat method, are mentioned.

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 at the temperature of 60-110 degreeC normally.

It is preferable that the said photosensitive film is wound up, for example in a cylindrical core, and rolled up to a long shape and stored.

There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. 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, OOm into roll shape. In this case, the support is preferably wound up to the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. In storage, it is preferable to provide a separator (particularly moisture-proof and desiccant-containing) on the end face from the viewpoint of protecting the end face and preventing edge fusion, and it is preferable to use a material having low packing moisture permeability.

By using the photosensitive composition of this invention, the photosensitive film of this invention is free of edge fusion (cross-sectional fusion), and is excellent in tackiness and performance stability at time, and it is easy to film, and forms a highly detailed permanent pattern efficiently It is possible to form various patterns such as permanent patterns such as protective films, interlayer insulating films, and solder resist patterns, for the production of liquid crystal structural members such as color filters, aggregate materials, rib materials, spacers, partition walls, holograms, micromachines, and proofs. It can be used preferably for pattern formation, such as these, and especially can be used for permanent pattern formation of a printed circuit board.

In addition, since the photosensitive film of this invention is uniform in thickness, even when a permanent pattern (protective film, an interlayer insulation film, a soldering resist, etc.) is thinned at the time of formation of a permanent pattern, in the high acceleration test (HAST), Since there is no occurrence of ion migration and a high-definition permanent pattern excellent in heat resistance and moisture resistance is obtained, lamination to the substrate is performed in more detail.

(Photosensitive laminated body)

The photosensitive laminated body of this invention has at least the photosensitive layer which consists of the photosensitive composition of this invention on a base, and laminates the other layer suitably selected according to the objective.

<Gas>

The substrate is a target substrate on which the photosensitive layer is formed, or a transfer target body on which at least the photosensitive layer of the photosensitive film of the present invention is transferred. There is no particular limitation, and the base can be appropriately selected according to the purpose. It can be arbitrarily selected from those having high smoothness to those having uneven surfaces. Plate-like gases are preferred, and so-called substrates are used. Specifically, the board | substrate (print board | substrate) for manufacturing a well-known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, a metal plate, etc. are mentioned.

[Production Method of Photosensitive Laminate]

As a manufacturing method of the said photosensitive laminated body, the method of apply | coating and drying the said photosensitive composition on the surface of the said base as a 1st aspect is mentioned, As a 2nd aspect, at least the photosensitive layer in the photosensitive film of this invention is heated. And a method of transferring and laminating while performing at least one of pressurization.

The manufacturing method of the photosensitive laminated body of a said 1st aspect apply | coats and dries the said photosensitive composition on the said base | substrate, and forms a photosensitive layer.

There is no restriction | limiting in particular as a method of the said application | coating and drying, According to the objective, it can select suitably, For example, the photosensitive composition solution is prepared by melt | dissolving, emulsifying, or disperse | distributing the said photosensitive composition to the surface of the said base in water or a solvent, And a method of laminating by directly applying the solution and drying.

There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent used for the said photosensitive film is mentioned. 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 and drying conditions, According to the objective, it can select suitably, It is performed by the same method and conditions as what was used for the said photosensitive film.

The manufacturing method of the photosensitive laminated body of a said 2nd aspect is laminated | stacked on the surface of the said base | substrate, performing at least any one of heating and pressurization of the photosensitive film of this invention. 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 | substrate.

There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.

There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

There is no restriction | limiting in particular as an apparatus which performs at least one of the said heating, According to the objective, it can select suitably, For example, a laminator (for example, Daesung Laminator Co., Ltd. VP-II and Nichigo-Morton Co., Ltd. VP130) ) And the like are preferably listed.

By using the photosensitive composition of the present invention, the photosensitive laminate of the present invention is free of edge fusion (cross-section fusion), has excellent performance stability under tackiness and aging, and can effectively form a high-definition permanent pattern, thereby providing a protective film. For forming various patterns such as permanent patterns such as interlayer insulating films and solder resist patterns, for producing liquid crystal structural members such as color filters, aggregates, ribs, spacers and partition walls, for forming patterns such as holograms, micromachines, and proofs It can use preferably etc., Especially, it can use preferably for the permanent pattern of a printed circuit board.

(Pattern forming apparatus and permanent pattern forming method)

The pattern forming apparatus of the present invention includes the photosensitive layer, and includes at least light irradiation means and light modulating means.

The permanent pattern forming method of the present invention includes at least an exposure step, and includes other steps such as an appropriately selected developing step.

Moreover, the said pattern forming apparatus of this invention confirms through description of the said permanent pattern formation method of this invention.

Exposure process

The said exposure process is a process of exposing to the photosensitive layer in the photosensitive film of this invention. The material of the photosensitive film of the present invention and the base material is as described above.

As an object of the said exposure, there is no restriction | limiting in particular as long as it is a photosensitive layer in the said photosensitive film, According to the objective, it can select suitably, For example, as mentioned above, at least any of heating and pressurizing a photosensitive film on a base material It is preferable to carry out with respect to the laminated body formed by laminating | stacking while performing one.

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 analogue exposure, According to the objective, it can select suitably, For example, the method of exposing with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xetone lamp, etc. through the negative mask which has a predetermined pattern is mentioned.

There is no restriction | limiting in particular as said digital exposure, According to the objective, it can select suitably, For example, it is preferable to generate | generate a control signal based on the pattern formation information to form, and to carry out using the light modulated according to the said control signal. For example, with respect to the said photosensitive layer, it has a light irradiation means, and n pieces (where n is a natural number of two or more), which are light-receiving means and the light emitted from the said light irradiation means, are arranged in two dimensions. An exposure head including light modulating means capable of controlling the drawing part in accordance with pattern information, wherein the exposure head is disposed so that the column direction of the drawing part makes a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. The exposure head is used for exposure among N (where N is a natural number of two or more) among the available drawing parts by use drawing part designation means. The drawing part to be specified is specified, and the drawing part control means controls the drawing part so that only the drawing part specified by the use drawing part designation means is involved in exposure to the exposure head, and to the photosensitive layer. In contrast, a method of moving the exposure head relatively in the scanning direction is preferable.

In the present invention, &quot; N-exposure exposure &quot; means N light spots in which almost straight lines parallel to the scanning direction of the exposure head are irradiated on the exposed surface in almost all regions of the exposed region on the exposed surface of the photosensitive layer. Exposure by the setting as it intersects with the pixel column). Here, "light spot row" (pixel row) means an array in a direction in which the angle formed by the scanning direction of the exposure head is smaller in the array of light spots (pixels) as the drawing units generated by the drawing section. In addition, the arrangement of the drawing portions may not necessarily be a rectangular lattice, for example, a parallelogram arrangement or the like.

Here, the term "approximately all areas" of the exposure area means that the number of the seedling row of the using seedling section intersecting a straight line parallel to the scanning direction of the exposure head by inclining the row of drawing sections at both edges of each drawing section, In such a case, even if a plurality of exposure heads are used to be connected to each other, the number of drawing rows in the use drawing section intersecting a straight line parallel to the scanning direction may slightly increase or decrease due to an error such as an installation angle or an arrangement of the exposure heads. In addition, in the very small part less than the resolution of the connection between the drawing section row of each using drawing section, the pitch of the drawing section along the direction orthogonal to the scanning direction by the error of the installation angle or the drawing section arrangement Use gravel which does not exactly match pitch of graveyard part and intersects straight line parallel to scanning direction The number of graves portion of heat is because, in some cases increasing or decreasing the range of ± 1. In addition, in the following description, N double exposure which N is a natural number of two or more is generically called "multiple exposure." In addition, in the following description, about the form which implemented the exposure apparatus or the exposure method of this invention as a drawing apparatus or the drawing method, it is a term corresponding to "N-exposure exposure" and "multiple exposure". The term "multiple drawing" shall be used.

There is no restriction | limiting in particular if N of exposure of N is two or more natural numbers, Although it can select suitably according to the objective, Three or more natural numbers are preferable and three or more natural numbers are more preferable.

An example of a pattern forming apparatus according to the permanent pattern forming method of the present invention will be described with reference to the drawings.

As the pattern forming apparatus, a so-called flatbed type exposure apparatus, and as shown in FIG. 1, is formed in a sheet-like photosensitive material 12 formed by stacking at least the photosensitive layer in the photosensitive transfer film (hereinafter, A flat plate moving stage 14 for absorbing and retaining the "photosensitive layer 12" may be provided on the surface. On the upper surface of the thick plate-shaped mounting table 18 supported by the four leg portions 16, two guides 20 extending along the stage moving direction are provided. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction and is supported to be reciprocated by the guide 20. In addition, the pattern forming apparatus 10 is provided with a stage driving device (not shown) for driving the stage 14 along the guide 20.

A c-shaped gate 22 is formed at the center of the mounting table 18 to cover the movement path of the stage 14. Each end of the c-shaped gate 22 is fixed to both sides of the mounting table 18. A scanner 24 is provided on one side with the gate 22 interposed therebetween, and a plurality (for example, two) sensors 26 for detecting the front and rear ends of the photosensitive material 12 on the other side. It is installed. The scanner 24 and the sensor 26 are attached to the gate 22, respectively, and are fixedly arranged above the movement path of the stage 14. In addition, the scanner 24 and the sensor 26 are connected to the controller which is not shown in figure which controls these.

Here, for the sake of explanation, in the plane parallel to the surface of the stage 14, as shown in FIG.

The slit 28 formed in the "ku" shape which opens toward the X-axis direction is equally spaced at the edge of the upstream side (henceforth only "upstream side") along the scanning direction of the stage 14. 10 pieces are formed. Each slit 28 is composed of a slit 28a located on the upstream side and a slit 28b located on the downstream side. The slits 28a and the slits 28b are orthogonal to each other, and the slits 28a have an angle of -45 degrees and the slits 28b have an angle of +45 degrees with respect to the X axis.

The position of the slit 28 substantially coincides with the center of the exposure head 30. In addition, the size of each slit 28 becomes the size which fully covers the width | variety of the exposure area 32 by the corresponding exposure head 30. As shown in FIG. In addition, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between adjacent exposed areas 34. In this case, the size of each slit 28 is a size which sufficiently covers the width of the overlapping portion between the exposed areas 34.

At the lower position of each slit 28 inside the stage 14, a single cell photodetector (not shown) is provided as a light spot position detecting means for detecting a light spot as a drawing unit in the use drawing section designation process described later. have. In addition, each photodetector is connected to the arithmetic unit (not shown) as a drawing part selecting means which selects the drawing part in the use drawing part designation process mentioned later.

