JP2007310060A - Photosensitive resin composition and photosensitive film, permanent pattern forming method, and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in various properties such as pattern forming property, plating resistance and peeling property, having high sensitivity and good resolution, and capable of efficiently forming a high-definition permanent pattern, in order to form a permanent pattern such as a solder resist, and to provide a photosensitive film, a permanent pattern forming method using the photosensitive resin composition, and a printed wiring board on which a permanent pattern is formed by the permanent pattern forming method. <P>SOLUTION: The photosensitive resin composition comprises a binder, a polymerizable compound, a photopolymerization initiator, a heat crosslinking agent and a polymerizable compound, wherein the binder comprises an acid modified vinyl group-containing epoxy resin, the photopolymerization initiator comprises compound represented by formula (1) (wherein R<SP>1</SP>represents acyl, alkoxycarbonyl or the like; R<SP>2</SP>represents alkyl; and R<SP>3</SP>represents naphthyl), and the heat crosslinking agent comprises an epoxy compound having two or more epoxy groups per molecule. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in various characteristics such as pattern formability, plating resistance, and peelability, has high sensitivity, excellent resolution, and high-definition permanent patterns (such as protective films, interlayer insulating films, and solder resist patterns) efficiently. The present invention relates to a photosensitive resin composition that can be formed, a photosensitive film, a permanent pattern forming method using the photosensitive resin composition, and a printed wiring board on which a permanent pattern is formed by the permanent pattern forming method.

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

The resist material made of such a photosensitive resin composition is mainly of an alkali developing type using a sodium hydrogen carbonate solution as a developing solution at the time of pattern formation.
However, in the resist material comprising such a photosensitive resin composition, in order to improve the productivity of the printed wiring board, the exposure amount is often reduced with respect to the photosensitive layer, and the resolution is reduced during development. Defects sometimes occurred. In addition, there is a problem that a resolution failure may occur with the increase in the wiring density of the printed wiring board, resulting in many defects.

For this reason, the photosensitive resin composition which can raise sensitivity and can improve resolution is proposed (refer patent documents 1 and 2).
However, these photosensitive resin compositions are not satisfactory in terms of sensitivity and resolution, and further improvements are required.

  In other words, not only the characteristics such as pattern forming property, plating resistance, and peelability as a photosensitive resist material, but also high sensitivity, and there are very few resist pattern chips and defects after development, and the yield is improved. Development of a photosensitive resin composition exhibiting such excellent performance is desired.

JP 2002-107926 A JP-A-5-281733

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is a photosensitive resin composition that is excellent in various properties such as pattern formability, plating resistance, and peelability, has high sensitivity, has good resolution, and can efficiently form a high-definition permanent pattern. It is an object of the present invention to provide a photosensitive film, a permanent pattern forming method using the photosensitive resin composition, and a printed wiring board on which a permanent pattern is formed by the permanent pattern forming method.

Means for solving the problems are as follows. That is,
<1> A binder, a photopolymerization initiator, a thermal crosslinking agent, and a polymerizable compound, wherein the binder contains an acid-modified vinyl group-containing epoxy resin, and the photopolymerization initiator is represented by the following general formula (1 ), And the thermal cross-linking agent contains an epoxy compound having two or more epoxy groups in one molecule.
In general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents an alkyl group, and R ³ represents a naphthyl group. R ¹ , R ² , and R ³ may be further substituted with a substituent.
<2> The acid-modified vinyl group-containing epoxy resin is a novolac type epoxy resin represented by the following general formula (A-1), a bisphenol type epoxy resin represented by the following general formula (A-2), and the following general formula: <1>, which is a resin obtained by reacting at least one epoxy resin selected from the group consisting of a salicylaldehyde type epoxy resin represented by (A-3) and a vinyl group-containing monocarboxylic acid. It is the photosensitive resin composition as described in above.