As the operation form of the pattern forming apparatus at the time of exposure, it may be a form in which exposure is continuously performed while always moving the exposure head, or the exposure operation is stopped by stopping the exposure head at a position before each movement while moving the exposure head in stages. The form may be performed.

<< exposure head >>

Each of the exposure heads 30 is provided to the scanner 24 so that each drawing part (micromirror) column direction of the internal digital micromirror device (DMD) 36, which will be described later, forms a scanning direction and a predetermined set inclination angle θ. Attached. For this reason, the exposure area 32 by each exposure head 30 turns into a rectangular area inclined with respect to a scanning direction. As the stage 14 moves, a band-shaped exposure completed area 34 is formed in each of the exposure heads 30 in the photosensitive layer 12. In the example shown to FIG. 2 and FIG. 3B, the scanner 24 is equipped with ten exposure heads arrange | positioned in substantially matrix form of 2 rows 5 columns.

In addition, below, when showing the individual exposure head arrange | positioned at the m-th nth column, it represents with the exposure head _30mn , and shows the exposure area by the individual exposure heads arranged in the nth-th row of the mth line. In this case, the exposure area 32 _mm is indicated.

3A and 3B, the exposure heads 30 in each row arranged in a line so that each of the stripe-exposed areas 34 partially overlaps the adjacent exposed area 34. As shown in FIGS. Are arranged so as to shift a predetermined interval (natural arrangement of the long sides of the exposure area, twice in this embodiment) in the arrangement direction thereof. For this reason, can not be exposed between the parts of the first row of the exposure area (32 ₁₁₎ and the exposed area (32 ₁₂₎ can be exposed by an exposure area _(21, 32) of the second row.

4, 5A, and 5B, each of the exposure heads 30 is a light modulating means (spatial light modulating element for modulating for each drawing part) which modulates incident light for each drawing part in accordance with image data. DMD 36 (manufactured by Texas Instruments, Inc.) is provided. The DMD 36 is connected to a controller as a drawing unit control means including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving control of each micro mirror in the use area on the DMD 36 for each of the exposure heads 30 based on the input image data. In addition, the mirror drive control unit controls the reflection surface angle of each micromirror of the DMD 36 for each of the exposure heads 30 based on the control signal generated by the image data processing unit.

As shown in FIG. 4, on the light incidence side of the DMD 36, a fiber array having laser emitters arranged in a line along a direction in which the exit end (light emission point) of the optical fiber coincides with the long side direction of the exposure area 32. A lens system 40 for correcting the laser light emitted from the light source 38, the fiber array light source 38 and condensing on the DMD, and a mirror for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 ( 42 are arranged in this order. 4 schematically shows the lens system 40.

As shown in detail in FIGS. 5A and 5B, the lens system 40 includes a pair of combination lenses 44 for parallelizing the laser light emitted from the fiber array light source 38 and a light amount distribution of the parallel lighted laser light. A pair of combined lenses 46 for correcting to be uniform, and a condensing lens 48 for condensing laser light whose light amount distribution is corrected on the DMD 36.

On the light reflection side of the DMD 36, a lens system 50 is formed which forms the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12. The lens system 50 is composed of two lenses 52 and 54 arranged such that the DMD 36 and the exposed surface of the photosensitive layer 12 are in conjugated relationship.

In this embodiment, the laser light emitted from the fiber array light source 38 is substantially enlarged five times, and then set so that the light beam from each micromirror on the DMD 36 is narrowed to about 5 占 퐉 by the lens system 50. It is.

Light modulation means

The light modulating means is not particularly limited as long as it has the drawing parts arranged in two dimensions of n pieces (where n is a natural number of two or more), and the drawing parts can be controlled according to the pattern information. Can be selected, for example, a spatial light modulator is preferable.

Examples of the spatial light modulator include a digital micro mirror device (DMD), a spatial light modulator (SLM) of MEMS (Micro Electro Mechanical Systems) type, and an optical element that modulates transmitted light by an electro-optic effect. (PLZT element), liquid crystal light shutter (FLC), etc. are mentioned, DMD is mentioned preferably among these.

In addition, the light modulating means preferably 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.

Hereinafter, an example of the said optical modulation means is demonstrated, referring drawings.

As shown in FIG. 6, the DMD 36 is a drawing part that constitutes a drawing (pixel) on the SRAM cell (memory cell) 56, and is formed by arranging a plurality of micro mirrors 58 in a lattice form. Device. In this embodiment, the DMD 36 in which the micromirrors 58 of 1024 columns x 768 rows are arrange | positioned is used, Among these, the micromirror 58 which can be driven by the controller connected to the DMD 36, ie, can be used, is used. Should be 1024 columns x 256 rows only. The data processing speed of the DMD 36 has a limitation, and since the modulation speed per line is determined in proportion to the number of micro mirrors used, the modulation speed per line becomes faster by using only a part of the micro mirrors. Each micromirror 58 is supported by the support | pillar, and the material with high reflectivity, such as aluminum, is deposited on the surface. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch is 13.7 µm in both the vertical and horizontal directions. The SRAM cell 56 is of CM0S of a silicon gate fabricated in a conventional semiconductor memory manufacturing line through a strut including a hinge and a yoke, and the whole is monolithic (integrated).

When an image signal indicating the density of each point constituting a desired two-dimensional pattern in two values is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the post is diagonally formed. With respect to the center, the tilt is made at any one of ± α degrees (for example, ± 10 degrees) with respect to the substrate side where the DMD 36 is arranged. FIG. 7A shows the tilted state at + α degrees with the micromirrors 58 on, and FIG. 7B shows the tilted state at −α degrees with the micromirrors 58 off. Thus, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 in accordance with the image signal as shown in FIG. 6, the laser beam B incident on the DMD 36 is each different. It is reflected in the inclined direction of the micro mirror 58.

6 shows an example of a state in which a part of the DMD 36 is enlarged so that each micromirror 58 is controlled at + α degrees or α degrees. On-off control of each micromirror 58 is performed by the said controller connected to DMD36. In addition, a light absorber (not shown) is disposed in the direction in which the laser light B reflected from the off-state micromirror 58 travels.

-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 lamp, xenon lamp, carbon arc lamp, halogen lamp, fluorescent lamps for copiers, LED, semiconductor laser, etc. The known light source or means which can synthesize | combine and irradiate 2 or more lights are mentioned, Among these, the means which can synthesize | combine and irradiate 2 or more lights are preferable.

As light irradiated from the light irradiation means, for example, in the case of performing light irradiation through a support, electromagnetic waves that transmit the support and activate a photopolymerization initiator or a sensitizer used, visible light from ultraviolet rays, electron beams, X-rays The laser beam etc. are enumerated, Among these, a laser beam is preferable and the laser which synthesize | combined two or more lights (Hereinafter, it may be called "a combined wave laser") is more preferable. Moreover, the same light can be used also when light irradiation is performed after peeling a support body.

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

As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330-500 nm is still more preferable, 400-450 nm is especially preferable.

As means for irradiating the haptic laser, for example, a means having a plurality of lasers, a multimode optical fiber and a collective optical system for condensing the laser beams irradiated from the plurality of lasers and coupling them to the multimode optical fiber is preferable. .

As means (fiber array light source) which can irradiate the said combining laser, the means described in Unexamined-Japanese-Patent No. 2005-258431-[0146] is mentioned, for example.

<< use cemetery designation means >>

As the use drawing part designation means, a light point position detecting means for detecting the position of a light spot as a drawing unit on the exposed surface, and a drawing used for realizing N-exposure based on the detection result by the light spot position detecting means. It is preferable to provide at least the drawing part selecting means which selects a part.

Hereinafter, the example of the designation method of the drawing part used for N exposure by the said use drawing part designation means is demonstrated.

(1) Designation method of use drawing part in single exposure head

In this embodiment (1), when the double exposure is performed on the photosensitive material 12 by the pattern forming apparatus 10, the variation and density deviation of the resolution resulting from the installation angle error of each exposure head 30 are eliminated. The designation method of the use drawing part for reducing an ideal double exposure is demonstrated.

As the set inclination angle θ in the column direction of the drawing part (micromirror 58) with respect to the scanning direction of the exposure head 30, 1024 rows X which can be used in an ideal state without an installation angle error of the exposure head 30, etc. It is assumed that an angle slightly larger than the angle (θ _ideal ) to be exactly double exposure is used using 256 rows of drawing parts.

This angle θ _ideal is such that the number N of exposures in N, the number s in the column direction of the usable micromirrors 58, the spacing p in the column direction of the usable micromirrors 58, and the exposure head 30 are inclined. Regarding the pitch δ of the scan line formed by the micromirror in the state of

spsinθ _ideal ≥Nδ (Equation 1)

Is given by In the DMD 36 according to the present embodiment, as described above, a plurality of micromirrors 58 having the same vertical and horizontal arrangement intervals are arranged in a rectangular lattice shape.

pcosθ _ideal = δ (Equation 2)

Equation 1 is

stanθ _ideal = N (Equation 3)

Becomes In this Embodiment (1), since s = 256 and N = 2 as above-mentioned, the angle (theta) _ideal from the said Formula 3 is about 0.45 degree. Therefore, as setting inclination angle (theta), an angle of about 0.50 degree may be employ | adopted, for example. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the installation angle of each exposure head 30, that is, each DMD 36, becomes an angle close to this set inclination angle θ within the adjustable range.

FIG. 8 is an explanatory diagram showing an example of nonuniformity generated in a pattern on an exposed surface due to an influence of an installation angle error of one exposure head 30 and pattern deformation in the pattern forming apparatus 10 initially adjusted as described above. to be. In the following drawings and descriptions, the light spot in the m-th row is represented by r (m) and the light spot in the nth column with respect to the light spot generated by each drawing unit (micromirror) and constitutes an exposure area on the exposed surface. Light points of c (n) and mth row nth columns are denoted by P (m, n), respectively.

The upper part of FIG. 8 shows a pattern of groups of light spots from usable micromirrors 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 stationary, the lower part being shown in the upper part. The state of the exposure pattern formed on the to-be-exposed surface is shown when the stage 14 is moved and the continuous exposure is performed in the state which the pattern of a group of light spots is revealed.

In addition, although FIG. 8 shows the exposure pattern by the odd row and the exposure pattern by the even row of the micromirror 58 which can be used for convenience of description, the exposure pattern on an actual to-be-exposed surface is these two exposures. The pattern was polymerized.

In the example of FIG. 8, since the setting inclination angle (theta) is a slightly larger angle than said angle (theta) _ideal , since fine adjustment of the installation angle of the exposure head 30 is difficult, the actual installation angle is difficult. As a result of the difference between the set inclination angle θ and an error, concentration variations occur in either of the regions on the exposed surface. Specifically, in the overlapping exposure area formed on the exposed surface formed by the plurality of rows of mausoleum in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, the overexposure to the ideal double exposure occurs. The area | region in which drawing is made long is produced | generated, and the density | variation fluctuation arises.

In addition, in the example of FIG. 8, as an example of the pattern distortion which appears on a to-be-exposed surface, the "angle distortion" which the inclination angle of each pixel string projected on the to-be-exposed surface does not become uniform has arisen. Examples of such angular distortion include various aberrations and alignment misalignments between the optical system between the DMD 36 and the exposed surface, deformation of the DMD 36 itself, an arrangement error of the micromirror, and the like.

The angle deformation shown in the example of FIG. 8 is a deformation | transformation in which the inclination | tilt angle with respect to a scanning direction is smaller for the column of the left side of a figure, and is larger for the column of the right side of a figure. As a result of this angular deformation, the area which becomes overexposure is smaller on the to-be-exposed surface shown on the left side of the figure, and becomes larger on the to-be-exposed surface shown on the right side of the figure.

In order to reduce the concentration variation in the overlapping exposure area on the exposed surface formed by a plurality of rows of the drawing parts as described above, the exposure head 30 is used as the light spot position detecting means using a set of slits 28 and a photodetector. A micrometer used for actual exposure using the arithmetic unit connected to the photodetector as the drawing unit selecting means based on the actual inclination angle θ 'for each of the? The process of selecting a mirror is performed.

The actual inclination angle [theta] 'is an angle formed between the column direction of the light spot on the exposed surface and the scanning direction of the exposure head in a state where the exposure head is inclined based on the at least two light spot positions detected by the light spot position detecting means. Is specified by.

Hereinafter, the specification of the actual inclination angle [theta] 'and the use pixel selection process are demonstrated using FIG.9 and FIG.10.

Specific of the actual inclination angle θ '

9 is a top view showing the positional relationship between the exposure area 32 and the corresponding slit 28 by one DMD 36. The size of the slit 28 is made to cover the width of the exposure area 32 enough.

In the example of this embodiment frame 1, the angle formed between the light spot array of the 512th row and the scanning direction of the exposure head 30 located approximately at the center of the exposure area 32 is measured as the actual inclination angle θ '. do. Specifically, the micromirrors 58 of the first row 512th column and the micromirrors 58 of the 256th row 512th column on the DMD 36 are turned on, and the light spots P (on the corresponding exposed surface, respectively) The positions of 1, 512 and P (256, 512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual inclination angle [theta] '.

10 is a top view illustrating a method of detecting light spots P (256, 512) positions.

First, in the state where the micromirrors 58 of the 256th row and the 512th row are turned on, the stage 14 is slowly moved to move the slit 28 relatively along the Y-axis direction, so that the light spots P (256, 512) are moved. The slit 28 is positioned at any position coming between the slit 28a on the upstream side and the slit 28b on the downstream side. The coordinate of the intersection of the slit 28a and the slit 28b at this time is set to (X0, Y0). The values of these coordinates (X0, Y0) are determined from the moving distance of the stage 14 to the position indicated by the drive signal given to the stage 14, and the X-direction position of the known slit 28, and recorded.

Next, the stage 14 is moved to relatively move the slit 28 to the right side in FIG. 10 along the Y axis. As shown by a dashed-dotted line in FIG. 10, the light at the light spots P (256, 512) passes through the slit 28 b on the left side and stops the stage 14 where it is detected by the photodetector. The coordinates (X0, Y1) of the intersections of the slit 28a and the slit 28b at this time are recorded as the positions of the light points P (256, 512).

Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. 10. As shown by a dashed-dotted line in FIG. 10, the stage 14 is stopped where light at the light points P 256 and 512 passes through the slit 28a on the right side and is detected by the photodetector. The coordinates (X0, Y2) of the intersections of the slit 28a and the slit 28b at this time are recorded as the positions of the light points P (256, 512).

From the above measurement result, the coordinate (X, Y) which shows the position on the to-be-exposed surface of light spot P (256, 512) is set to X = X0 + (Y1-Y2) / 2, Y = (Y1 + Y2) / 2. Determined by the calculation of. By the same measurement, the coordinates indicating the positions of P (1, 512) are also determined, and the inclination angle formed by the straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is the actual inclination angle (θ). It is specified as').

-Selection of use cemetery part-

The computing device connected to the photodetector using the actual inclination angle θ 'specified in this manner is expressed by the following equation 4

ttanθ '= N (Equation 4)

The natural number T closest to the value t satisfying the relation of D is derived, and a process of selecting the micromirrors in the T-th row from the first row on the DMD 36 as the micromirrors actually used in the present exposure is performed. . Thereby, in the exposure area around the 512th row, the micromirror which minimizes the area total of the area which becomes overexposure and the area underexposure with respect to ideal double exposure can be selected as a micromirror actually used.

Here, instead of deriving the natural number closest to the value t, the smallest natural number equal to or greater than the value t may be derived. In that case, the micromirror which uses the micromirror which does not produce the area of the area which becomes overexposure to the ideal double exposure in the exposure area of the 512th column vicinity, and the area which becomes underexposure is actually used as a micromirror. You can choose.

Further, the maximum natural number below the value t may be derived. In that case, in the exposure area near the 512th row, the area of the area which becomes underexposed to the ideal double exposure is minimized, and the micromirror which does not produce the area which becomes overexposure is selected as a micromirror which actually uses. Can be.

FIG. 11 is an explanatory diagram showing how unevenness on the exposed surface shown in FIG. 8 is improved in exposure performed using only the light points generated by the micromirrors selected as the micromirrors actually used as described above.

In this example, it is assumed that T = 253 is derived as the natural number T described above, and the micromirrors of the first to the 253rd rows are selected. The micromirrors of the 254th to 256th rows that are not selected are always sent by the above-mentioned drawing unit control means to set a signal to be set to the off-state angle, and those micromirrors do not substantially participate in exposure. As shown in FIG. 11, in the exposure area near the 512th column, the overexposure and the underexposure are almost completely eliminated, and uniform exposure very close to the ideal double exposure is realized.

On the other hand, in the region on the left side of FIG. 11 (near c (1) in the drawing), the inclination angle of the light spot on the exposed surface is changed in the region near the center (near c (512) in the drawing) by the above-described angle transformation. It is smaller than the inclination angle of the light ray. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ 'measured on the basis of c (512), the ideal double in each of the exposure pattern with even rows and the exposure pattern with odd rows The area which becomes underexposure with respect to exposure arises slightly.

However, in the actual exposure pattern formed by polymerizing the exposure pattern by odd-numbered rows and the exposure pattern by even-numbered rows, the areas where the exposure amount is insufficient are compensated for each other, and the effect of supplementing the exposure deviation due to the angle deformation by double exposure It can be minimized by.

In addition, in the area | region on the right side of FIG. 11 (near c (1024) in a figure), the angle of inclination of the ray of light on a to-be-exposed surface by the said angular deformation is in the area | region near a center (near c (512) in a figure). It is larger than the inclination angle of the ray train. Therefore, in the exposure by the micromirror selected based on the actual inclination angle θ 'measured on the basis of c (512), as shown in the drawing, a region slightly overexposed to the ideal double exposure occurs. .

However, in an actual exposure pattern formed by polymerizing an exposure pattern with odd columns and an exposure pattern with even rows, an area of overexposure is compensated for each other, and the effect of supplementing the concentration variation due to the angular deformation by double exposure is obtained. It can be minimized by.

In the present embodiment (1), as described above, the actual inclination angle θ 'of the light beam of the 512th row is measured, and T derived by the above formula (4) using the actual inclination angle θ'. Although the micromirror 58 used was selected based on the above, as a specific method of the said actual inclination angle (theta) ', the several actual inclination angle which the column direction (light spot array) of the several drawing parts and the scanning direction of the said exposure head make | form. Are respectively measured, and any one of their average value, median value, maximum value, and minimum value is specified as the actual inclination angle θ ', and in the form of selecting the micromirror actually used during the actual exposure by Equation 4 or the like. You may also

When the average value or the median value is set to the actual inclination angle θ ', exposure with good balance between the area overexposed and the area underexposed with respect to the ideal N-level exposure can be realized. For example, the total area of the area overexposed and the area underexposed is suppressed to the minimum, and the number of photo units (light points) in the area overexposed and the number of writer units in the underexposed area ( It is possible to realize exposure in which the light points) are the same.

In addition, when the maximum value is set to the actual inclination angle θ ', it is possible to realize exposure in which the exclusion of the area that is overexposure with respect to the ideal N-exposure is more important. It is possible to minimize the exposure and to realize the exposure so as not to produce an area that becomes excessive exposure.

When the minimum value is set to the actual inclination angle θ ', it is possible to realize exposure in which the exclusion of the area underexposure is more important than the ideal N-exposure. For example, the area of the area that becomes overexposure is minimized. It is possible to suppress the exposure and to realize the exposure so as not to generate a region in which exposure is insufficient.

On the other hand, the specification of the said actual inclination angle (theta) 'is not limited to the method based on the position of at least 2 light spots among the columns (light spot string) of the same drawing part. For example, the angle obtained from the position of one or a plurality of light spots in the same seedling section column c (n) and the position of one or a plurality of light spots in the heat near c (n) is obtained by the actual inclination angle θ '. It may be specified as.

Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a straight line near the light spot along the scanning direction of the exposure head are detected, and the actual inclination angle ( θ ') can be obtained. Further, the angle obtained based on the position of at least two light spots (for example, two light spots arranged to cover c (n)) in the light spot near the c (n) column is used as the actual inclination angle θ '. You may specify.

As mentioned above, according to the designation method of the use drawing part of this embodiment (1) using the pattern forming apparatus 10, the dispersion | variation in the dispersion | variation in the unevenness and density | concentration of the resolution by the influence of the installation angle error of each exposure head and pattern distortion is reduced. The ideal N-level exposure can be realized.

(2) Designation method of use drawing part between plural exposure heads <1>

In this embodiment (2), when the double exposure is performed on the photosensitive material 12 by the pattern forming apparatus 10, the head-to-head connection which is an overlapping exposure area on the to-be-exposed surface formed by the some exposure head 30 is carried out. Ideal double by reducing unevenness and density deviation of the resolution caused by the deviation from the ideal state of the relative position of the two exposure heads (for example, the exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction in the area. The designation method of the drawing material part for realizing exposure is demonstrated.