However, in general formula (A-1), (A-2), and (A-3), X represents either a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group ( The molar amount of the hydrogen atom / the molar amount of the glycidyl group represents 0/100 to 30/70, R represents one of a hydrogen atom and a methyl group, and n represents an integer of 1 or more. .
<3> The bisphenol type epoxy resin represented by the general formula (A-2) is any one of the bisphenol A type epoxy resin and the bisphenol F type epoxy resin, according to any one of the items <1> to <2>. It is the photosensitive resin composition of description.
<4> The solid content of the acid-modified vinyl group-containing epoxy resin is 5 to 80% by mass with respect to the total solid content of the photosensitive resin composition, according to any one of <1> to <3>. The photosensitive resin composition.
<5> The photosensitive material according to any one of <1> to <4>, wherein the compound represented by the general formula (1) is a compound represented by any one of the following general formulas (2) and (3). It is an adhesive resin composition.
However, in general formula (2) and (3), R < ¹ > represents either an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > represents an alkyl group. R ¹ and R ² may be further substituted with a substituent.
<6> From <1> to <5, wherein the solid content of the compound represented by the following general formula (1) is 0.01 to 10% by mass with respect to the total solid content of the photosensitive resin composition. > The photosensitive resin composition according to any one of the above.
In general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents an alkyl group, and R ³ represents a naphthyl group. R ¹ , R ² , and R ³ may be further substituted with a substituent.
<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the photopolymerization initiator contains a photopolymerization initiator other than the compound represented by the general formula (1).
<8> The photosensitive resin composition according to any one of <1> to <7>, containing a sensitizer.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the polymerizable compound is a liquid photosensitive compound having one or more unsaturated double bonds in one molecule. It is a thing.
<10> The photosensitive property according to any one of <1> to <9>, wherein the solid content of the polymerizable compound is 2 to 50% by mass with respect to the total solid content of the acid-modified vinyl group-containing epoxy resin. It is a resin composition.
<11> The photosensitive resin composition according to any one of <1> to <10>, including any one of an inorganic filler and an organic filler.

<12> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive resin composition according to any one of <1> to <11> on the support. is there.
<13> The photosensitive film according to <12>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<14> The photosensitive film according to any one of <12> to <13>, wherein the support includes a synthetic resin and is transparent.
<15> The photosensitive film according to any one of <12> to <14>, wherein the support has a long shape.
<16> The photosensitive film according to any one of <12> to <15>, which is long and wound in a roll shape.
<17> The photosensitive film according to any one of <12> to <16>, having a protective film on the photosensitive layer.

<18> A light irradiation means capable of irradiating light, and a photosensitive layer formed of the photosensitive resin composition according to any one of <1> to <11>, wherein light from the light irradiation means is modulated. The pattern forming apparatus includes at least light modulation means for performing exposure on the pattern. In the pattern forming apparatus according to <18>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation unit modulates light received from the light irradiation unit. The light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<19> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. It is a pattern formation apparatus as described in said <18> modulated according to. In the pattern forming apparatus according to <19>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit corresponds to the control signal generated by the pattern signal generation unit. Modulated.
<20> The light modulation means has n pixel parts, and forms any less than n pixel elements continuously arranged from the n pixel parts. The pattern forming apparatus according to any one of <18> to <19>, which can be controlled according to pattern information. In the pattern forming apparatus according to <20>, an arbitrary less than n pixel portions arranged continuously from n pixel portions in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<21> The pattern forming apparatus according to any one of <18> to <20>, wherein the light modulation unit is a spatial light modulation element.
<22> The pattern forming apparatus according to <21>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<23> The pattern forming apparatus according to any one of <20> to <22>, wherein the picture element portion is a micromirror.
<24> The pattern forming apparatus according to any one of <18> to <23>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the pattern forming apparatus according to <24>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<25> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. The pattern forming apparatus according to any one of <18> to <24>. In the pattern forming apparatus according to <25>, the light irradiation unit can condense the laser beams irradiated from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<26> A method for forming a permanent pattern, comprising exposing the photosensitive layer formed of the photosensitive resin composition according to any one of <1> to <11>.
<27> The method for forming a permanent pattern according to <26>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <12> to <17>.
<28> The method for forming a permanent pattern according to <26>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<29> The method for forming a permanent pattern according to any one of <26> to <28>, wherein the exposure is performed imagewise based on pattern information to be formed.