As the setting inclination angle (θ) of each exposure head 30, that is, each DMD 36, an ideal state in which there is no installation angle error of the exposure head 30, etc., 1024 rows x 256 rows of drawing part micros can be used. By using the mirror 58, it is assumed that the angle θ _ideal is _achieved by exactly double exposure.

This angle θ _ideal is obtained from the above formulas 1 to 3 in the same manner as in the first embodiment (1). In the present embodiment (2), the pattern forming apparatus 10 is initially adjusted so that the installation angle of each exposure head 30, that is, each DMD 36 is at this angle θ _ideal .

FIG. 12 shows the deviation from the ideal state of the relative position in the X-axis direction of the two exposure heads (for example, the exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which showed the example of the density | variation difference which arises in the pattern on a to-be-exposed surface under influence. The shift of the relative position with respect to the X-axis direction of each exposure head may arise because fine adjustment of the relative position between exposure heads is difficult.

The upper portion of FIG. 12 shows usable micromirrors 58 of the DMD 36 with the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive material 12 with the stage 14 stationary. It is a figure which shows the pattern of the light spot group from a. 12 shows the state of the exposure pattern formed on the exposed surface when the continuous exposure is performed by moving the stage 14 in the state where the light spot group pattern as shown in the upper portion is revealed. ₁₂ and 32 ₂₁ ).

In addition, although FIG. 12 shows the exposure pattern of every other column of the usable micromirror 58 for the convenience of description, it divides into the exposure pattern by the pixel column group A, and the exposure pattern by the pixel column group B, but it is an actual to-be-exposed surface. The exposure pattern in a phase superpose | polymerizes these two exposure patterns.

In the example of FIG. 12, the exposure pattern by the pixel column group A and the exposure by the pixel column group B as a result of the deviation from the ideal state of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction described above. In both of the patterns, portions in excess of the exposure amount occur in the connection area between the heads of the exposure areas 32 ₁₂ and 32 ₂₁ than in the ideal double exposure state.

In this embodiment (2), the slit 28 and the light are used as the light spot position detecting means in order to alleviate the concentration variation in the connection area between the heads formed on the exposed surface by the plurality of exposure heads as described above. Using a set of detectors, the position (coordinate) is detected for some of the light spots constituting the head-to-head connection region formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 ₂₁ . Based on the position (coordinate), a process of selecting a micromirror used for actual exposure is performed by using a computing device connected to the photodetector as the drawing unit selection means.

Detection of position (coordinates)

FIG. 13 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ and the slits 28 corresponding to those in FIG. 12. The size of the slit 28 is Pinot light surface by the exposure head (30, ₁₂ and 30, ₂₁₎ substantially covers the size of the width of the overlapping portion between the exposure completion region 34 by, i.e., exposure head (30 ₁₂ and 30 ₂₁₎ It is size enough to fully cover the said head-to-head connection area | region formed on.

14 is a top view illustrating a detection method when detecting the positions of light spots P (256, 1024) of the exposure area 32 ₂₁ as an example.

First, while the micromirror of the 256th row 1024th column is turned on, the stage 14 is moved slowly, and the slit 28 is moved relatively along the Y-axis direction, and the light spots P (256, 1024) are located upstream. The slit 28 is positioned at any position coming between the slit 28a and the downstream slit 28b. The coordinate of the intersection of the slit 28a and the slit 28b at this time is set to (X0, Y0). The values of these coordinates (X0, Y0) are determined from the moving distance of the stage 14 to the position indicated by the drive signal given to the stage 14, and the X-direction position of the known slit 28, and recorded.

Next, the stage 14 is moved to relatively move the slit 28 to the right side in FIG. 14 along the Y axis. As shown by the dashed-dotted line in FIG. 14, the light at the light spots P (256, 1024) passes through the slit 28 b on the left side and stops the stage 14 where it is detected by the photodetector. The coordinates (X0, Y1) of the intersections of the slit 28a and the slit 28b at this time are recorded as the positions of the light points P (256, 1024).

Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. 14. As shown by the dashed-dotted line in FIG. 14, the light at the light spots P (256, 1024) passes through the slit 28a on the right side and stops the stage 14 where it is detected by the photodetector. The coordinates (X0, Y2) of the intersections of the slit 28a and the slit 28b at this time are recorded as light points P (256, 1024).

From the above measurement result, calculation of X = X0 + (Y1-Y2) / 2 and Y = (Y1 + Y2) / 2 is calculated | required the coordinate (X, Y) which shows the position in the to-be-exposed surface of light spot P (256, 1024). Decide by

Specific-of the unused cemetery part

In the example of FIG. 12, first, the position of the light spot P (256, 1) of the exposure area 32 ₁₂ is detected by the set of the slit 28 and the photodetector as said light spot position detection means. Subsequently, the positions of the respective light spots on the light spot row r (256) of the 256th row of the exposure area 32 ₂₁ are set to P (256, 1024), P (256, 1023). Of going to the detection order, the exposure area (32 _12), the light spot P (256, 1) of the exposure area (32 ₂₁₎ indicating the largest X coordinate than the light spot P (256, n) to terminate the detection operation in the detection area do. Then, specified as the exposure area (32 _21), the micromirror corresponding to the light spots constituting the c (1024) from the radiant heat c (n + 1), micro-mirror (sub unused graves) is not used at the time of the exposure .

For example, in FIG. 12, the light spots P (256, 1020) of the exposure area 32 ₂₁ represent an X coordinate larger than the light spots P (256, 1) of the exposure area 32 ₁₂ , and the exposure area 32. _{If the} detection operation is terminated where the light spots P (256, 1020) of ₂₁ are detected, the first to 1024th rows of the exposure area 32 ₂₁ corresponding to the portion 70 covered with the diagonal lines in FIG. The micromirror corresponding to the light spot which comprises a row is specified as a micromirror which is not used at the time of this exposure.

Next, the position of the light spot P (256, N) of the exposure area 32 ₁₂ is detected with respect to the number N of exposures among N. In the present embodiment (2), since N = 2, the positions of the light spots P (256, 2) are detected.

Subsequently, among the light spots of the exposure area 32 ₂₁ , the positions of the light spots constituting the rightmost 1020 column are determined except as specified as the light spots corresponding to the micromirrors not used in the present exposure. , P (1, 1020), P (2, 1020) in order from P (1, 1020). Go to detect and terminates the detecting operation in the light spot P (m, 1020) the detected change indicating greater than the X coordinate of the light spot P (256, 2) of the exposure area (32 ₁₂₎ to.

After that in the computing device connected to the photo detector, the X coordinate and the exposed area (32 ₂₁₎ of the light spot P (256, 2) of the exposure area (32 _12), the light spot P (m, 1020), and P (m- When the X coordinates of 1, 1020 are compared, and the X coordinate of the light point P (m, 1020) of the exposure area 32 ₂₁ is close to the X coordinate of the light point P (256, 2) of the exposure area 32 ₁₂ . There are certain points of light from the P (1, 1020) of the exposure area _(21, 32) as a micromirror micro-mirror is not used for the exposure corresponding to P (m-1, 1020) .

Further, when the X-coordinate-side of the light spot P (m-1, 1020) of the exposure area (32 ₂₁₎ near to the X-coordinate of the light spot P (256, 2) of the exposure area (32 ₁₂₎ has exposed areas (32 ₂₁₎ From the light points P (1, 1020), the micromirrors corresponding to P (m-2, 1020) are specified as micromirrors not used for this exposure.

Further, the positions of the light spots P (256, N-1) of the exposure area 32 ₁₂ , that is, the positions of the light spots P (256, 1) and the respective light spots constituting the tenth column, which is the next column of the exposure area 32 ₂₁ . The same detection processing and specifying the unused micromirror is performed for the same.

As a result, for example, the micromirror corresponding to the light point which comprises the area | region 72 covered by hatching in FIG. 15 is added as a micromirror which is not used at the time of actual exposure. These micromirrors are always sent a signal which sets the angle of the micromirror to the off state angle, and these micromirrors are practically not used for exposure.

In this way, by specifying the micromirrors not used at the time of actual exposure and selecting the one except the unused micromirrors as the micromirrors used at the time of actual exposure, the above-mentioned exposure of the exposure area 32 ₁₂ and 32 ₂₁ is performed. In the head-to-head connection area, the total area of the overexposed area and the underexposed area can be minimized with respect to the ideal double exposure, and as shown in the lower part of FIG. 15, very close to the ideal double exposure. Uniform exposure can be realized.

In the above example, at the time of specifying the light point constituting the region 72 covered by hatching in FIG. 15, the X coordinate of the light spots P (256, 2) of the exposure area 32 ₁₂ and the exposure area ( 32 ₂₁ ) from the light point P (1, 1020) of the exposure area 32 ₂₁ immediately without comparing the X coordinates of the light point P (m, 1020) and P (m-1, 1020). The micromirrors corresponding to 2, 1020 may be specified as a micromirror not used at the time of this exposure. In this case, a micromirror in which the area of overexposure becomes the minimum and the area underexposed to the ideal double exposure in the head-to-head connection area can be selected as the micromirror used in practice. have.

Also, P (m-1, 1020 ) a micro-mirror may be specified as micro mirrors not to use in the exposure corresponding to the light spots from the P (1, 1020) of the exposure area (32 _21). In this case, it is possible to select as a micromirror which actually uses a micromirror in which the area of underexposure becomes the minimum and the area in which the overexposure occurs in the ideal double exposure in the head-to-head connection area.

In addition, in the head-to-head connection area, the microcomputer actually used so that the drawing unit number (light point number) of the overexposed area and the drawing unit number (light point number) of the area underexposed are equal to the ideal double drawing. The mirror may be selected.

As mentioned above, according to the designation method of the use drawing part of this embodiment (2) which used the pattern forming apparatus 10, the nonuniformity of a resolution and density | variation variation resulting from the shift of the relative position with respect to the X-axis direction of a some exposure head. It is possible to realize the ideal N-level exposure by reducing the

(3) Designation method of use drawing part between plural exposure heads <2>

In this embodiment (3), when performing double exposure with respect to the photosensitive material 12 by the pattern forming apparatus 10, between heads which are overlapping exposure areas on the to-be-exposed surface formed by the some exposure head 30. FIG. In the connection area, the deviation from the ideal state of the relative position of the two exposure heads (for example, the exposure heads 30 ₁₂ and 30 ₂₁ ) with respect to the X-axis direction, the installation angle error of each exposure head, and the two exposures. A method of designating the use drawing part for reducing an unevenness and density variation of the resolution caused by the relative installation angle error between the heads and realizing the ideal double exposure will be described.

As the setting inclination angle of each exposure head 30, that is, each DMD 36, if there is no installation angle error or the like of the exposure head 30, 1024 rows x 256 rows of drawing parts (micromirror ( 58)), an angle slightly larger than the angle (θ _ideal ) for exactly double exposure is adopted.

This angle θ _ideal is a value obtained by using the above formulas 1 to 3 in the same manner as in the embodiment (1). In the present embodiment, as described above, since s = 256 and N = 2, the angle θ _ideal ) is about 0.45 degrees. Therefore, the set tilt angle θ may be, for example, an angle of about 0.50 degrees. The pattern forming apparatus 10 shall be initially adjusted so that the installation angle of each exposure head 30, ie, each DMD 36 may become an angle close to this set inclination angle (theta) within the adjustable range.

FIG. 16 shows two exposure heads (for example, exposure heads 30 ₁₂ and 1) in the pattern forming apparatus 10 in which the installation angles of the respective exposure heads 30, that is, each DMD 36 are initially adjusted as described above. 30 ₂₁ )) is an explanatory diagram showing an example of nonuniformity generated in the pattern on the exposed surface due to the influence of the installation angle error, the relative installation angle error between each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the shift of the relative position. .

In the example of FIG. 16, as a result of misalignment of the relative positions of the exposure heads 30 ₁₂ and 30 ₂₁ with respect to the X-axis direction as in the example of FIG. 12, the light spot groups (pixel row groups A and B) of every other row are used. In both of the exposure patterns, in the exposure area overlapping on the coordinate axis orthogonal to the scanning direction of the exposure head on the exposed surfaces of the exposure areas 32 ₁₂ and 32 ₂₁ , the area 74 with an excessive exposure amount than the ideal double exposure state Occurs, and this causes a concentration variation.

In addition, in the example of FIG. 16, the result of having set the inclination angle (theta) of each exposure head slightly larger than the angle (theta) _ideal which satisfy | _fills said Formula (1), and fine-adjusting the installation angle of each exposure head is shown. This is difficult, and as a result of the fact that the actual installation angle is shifted from the set inclination angle θ, even in areas other than the exposure area overlapping on the coordinate axis orthogonal to the scanning direction of the exposure head on the exposed surface, one row In both of the exposure patterns by different light spot groups (pixel row groups A and B), in the drawing part hot-coupling area, which is an overlapping exposure area on the exposed surface formed by the plurality of drawing part rows, the exposure is overexposure than the ideal double exposure state. The area | region 76 to become becomes, and this causes a new density | variation variation.

In the present embodiment (3), first, a use pixel selection process for reducing the concentration variation caused by the influence of the installation angle error and the deviation of the relative installation angle of each exposure head 30 ₁₂ and 30 ₂₁ is performed.

Specifically, using the set of slits 28 and photodetectors as the light spot position detecting means, the actual tilt angle θ 'is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual tilt Based on the angle [theta] ', a process of selecting a micromirror used for the actual exposure is performed by using an arithmetic unit connected to a photodetector as the drawing unit selection means.

Specific of the actual inclination angle θ '

The specification of the actual inclination angle θ 'means that the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ with respect to the exposure head 30 ₁₂ are set to the exposure head 30 ₂₁ . For example, the positions of the light spots P (1, 1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected by the set of slits 28 and the photodetectors used in the above-described embodiment (2), respectively. It is performed by measuring the angle which the inclination angle of the straight line which connects them and the scanning direction of an exposure head make.

Specific-of the unused cemetery part

In this way, the computing device connected to the photodetector using the specified actual tilt angle θ 'is the same as the computing device in Embodiment (1) described above.

ttanθ '= N (Equation 4)

The natural number T closest to the value t satisfying the relation of D is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the second to the 256th row from the (T + 1) th row on the DMD 36. The process of specifying the micromirror as a micromirror not used for this exposure is performed.

For example, assuming that T = 254 for the exposure head 30 ₁₂ and T = 255 for the exposure head 30 ₂₁ , the light spots constituting the portions 78 and 80 covered with diagonal lines in FIG. 17. The micromirror corresponding to this is specified as a micromirror not used for this exposure. Accordingly, the sum of the areas of the exposed area (32 ₁₂ and 32 ₂₁₎ area to which the exposure excessive with respect to the exposure of the ideal 2 in each of regions other than the one connected region between the head, and that the underexposure region can be minimized.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number of the value t or more may be derived. That case, the exposure area (32 ₁₂ and 32 ₂₁₎ a plurality of in each area of Pinot other than the connection area between head overlapping the exposure area on the light surface formed by the exposure head, the ideal second area where the light exposure over against the exposure of the The area which becomes the minimum and becomes short of an exposure amount can be made not to arise.

Alternatively, the maximum natural number below the value t may be derived. In that case, in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads of the exposure areas 32 ₁₂ and 32 ₂₁ , the area of the exposure underexposure with respect to the ideal double exposure. The area can be minimized and the area where the exposure becomes excessive can be prevented.

In each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads, the number of drawing units (light number) of the area that is overexposed to the ideal double exposure, and the exposure is insufficient. The micromirrors not used at the time of this exposure may be specified so that the number of drawing units (light spot number) of the region may be the same.

Subsequently, a process similar to the present embodiment (3) described with reference to Figs. 12 to 15 with respect to the micromirrors corresponding to the light points other than the light points constituting the diagonally covered areas 78 and 80 in Fig. 17. 17, a micromirror corresponding to a light point constituting the region 82 covered with diagonal lines and the region 84 covered with hatching is specified, and added as a micromirror not used during the present exposure. .

With respect to the micromirror specified as not being used during these exposures, a signal for setting at an off-state angle is always sent by the drawing element control means, and these micromirrors do not substantially participate in exposure.

As mentioned above, according to the designation method of the using drawing part of this embodiment (3) using the pattern forming apparatus 10, the shift | offset | difference of the relative position with respect to the X-axis direction of several exposure heads, and the installation angle error of each exposure head. It is possible to realize the ideal N-level exposure by reducing the variation in the resolution and the concentration variation due to the relative installation angle error between the exposure head and the exposure head.

As mentioned above, although the use drawing part designation method by the pattern forming apparatus 10 was demonstrated in detail, the said embodiment (1)-(3) is only one example, and various changes are possible without deviating from the scope of the present invention. Do.

Moreover, although the said embodiment (1)-(3) used the set of the slit 28 and the single cell type photodetector as a means for detecting the position of the light spot on a to-be-exposed surface, it is not limited to this, What kind of thing is used A two-dimensional detector or the like may be used, for example.

In the above embodiments (1) to (3), the actual tilt angle θ 'is obtained from the position detection result of the light spot on the exposed surface by the slit 28 and the set of the photodetectors, and the actual tilt angle θ Although the micromirror used was selected based on "), you may make it the form which selects the usable micromirror, without deriving the actual inclination angle (theta) '. The scope of the invention also includes, for example, performing reference exposure using all available micromirrors, and manually specifying the micromirrors used by the operator, for example, by visually confirming the resolution and density deviation of the reference exposure result. It is included in.

In addition, there are various forms of pattern deformation that may occur on the exposed surface, in addition to the angle deformation described in the above examples.

As an example, as shown to FIG. 18A, there exists a form of the magnification distortion which the light beam from each micromirror 58 on DMD 36 reaches the exposure area 32 on an exposure surface with a different magnification.

As another example, as shown in FIG. 18B, a form of beam diameter deformation in which a light beam from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposed surface at a different beam diameter. There is also. These magnification deformations and beam diameter deformations are mainly caused by various aberrations and alignment misalignments of the optical system between the DMD 36 and the exposed surface.

As another example, there is also a form of light quantity deformation in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposed surface at different amounts of light. This light quantity deformation is not only various aberrations and alignment misalignments, but also the positional dependence of the transmittance of the optical element (for example, the lenses 52 and 54 of FIGS. 5A and 5B, which are single-lens lenses) between the DMD 36 and the exposed surface, It arises because of the light quantity variation by DMD 36 itself. Pattern deformation of these forms also causes variations in resolution and density in the pattern formed on the exposed surface.

According to the above embodiments (1) to (3), the residual elements of the pattern deformation of these forms after the micromirror actually used for the present exposure are also selected by the effect of replenishment by multiple exposure, like the residual elements of the angular deformation. It can make it uniform and can reduce the dispersion | variation in a resolution and density | concentration over the whole exposure area of each exposure head.

<< reference exposure >>

As a modification of the above-mentioned embodiments (1) to (3), among the usable micromirrors, the micromirror columns of every (N-1) columns or adjacent rows corresponding to 1 / N rows of all light spot rows are configured. The micromirrors not used at the time of actual exposure may be specified among the micromirrors used for the above-mentioned reference exposure so as to perform the reference exposure using only the micromirror group to be realized and to realize uniform exposure.

The result of the reference exposure by the reference exposure means is sampled, and the analysis of the output reference exposure result is performed by checking the variation of the resolution and the variation of the concentration and estimating the actual tilt angle. The analysis of the result of the reference exposure may be an analysis by the naked eye of the operator.

19A and 19B are explanatory diagrams showing an example of a form in which a reference exposure is performed using a single exposure head and using only the micromirrors in every (N-1) rows.

In this example, the exposure is assumed to be double exposure, so N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots of odd rows shown in solid lines in Fig. 19A, and the reference exposure results are sampled. The micromirror used at the time of this exposure can be specified by confirming the nonuniformity of a resolution and the dispersion | variation of a density based on the said sample-output reference exposure result, or estimating an actual inclination angle.

For example, micromirrors other than the micromirrors corresponding to the light spots covered with diagonal lines in FIG. 19B are designated as actually used in the present exposure among the micro mirrors constituting the odd light spots. For the even-numbered light spots, the micromirrors used in the present exposure may be designated similarly by the reference exposure, or the same pattern as the pattern for the light spots in the odd-numbered rows may be applied.

In this way, by specifying the micromirrors used in the present exposure, in the present exposure using the micromirrors in both odd and even columns, an ideal state of near double exposure can be realized.

It is explanatory drawing which showed the example of the form which performs a reference exposure using only the micromirror of every (N-1) columns using a some exposure head.

In this example, the exposure is assumed to be double exposure, so N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots of odd rows of two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction shown by solid lines in FIG. 20. The exposure result is sampled. Based on the output result of the reference exposure, two non-exposed heads confirm the unevenness of the resolution or the variation of the concentration in an area other than the connection area between the heads formed on the exposed surface, or estimate the actual inclination angle. The micromirror used at the time of exposure can be specified.