<30> Exposure has light irradiation means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means, An exposure head provided with a light modulation means capable of controlling the picture element portion in accordance with pattern information, wherein the column direction of the picture element portion forms a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged as follows:
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The permanent pattern formation method according to any one of <26> to <29>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the permanent pattern forming method according to <30>, the exposure head is subjected to N multiple exposures (where N is a natural number equal to or greater than 2) among the usable pixel parts by the used pixel part designating unit. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. . By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<31> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the joint area between the heads, which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. It is the permanent pattern forming method according to <30>, wherein, among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the permanent pattern forming method according to the above <31>, the exposure is performed by a plurality of exposure heads, and the used pixel part designating unit is an overlapping exposure region on an exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the connection area between the heads, by specifying the picture element part used for realizing the N-fold exposure in the connection area between the heads, the mounting position of the exposure head, Variations in the resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the mounting angle deviation are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<32> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to any one of <30> to <31>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area among the image element parts is designated. It is. In the method for forming a permanent pattern according to <32>, the exposure is performed by a plurality of exposure heads, and the used image element designating unit is an overlapping exposure region on an exposed surface formed by the plurality of exposure heads. Mounting of the exposure head by designating the picture element part used for realizing N double exposure in areas other than the inter-head connection area among the image element parts related to exposure other than the inter-head connection area Variations in the resolution and density unevenness of the pattern formed in areas other than the joint area between the heads on the exposed surface of the photosensitive layer due to a shift in position and mounting angle are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<33> When the set inclination angle θ is N, the number of N exposures, the number s of pixel parts in the column direction, the interval p in the column direction of the pixel parts, and the exposure head tilted. the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying the spsinθ _ideal ≧ Nδ, which is set to satisfy the relation of θ ≧ θ _ideal <30> to <32>.
<34> The method for forming a permanent pattern according to any one of <30> to <33>, wherein N in N-fold exposure is a natural number of 3 or more. In the method for forming a permanent pattern described in <34>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<35> Use pixel part designation means,
A light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface;
<30> to <34>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. This is a permanent pattern forming method.
<36> The permanent pattern forming method according to any one of <30> to <35>, wherein the used pixel part specifying unit specifies, in line units, the used pixel part used for realizing the N double exposure. It is.

<37> Based on at least two light spot positions detected by the light spot position detection means, the column direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted <35> to <36> wherein the inclination angle θ ′ is specified, and the drawing portion selection means selects the drawing portion used so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. The permanent pattern forming method according to any one of the above.
<38> The average inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. The method for forming a permanent pattern according to <37>, wherein the method is any one of a maximum value and a minimum value.
<39> The pixel part selection means derives a natural number T close to t satisfying the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <35> to <38> for selecting the pixel part from the first line to the T-th line in a line element (where m represents a natural number of 2 or more) arranged as a used pixel part The permanent pattern forming method according to any one of the above.
<40> The pixel part selection means derives a natural number T close to t satisfying the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part in the (T + 1) -th line to the m-th line is specified as an unused picture element part, and the unused picture element part is specified. The permanent pattern forming method according to any one of <35> to <39>, wherein the pixel part excluding the element part is selected as a use pixel part.

<41> In an area including at least an overlapped exposure area on an exposed surface formed by a plurality of pixel part columns,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that an area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) an ideal From <35>, which is one of means for selecting a used pixel part so that the area of an underexposed region is minimized and an overexposed region does not occur with respect to typical N double exposure It is a permanent pattern formation method as described in <40>.
<42> In the connection region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The method for forming a permanent pattern according to any one of <35> to <41>, which is any of the above.
<43> The permanent pattern forming method according to <42>, wherein the unused pixel parts are specified in units of rows.

<44> In order to specify the used pixel part in the used pixel part specifying means, among the pixel parts that can be used, with respect to N of N double exposure, the pixel part sequence for each (N-1) column The permanent pattern forming method according to any one of <35> to <43>, wherein the reference exposure is performed using only the picture element portion that constitutes. In the permanent pattern forming method according to the above <44>, in order to specify a used pixel part in the used pixel part specifying unit, among N of the usable pixel parts, N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<45> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel elements, a N / N line pixel part row is configured for N of N multiple exposures. The method for forming a permanent pattern according to any one of <35> to <44>, wherein the reference exposure is performed using only the pixel part. In the permanent pattern forming method according to the above <45>, in order to designate the use pixel part in the use pixel part designating unit, among the usable picture element parts, N is 1 for N double exposure. / Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<46> From the above <30> to <45, wherein the used pixel part specifying means includes a slit and a photodetector as the light spot position detecting means, and an arithmetic unit connected to the photodetector as the pixel part selecting means. > The permanent pattern forming method according to any one of the above.
<47> The method for forming a permanent pattern according to any one of <30> to <46>, wherein N of N-exposure is a natural number of 3 or more and 7 or less.

<48> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation unit is generated by the light irradiation unit. The method for forming a permanent pattern according to any one of <30> to <47>, wherein the modulation is performed according to. In the pattern forming apparatus according to <48>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit corresponds to the control signal generated by the pattern signal generation unit. Modulated.
<49> The permanent pattern formation method according to <48>, wherein the light modulation unit is a spatial light modulation element.
<50> The method for forming a permanent pattern according to <49>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<51> The permanent pattern forming method according to any one of <30> to <50>, wherein the picture element portion is a micromirror.
<52> From <30> to <30> further including conversion means for converting the pattern information so that a dimension of a predetermined part of the pattern represented by the pattern information matches a dimension of a corresponding part that can be realized by the designated used pixel part. 51>. The permanent pattern forming method according to any one of the above.