For example, among the micromirrors other than the micromirror corresponding to the light spot in the area | region 86 shown by the oblique line in FIG. 20, and the area | region 88 shown by hatching, the optical mirror of odd-numbered row | column is at the time of this exposure. It is specified as actually used. For the even-numbered light spots, the micromirrors used in the present exposure may be separately designated in the same manner, or the same pattern as that for the odd-numbered pixel columns may be applied.

By specifying the micromirrors actually used in the present exposure in this way, in the present exposure using the micromirrors of both odd and even columns, except for the head-to-head connection region formed on the exposed surface by the two exposure heads. It is possible to realize a state close to the ideal double exposure in the region of.

21A and 21B are explanatory diagrams showing an example of a reference exposure using a single exposure head and using only a micromirror group constituting adjacent rows corresponding to 1 / N rows of the total number of light spots.

In this example, the exposure is assumed to be double exposure, so N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots of the first to 128 (= 256/2) th rows shown by solid lines in FIG. 21A, and the reference exposure results are sampled. The micromirror used at the time of this exposure can be specified based on the sample exposure reference exposure result.

For example, micromirrors other than the micromirrors corresponding to the light spot group shown by oblique line shown in FIG. 21B can be designated as actually used at the time of this exposure among the micromirrors of the 1st to 128th rows. Similarly, the micromirrors used in the present exposure may be designated for the micromirrors of the 129th to 256th rows, and the same pattern as that for the micromirrors of the first to 128th rows may be applied. good.

In this way, by specifying the micromirrors used in the present exposure, a state close to the ideal double exposure can be realized in the present exposure using the entire micromirror.

FIG. 22 uses a plurality of exposure heads and corresponds to 1 / N rows of the total number of light spots, respectively, for two exposure heads adjacent to each other in the X-axis direction (for example, exposure heads 30 ₁₂ and 30 ₂₁ ). It is explanatory drawing which showed an example of the form which carries out a reference exposure using only the micromirror group which comprises the adjacent row to make.

In this example, the exposure is assumed to be double exposure, so N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots of the first to 128th (= 256/2) th rows shown by solid lines in FIG. 22, and the reference exposure results are sampled. On the basis of the sampled reference exposure result, the present exposure can be realized by minimizing the variation in the resolution and the variation in the concentration in an area other than the connection area between the heads formed on the exposed surface by the two exposure heads. The micromirror used at the time of this exposure can be specified so that it may be used.

For example, the micromirrors other than the micromirror corresponding to the light spot in the area | region 90 shown by the oblique line in FIG. 22, and the area | region 92 shown by hatching show at the time of this exposure among the micromirrors of the 1st row to the 128th row. It is specified as actually used in. The micromirrors used for this exposure may be designated similarly to the micromirrors of the 129th to 256th rows, and the same pattern as the pattern for the micromirrors of the first to 128th rows may be applied. .

By designating the micromirrors used in this exposure in this manner, it is possible to realize a state close to the ideal double exposure in an area other than the inter-head connection area formed on the exposed surface by the two exposure heads.

In the above embodiments (1) to (3) and the modification examples, the case where the present exposure is a double exposure has been described. However, the present invention is not limited to this, and may be any multi-exposure above the double exposure. In particular, when the exposure time is about triple to seven times, the high resolution can be ensured, and the exposure can be realized in which the unevenness and density variation of the resolution are reduced.

In addition, the exposure apparatus according to the above embodiments and modifications further converts the image data so that the dimensions of the predetermined portion of the two-dimensional pattern represented by the image data match the dimensions of the corresponding portion that can be realized by the selected use pixel. It is preferable that a mechanism is provided. By converting the image data in this manner, a high-definition pattern in accordance with a desired two-dimensional pattern can be formed on the exposed surface.

[Developing process]

The development is performed by removing the unexposed portion of the photosensitive layer.

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, alkaline aqueous solution, an aqueous developing solution, an organic solvent, etc. are mentioned, Among these, a slightly alkaline aqueous solution is preferable. Examples of the base component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, Potassium pyrophosphate, borax and the like.

For example, the pH of the weakly alkaline aqueous solution is preferably about 8 to 12, and more preferably about 9 to 11. As said weakly alkaline aqueous solution, 0.1-5 mass% sodium carbonate aqueous solution or potassium carbonate aqueous solution etc. are mentioned, for example.

Although the temperature of the said developing solution can be suitably selected according to the developability of the said photosensitive layer, about 25-40 degreeC is preferable, for example.

The developer may be a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.), or development. In order to make it use, you may use together with an organic solvent (for example, alcohol, ketone, ester, ether, amide, lactone, etc.). The developing solution may be an aqueous developing solution obtained by mixing water or an alkali aqueous solution with an organic solvent, or may be an organic solvent alone.

Curing Treatment Process

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

There is no restriction | limiting in particular as said hardening process process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned preferably.

As a method of the said whole 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 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, the exposure machine for xenon lamp use, a laser exposure machine, etc. are mentioned preferably. The exposure amount is usually 10 to ² , OOmJ / cm ² .

As said 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 is mentioned. By the whole surface heating, the film strength of the surface of the permanent pattern is increased.

120-250 degreeC is preferable and, as for the heating temperature in the said whole surface heating, 120-200 degreeC is more preferable. When the said heating temperature is less than 120 degreeC, the improvement of the film strength by heat processing may not be obtained, and when it exceeds 250 degreeC, decomposition | disassembly of resin in the said photosensitive composition may arise and a film quality may fall weakly. .

10-120 minutes are preferable and, as for the heat time in the said whole surface heating, 15-60 minutes are more preferable.

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

Protective film, interlayer insulating film, solder resist pattern formation method

When the pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, a permanent pattern is formed on the printed wiring board by the permanent pattern forming method. Soldering can be performed similarly.

That is, by the said development, 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 to the site | part of the metal layer exposed on 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, an insulating film (interlayer insulation film), and a soldering resist, and the impact from the outside and the conduction of the electrodes of neighbors are prevented.

In the pattern forming apparatus and the permanent pattern forming method, if the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, wiring can be protected from impact or warp from the outside, and in particular, the interlayer insulating film In one case, for example, it is useful for high-density mounting of semiconductors and components to multilayer wiring boards, build-up wiring boards, and the like.

The permanent pattern forming method of the present invention is a color filter for forming various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a soldering resist pattern, a corrugated material, a rib material, and a spacer in order to use the photosensitive laminate of the present invention. It can be used suitably for manufacture of liquid crystal structural members, such as a partition and a hologram, a micromachine, a proof, etc., and can especially use for formation of a permanent pattern of a printed circuit board.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these.

Synthesis Example 1

159 g of 1-methoxy-2-propanol was put into a 100 mL three-neck flask, and it heated to 85 degreeC under nitrogen stream. 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by KKK) were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was heated for 5 hours and further reacted. Then, heating was stopped and the copolymer of benzyl methacrylate / methacrylic acid (30/70 mol% ratio) was obtained.

Subsequently, 120.0 g of the above-mentioned conjugate solution was transferred to a 30 mL three-necked flask, 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added, followed by stirring to dissolve. After dissolution, 2.4 g of tetraethylammonium chloride was added, heated at 100 ° C, and addition reaction was performed. It was confirmed by gas chromatography that glycidyl methacrylate disappeared, and heating was stopped. 1-methoxy-2-propanol was added and the solution of the high molecular compound 1 represented by the following structural formula of 30 mass% of solid content was prepared.

The mass average molecular weight (Mw) of the obtained high molecular compound was 15,000 when measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

In addition, from titration using sodium hydroxide, the acid value (content of the carboxyl group) per solid content was 2.2 meq / g.

In addition, content (C = C value) of the ethylenically unsaturated bond of solid sugar calculated | required by iodine titration was 2.1 meq / g.

* 1 represents the mixture of the structure represented by the following structural formula (a) and the structure represented by the following structural formula (b).

Synthesis Example 2

159 g of 1-methoxy-2-propanol was put into a 100 mL three-neck flask, and it heated to 85 degreeC under nitrogen stream. 36 g of methyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by KKK) were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was heated for 5 hours and further reacted. Then, heating was stopped and the copolymer of methyl methacrylate / methacrylic acid (30/70 mol% ratio) was obtained.

Then, 120.0 g of the copolymer solution was transferred to a 30 mL three-necked flask, 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, triphenylphosphine 2.4 g was added, it heated at 100 degreeC, and addition reaction was performed. It was confirmed by gas chromatography that glycidyl methacrylate disappeared, and heating was stopped. 1-methoxy-2-propanol was added and the solution of the high molecular compound 2 represented by the following structural formula of 30 mass% of solid content was prepared.

The mass average molecular weight (Mw) of the obtained high molecular compound was 15,000 when measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

Moreover, the acid value of solid sugar was 2.3 meq / g from the titration using sodium hydroxide.

In addition, content (C = C value) of the ethylenically unsaturated bond of solid sugar obtained by titration of iodine was 2.6 meq / g.

* 1 represents the mixture of the structure represented by the structural formula (a) and the structure represented by the structural formula (b).

(Example 1)

Preparation of Photosensitive Composition

Each component was mix | blended in the following quantity and the photosensitive composition solution was prepared.

[Each component amount of photosensitive composition solution]

-The said polymeric compound 1 (30 mass% of solid content mass in the said 1-methoxy- 2-propanol solution). 87.4 parts by mass

· Dipentaerythritol hexaacrylate (polymerizable compound). 13 parts by mass

Ilgacua 819 (acylphosphine oxide compound, photoinitiator I-1). 6 parts by mass

· Sensitizer (thioxanthone compound) represented by the following formula S-1. 0.6 parts by mass

Efototo YD-8125 (epoxy equivalent 170g / eq. Manufactured by Dongbu Chemical Co., Ltd., bisphenol A epoxy resin). 8 parts by mass

Thermosetting agent (dicyandiamide). 0.77 parts by mass

XSK-500 (20 mass% methyl ethyl ketone solution, manufactured by Nippon Synthetic Rubber Co., Ltd., styrene-based (styrene butadiene) elastomer). 50 parts by mass

Fluorine-based surfactants (megapack F-176, manufactured by Dai Nippon Ink Chemical Co., Ltd., 30 mass% 2-butanone solution); 0.2 parts by mass

Barium sulfate dispersion (manufactured by Sakai Chemical Co., Ltd., B-30). 80 parts by mass

The barium sulfate dispersion was prepared by adding 10 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30) and 29.2 parts by mass of a polymer compound 1 (30 mass% of solids by mass in the 1-methoxy-2-propanol solution); After mixing 0.2 parts by mass of CI Pigment Blue 15: 3 and 0.05 parts by mass of CI Pigment Yellow 185 and 40.55 parts by mass of methyl ethyl ketone, zirconia with a diameter of 1.0 mm was obtained by motor mill M-200 (manufactured by Iger). It was prepared by dispersing 3.5 hours at 9m / s circumference using beads.

Preparation of Photosensitive Laminate

Next, as the substrate, a chemical polishing treatment was performed on the surface of the copper-clad laminate (no through hole, copper thickness of 12 µm) of the wiring formation completed as a printed circuit board. On the copper-clad laminate, the photosensitive composition was applied by screen printing to a thickness of 30 µm after drying using a 120-mesh Tetron screen, and dried at 80 ° C. for 15 minutes using a hot air circulation dryer to dry the photosensitive layer. The photosensitive laminated body by which the said copper clad laminated board and the said photosensitive layer were laminated | stacked in this order was prepared.

About the said photosensitive laminated body, the shortest developing time, the sensitivity, the resolution, the tackiness, and the edge roughness were evaluated with the following method, respectively. Table 2 shows the results other than the shortest developing time.

<Evaluation of shortest developing time>

A 30% 1 mass% aqueous sodium carbonate solution was sprayed at a pressure of 0.15 MPa on the entire surface of the photosensitive layer on the copper clad laminate, and the time required until the photosensitive layer on the copper clad laminate was dissolved and removed from the start of spraying the aqueous sodium carbonate solution. This was made into the shortest developing time. The shortest developing time was 18 seconds.

<Evaluation of sensitivity>

With respect to the photosensitive layer in the photosensitive laminated body prepared by using the pattern forming apparatus to be described below as 2 ^1/2 times the distance from the O.1mJ / cm ^2, the amount of light energy to 100mJ / ㎠ emits a different light Double exposure was used to cure a portion of the photosensitive layer. After allowing to stand at room temperature for 10 minutes, an aqueous solution of 1% by mass of sodium carbonate at 30 ° C. was sprayed at a spray pressure of 0.15 MPa for twice the shortest developing time to dissolve the uncured region on the entire surface of the photosensitive layer on the copper clad laminate. It removed and measured the thickness of the remaining hardened | cured area. Next, the relationship between the dose of light and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the said sensitivity curve, the amount of light energy when the thickness of a hardened area | region became 30 micrometers like the photosensitive layer before exposure was made into the amount of light energy required in order to harden a photosensitive layer.

<< pattern forming apparatus >>

As the light irradiation means, the haptic laser light source described in Japanese Patent Application Laid-Open No. 2005-258431 and the micromirror rows in which 1024 micromirrors are arranged in the main scanning direction shown in the schematic diagram in FIG. Pattern having a DMD 36 controlled to drive only 1024 x 256 rows of 768 sets arranged and an exposure head 30 having an optical system for forming the light shown in FIGS. 5A and 5B onto the photosensitive transfer film. The forming apparatus 10 was used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, it is slightly larger than the angle (theta) _ideal which is exactly double exposure using the micromirror 58 of 1024 columns x 256 rows which can be used. Angle was adopted. This angle θ _ideal is such that the number N of exposures in N, the number s in the column direction of the usable micromirrors 58, the spacing p in the column direction of the usable micromirrors 58, and the exposure head 30 are inclined. Regarding the pitch δ of the scan line formed by the micromirror in the state of

spsinθ _ideal ≥Nδ (Equation 1)

Is given by In the DMD 36 according to the present embodiment, as described above, a plurality of micromirrors 58 having the same vertical and horizontal arrangement intervals are arranged in a rectangular lattice shape.

pcosθ _ideal = δ (Equation 2)

Equation 1 is

stanθ _ideal = N (Equation 3)

Since s = 256 and N = 2, the angle θ _ideal is about 0.45 degrees. Therefore, 0.50 degree was employ | adopted as setting inclination-angle (theta), for example.

First, the state of the exposure pattern of the to-be-exposed surface was investigated in order to correct the nonuniformity and the exposure deviation of the resolution in double exposure. The results are shown in FIG. In FIG. 16, from the usable micromirrors 58 of the DMD 36 included in the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive transfer film 12 with the stage 14 stopped. The light spot group pattern of was shown. In addition, when the continuous exposure is performed by moving the stage 14 in a state where the light spot group pattern as shown in the upper portion is exposed at the lower portion, the exposure pattern formed on the exposed surface is exposed to an exposure area 32 _12. And 32 ₂₁ ). In addition, in FIG. 16, for the convenience of explanation, although the exposure pattern of every other column of the micromirror 58 which can be used was divided into the exposure pattern by the pixel column group A, and the exposure pattern by the pixel column group B, it shows an actual pino. The exposure pattern on a light surface superposes | polymerizes these two exposure patterns.

As shown in Fig. 16, as a result of the deviation from the ideal state of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ , the exposure area (in both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B) It can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure heads 32 ₁₂ and 32 ₂₁ ), an area overexposing than the state of an ideal double exposure occurs.

A set of slits 28 and a photodetector are used as the light spot position detecting means, and the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ with respect to the exposure head 30 ₁₂ . For the exposure head 30 ₂₁ , the positions of the light spots P (1, 1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected, and the inclination angle of the straight line connecting them is scanned and the exposure head is scanned. The angle formed by the direction was measured.

Using the actual tilt angle θ ', the following equation 4

ttanθ '= N (Equation 4)

The natural number T closest to the value t satisfying the relationship of was derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 was obtained for the exposure head 30 ₁₂ and T = 255 was derived for the exposure head 30 ₂₁ , respectively. As a result, in Fig. 17, the micromirrors constituting the portions 78 and 80 covered with diagonal lines were identified as the micromirrors not used during this exposure.

Subsequently, with respect to the micromirrors corresponding to the light points other than the light points constituting the areas 78 and 80 covered with diagonal lines in FIG. 17, the areas 82 and hatched covered with diagonal lines in FIG. 17 are similarly applied. The micromirror corresponding to the light point which comprises the covered area | region 84 was specified, and was added as a micromirror which is not used at the time of this exposure.

With respect to the micromirror specified as not being used during these exposures, a signal for setting at an off-state angle is always sent by the drawing element control means, so that the micromirror is controlled so as not to substantially participate in the exposure.

Accordingly, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads, an area that becomes overexposed to the ideal double exposure. , And the total area of the areas that become underexposed can be minimized.

<Evaluation of resolution>

The said photosensitive laminated body was produced by the same method and conditions as the evaluation method of the said shortest image development time, and it left still for 10 minutes at room temperature (23 degreeC, 55% RH). On the photosensitive layer of the obtained photosensitive laminated body, each line | wire width is exposed by 1 micrometer interval to line width 10 / 1-100 micrometers with line / space = 1/1 using the said pattern forming apparatus. The exposure amount at this time is an amount of light energy required for curing the photosensitive layer. After allowing to stand at room temperature for 10 minutes, the entire surface of the photosensitive layer on the copper clad laminate was sprayed with a 30% 1 mass% sodium carbonate aqueous solution at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove the uncured region. do. The surface of the copper clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the line width of the cured resin pattern was free from abnormalities such as clogging and twisting, and the minimum line width that can form a space was measured. . The smaller the numerical value, the better.

<Evaluation of Tajik>

The tackiness of the surface of the photosensitive layer in the said photosensitive laminated body was evaluated based on the following criteria. The results are shown in Table 2.

[Evaluation standard]

(Double-circle): Tackiness was not confirmed at all on the surface of a photosensitive layer.

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

(Triangle | delta): Tackiness was confirmed to the surface of the photosensitive layer a little.

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

<Evaluation of edge roughness>

The photosensitive laminate is irradiated so as to form a horizontal line pattern in a direction orthogonal to the scanning direction of the exposure head using the pattern forming apparatus, and subjected to double exposure, and a region of a part of the photosensitive layer is measured in the measurement of the resolution. The pattern was formed in the same manner as in 3). Of the obtained patterns, any five places having a line width of 50 µm were observed using a laser microscope (VK-9500, manufactured by Gence Co., Ltd .; objective lens 50 times), and most protruded among the edge positions in the field of view. The difference between the point (mountain) and the most concave point (curve) was calculated as an absolute value, and the average value of the five observed points was calculated, which was called edge roughness. The edge roughness is preferable because the smaller the value, the better the performance.

(Example 2)

Production of Photosensitive Film

The photosensitive composition solution obtained in Example 1 was applied with a bar coater on a PET (polyethylene terephthalate) film having a thickness of 16 μm, a width of 300 mm, and a length of 200 m as the support, and dried in an 80 ° C. hot air circulation type dryer to have a thickness of 30 μm. The photosensitive layer was formed. Subsequently, as a protective film, the polypropylene film of 20 micrometers of thickness, 310 mm in width, and 210 m in length was laminated | stacked by the lamination, and the said photosensitive film was manufactured on the said photosensitive layer.

Preparation of Photosensitive Laminate

Next, as the base, the photosensitive layer of the photosensitive film is brought into contact with the copper clad laminate to peel the protective film of the photosensitive film on the same copper clad laminate as in Example 1, and then a vacuum laminator (Nichi-Moton (Note) ), A photosensitive laminate in which the copper clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were sequentially laminated were prepared.

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

The sensitivity, resolution, tackiness, storage stability, and edge roughness were evaluated for the photosensitive laminate. In addition, the resolution, tackiness, and edge roughness were evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Evaluation of sensitivity>

About the photosensitive layer of the photosensitive film in the prepared photosensitive laminated body, the area | region of one part of the said photosensitive layer was hardened similarly to Example 1 by the pattern forming apparatus demonstrated in Example 1 from the said support body side. After standing at room temperature for 10 minutes, the support was peeled from the photosensitive laminate, and the amount of light energy required to cure the photosensitive layer was measured in the same manner as in Example 1.

<Evaluation of Preservation Stability>

The photosensitive film was wound with a winder to prepare a photosensitive film disc roll.

The obtained photosensitive film master roll was slitted by the coaxial slitter, and it wound up by 150 mm in 250 mm width to the cylindrical core made of ABS resin of length 300mm and inner diameter 76mm, and produced the photosensitive film roll.

The photosensitive film roll obtained in this way was put into the normal bag (film thickness of 80 micrometers, water vapor transmission rate: 25 g / m <^2> / 24hr or less) made of black polyethylene, the polypropylene bush is pressed in the both ends of the winding core, and the said obtained The photosensitive film roll was put into the normal bag (film thickness: 80 micrometers, water vapor transmission rate: 25 g / m <^2> / 24hr or less) made of black polyethylene, and the polypropylene bush was pressed in the both ends of the winding core.

The roll-shaped sample which closed both ends with the said bush was preserve | saved at 25 degreeC and 55% RH for 40 days, and the presence or absence of sectional fusion was observed, and the storage stability was evaluated based on the following reference | standard.

[Evaluation standard]

(Circle): A state in which end surface fusion is not confirmed and a laminated body can be used favorably.

(Triangle | delta): The state in which a part of end surface has gloss and some amount of end surface fusion has occurred (use limit).

X: A state in which the entire surface of the end face has gloss and a large amount of end face welding occurs.

(Example 3)

Example 2 WHEREIN: Except having replaced XSK-500 by 25 mass parts of XER-91 (15 mass% methyl ethyl ketone solution, the Japan Synthetic Rubber Co., Ltd. make, polyolefin elastomer) as shown in Table 1. In the same manner as described above, sensitivity, resolution, tackiness, storage stability, and edge roughness were evaluated. The results are shown in Table 2.

(Example 4)

Example 2 WHEREIN: Except having replaced XSK-500 by 20 mass parts of XER-92 (15 mass% methyl ethyl ketone solution, the Japan Synthetic Rubber Co., Ltd. make, polyolefin elastomer) as shown in Table 1. In the same manner as described above, sensitivity, resolution, tackiness, storage stability, and edge roughness were evaluated. The results are shown in Table 2.

(Example 5)

In Example 2, sensitivity, resolution, and the like of Example 2 were changed except that XSK-500 was replaced with 10 parts by mass of VANDEX T-8190 (manufactured by DIC Bayer Polymer, urethane-based elastomer) as shown in Table 1. Tackiness, storage stability, and edge roughness were evaluated. The results are shown in Table 2.

(Example 6)

In Example 2, the sensitivity, resolution, and the likeness of Example 2 were changed in the same manner as in Example 2 except that XSK-500 was replaced by 5 parts by mass of Hytrel SB654 (a polyester-based elastomer manufactured by Toray Dupont) as shown in Table 1. Tackiness, storage stability, and edge roughness were evaluated. The results are shown in Table 2.

(Example 7)

Example 2 WHEREIN: Except that the said polymeric compound 1 was replaced with the polymeric compound 2 obtained by the synthesis example 2 as 87.4 mass parts as shown in Table 1, it carried out similarly to Example 2, and it showed the sensitivity, the resolution, the tackiness, and the preservation. The stability and edge roughness were evaluated. The results are shown in Table 2.

(Example 8)

In Example 2, except having replaced the sensitizer with 0.6 mass parts of N-methyl-acridones in 2 mass parts of the compound represented by following formula I-2, a photoinitiator, it carried out similarly to the sensitivity of Example 2, The resolution, tackiness, storage stability, and edge roughness were evaluated. The results are shown in Table 2.

(Example 9)

In Example 2, except for replacing the photoinitiator with 2 parts by mass of the compound represented by the following formula I-3 as shown in Table 1, and in the same manner as in Example 2, sensitivity, resolution, tackiness, storage stability, and Edge roughness was evaluated. The results are shown in Table 2.

(Example 10)

In Example 2, instead of the said pattern forming apparatus, the glass negative mask which has the same pattern as this was produced separately, this negative mask was made to contact on the photosensitive laminated body, and it exposed by the exposure amount of 40mJ / cm <^{2> with} an ultrahigh pressure mercury lamp. . Thereafter, development was carried out in the same manner as in Example 2, and the resolution, tackiness, storage stability, and edge roughness were evaluated in the same manner as in Example 2 except that the resolution was measured.

(Example 11)

In Example 2, the set inclination angle θ is calculated as N = 1 based on Equation 3, and the natural number T closest to the value t satisfying the relationship of ttanθ '= 1 is derived based on Equation 4, The sensitivity, the resolution, the tackiness, the storage stability, and the edge roughness were evaluated in the same manner as in Example 2 except that N exposure (N = 1) was performed. The results are shown in Table 2.

(Comparative Example 1)

In Example 2, the compound (30 mass% of solid content mass in 1-methoxy-2-propanol solution) of the said polymeric compound 1 represented by following formula B-1; Except having replaced by 87.4 mass parts, it carried out similarly to Example 2, and evaluated the sensitivity, the resolution, tackiness, storage stability, and edge roughness. The results are shown in Table 2.

(Comparative Example 2)

In Example 2, 52.4 parts by mass of the polymer compound 1 was represented by the following formula B-2 in an epoxy acrylate (50 wt% 1-methoxy-2-propanol solution: Mw: 8,000, acid value: 80 mgKOH / g). Except for being substituted, it carried out similarly to Example 2, and evaluated the sensitivity, the resolution, tackiness, storage stability, and edge roughness. The results are shown in Table 2.

type Elastomer bookbinder Photopolymerization initiator Exposure Example 1 Liquid resist Styrene series Polymer Compound 1 I-1 laser Example 2 film Styrene series Polymer Compound 1 I-1 laser Example 3 film Polyolefin Polymer Compound 1 I-1 laser Example 4 film Polyolefin Polymer Compound 1 I-1 laser Example 5 film Urethane Polymer Compound 1 I-1 laser Example 6 film Polyester Polymer Compound 1 I-1 laser Example 7 film Styrene series Polymer Compound 2 I-1 laser Example 8 film Styrene series Polymer Compound 1 I-2 laser Example 9 film Styrene series Polymer Compound 1 I-3 laser Example 10 film Styrene series Polymer Compound 1 I-1 analog Example 11 film Styrene series Polymer Compound 1 I-1 laser Comparative Example 1 film Styrene series B-1 I-1 laser Comparative Example 2 film Styrene series B-2 I-1 laser

Sensitivity (mJ / cm ² ) Resolution (μm) Tackiness Retention stability Edge Roughness (μm) Example 1 67 40 ◎ - 1.5 Example 2 42 30 ◎ ○ 1.3 Example 3 45 30 ◎ ○ 1.3 Example 4 47 30 ◎ ○ 1.3 Example 5 46 30 ◎ ○ 1.4 Example 6 50 30 ◎ ○ 1.4 Example 7 50 30 ◎ ○ 1.3 Example 8 27 30 ◎ ○ 1.3 Example 9 26 30 ◎ ○ 1.3 Example 10 - 37 ◎ ○ 2.3 Example 11 42 30 ◎ ○ 2 Comparative Example 1 140 37 ○ △ 1.3 Comparative Example 2 100 35 △ × 1.4

From the result of Table 2, since the photosensitive composition of this invention was used in Examples 1-11, it turned out that it is excellent in tackiness. In particular, in Examples 2-11 which produced the photosensitive film, it turned out that the resolution and storage stability are also high. Moreover, in Examples 2-9 and 11 which performed laser exposure, it also turned out that a sensitivity is high. In particular, in Example 8 and Example 9 using an oxime derivative, it turned out to be very sensitive.

On the other hand, the pattern of Examples 2-9 which correct | amended the nonuniformity of the resolution and exposure unevenness in double exposure turned out that edge roughness is also small.

The photosensitive composition, the photosensitive film, and the photosensitive laminate of the present invention have no edge fusion (cross-sectional fusion), are excellent in tackiness and performance stability over time, are easily formed into films, and can efficiently form high-definition permanent patterns. Therefore, various pattern formation such as permanent patterns such as protective films, interlayer insulating films, and solder resist patterns, production of liquid crystal structural members such as color filters, aggregate materials, rib materials, spacers, partition walls, production of holograms, micromachines, and proofs It can use preferably, etc., Especially it can use preferably for the permanent pattern formation of a printed board.

Since the method of forming a permanent pattern of the present invention uses the photosensitive laminate of the present invention, it is possible to form various patterns such as permanent patterns such as protective films, interlayer insulating films, and solder resist patterns, color filters, aggregate materials, rib materials, and spacers. It can be used suitably for manufacture of liquid crystal structural members, such as a partition, a hologram, a micromachine, a proof, etc., and especially can be used for formation of a permanent pattern of a printed circuit board.

Claims (14)

A binder, a polymeric compound, a photoinitiator, an elastomer, and a thermal crosslinking agent, The said binder contains the high molecular compound which has an acidic group and ethylenically unsaturated bond in a side chain. The method of claim 1, Said binder contains the high molecular compound which has an aromatic group and ethylenically unsaturated bond which may contain an acidic group and a heterocyclic ring in a side chain, The photosensitive composition characterized by the above-mentioned. The method according to claim 1 or 2, The acid group of the said high molecular compound is a carboxyl group, and content in the said high molecular compound of the said carboxyl group is 1.0-4.0 meq / g, The photosensitive composition characterized by the above-mentioned. The method according to any one of claims 1 to 3, Said high molecular compound contains 20 mol% or more of structural units represented by following structural formula (I), The photosensitive composition characterized by the above-mentioned.

[However, in the structural formula (I), R ₁ , R ₂ , and R ₃ represent a hydrogen atom or a monovalent organic group. L may represent an organic group and may be absent. Ar represents an aromatic group.] The method according to any one of claims 1 to 4, The elastomer is a photosensitive composition, characterized in that at least one selected from styrene-based elastomer, olefin-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic elastomer, and silicone-based elastomer. The method according to any one of claims 1 to 5, Content of the said elastomer is 2-50 mass parts with respect to 100 mass parts of binders, The photosensitive composition characterized by the above-mentioned. The method according to any one of claims 1 to 6, The photopolymerization initiator is a photosensitive composition, characterized in that it contains an oxime derivative. It has a support body and the photosensitive layer which consists of a photosensitive composition of any one of Claims 1-7 on the said support body, The photosensitive film characterized by the above-mentioned. The method of claim 8, It is elongate and is wound up in roll shape, The photosensitive film characterized by the above-mentioned. It has a photosensitive layer which consists of a photosensitive composition of any one of Claims 1-7 on a base body, The photosensitive laminated body characterized by the above-mentioned. The method of claim 10, The said photosensitive layer was formed of the photosensitive film of Claim 8 or 9, The photosensitive laminated body characterized by the above-mentioned. 12. A method for forming a permanent pattern, comprising the step of exposing the photosensitive layer in the photosensitive laminate according to claim 10 or 11. The method of claim 12, The said exposure is performed using the laser beam of the wavelength of 350-415 nm, The permanent pattern formation method characterized by the above-mentioned. The permanent pattern is formed by the permanent pattern formation method of Claim 12 or 13. The printed circuit board characterized by the above-mentioned.

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