<53> The permanent pattern forming method according to any one of <30> to <52>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <53>, the light irradiation unit can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<54> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser light irradiated from the plurality of lasers and couples the laser light to the multimode optical fiber. The method for forming a permanent pattern according to any one of <30> to <53>. In the method for forming a permanent pattern according to <54>, the light irradiating unit can collect the laser light emitted from the plurality of lasers by the collective optical system and couple the laser light to the multimode optical fiber. As a result, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<55> The method for forming a permanent pattern according to any one of <26> to <54>, wherein the photosensitive layer is developed after the exposure. In the permanent pattern formation method according to <55>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<56> The permanent pattern forming method according to <55>, wherein the permanent pattern is formed after the development.
<57> The method for forming a permanent pattern according to <56>, wherein after the development, the photosensitive layer is cured.
<58> The method for forming a permanent pattern according to <57>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.
<59> The permanent pattern forming method according to any one of <57> to <58>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. In the method for forming a permanent pattern according to <59>, since at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed, the wiring is externally provided due to the insulating property, heat resistance, and the like of the film. Protected from impact and bending.

  <60> A permanent pattern obtained by the method for forming a permanent pattern according to any one of <26> to <59>.

  <61> A printed wiring board obtained by the method for forming a permanent pattern according to any one of <26> to <59>.

  According to the present invention, conventional problems can be solved, and for the purpose of forming a permanent pattern such as a solder resist, it has excellent characteristics such as pattern formability, plating resistance, peelability, high sensitivity, and resolution. Photosensitive resin composition capable of efficiently forming a high-definition permanent pattern, a photosensitive film, a permanent pattern forming method using the photosensitive resin composition, and a permanent pattern formed by the permanent pattern forming method Printed wiring boards can be provided.

  The present invention has a photosensitive resin composition, a photosensitive film obtained by laminating a photosensitive layer made of the photosensitive resin composition, a permanent pattern forming method, and a permanent pattern obtained by the permanent pattern forming method. The printed wiring board will be described in the following order.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention includes at least a binder, a thermal crosslinking agent, a photopolymerization initiator, and a polymerizable compound, and includes other components appropriately selected as necessary.
The binder contains an epoxy resin containing an acid-modified vinyl group, the photopolymerization initiator contains a photopolymerization initiator represented by the following general formula (1), and the thermal crosslinking agent is in one molecule. It contains an epoxy compound having two or more epoxy groups.
The photosensitive resin composition of the present invention includes an epoxy resin containing an acid-modified vinyl group as the binder, and includes a photopolymerization initiator represented by the following general formula (1) as the photopolymerization initiator, By including an epoxy compound having two or more epoxy groups in one molecule as the thermal crosslinking agent, the pattern forming property, plating resistance, and peelability are excellent, the sensitivity is high, and the resolution is good.
In general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents an alkyl group, and R ³ represents a naphthyl group. R ¹ , R ² , and R ³ may be further substituted with a substituent.

<Binder>
The binder includes at least an epoxy resin containing the acid-modified vinyl group, and includes other binders appropriately selected as necessary.

-Epoxy resin containing acid-modified vinyl group-
The epoxy resin containing an acid-modified vinyl group is not particularly limited as long as it is an epoxy resin containing an acid-modified vinyl group. For example, a resin obtained by modifying an epoxy resin with a vinyl group-containing monocarboxylic acid is preferable.
Specific examples of the resin obtained by modifying the epoxy resin with a vinyl group-containing monocarboxylic acid include, for example, a novolac type epoxy resin represented by the following general formula (A-1) and a general formula (A-2) below. At least one epoxy resin selected from the group consisting of a bisphenol-type epoxy resin and a salicylaldehyde-type epoxy resin represented by the following general formula (A-3), and a vinyl group-containing monocarboxylic acid. The obtained resin is preferable.
A resin obtained by reacting an epoxy resin represented by any one of the following general formulas (A-1) to (A-3) with a vinyl group-containing monocarboxylic acid, wherein the epoxy resin containing the acid-modified vinyl group is When it is, plating tolerance and peelability may improve.

However, in general formula (A-1), (A-2), and (A-3), X represents either a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group ( The molar amount of the hydrogen atom / the molar amount of the glycidyl group represents 0/100 to 30/70, R represents one of a hydrogen atom and a methyl group, and n represents an integer of 1 or more. .

  As said n, it is preferable that it is an integer of 2-100, for example. When the n is an integer of 2 to 100, plating resistance and peelability may be improved.

Examples of the novolak type epoxy resin represented by the general formula (A-1) include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin.
There is no restriction | limiting in particular as a manufacturing method of the novolak-type epoxy resin represented by the said general formula (A-1), It can select suitably from well-known manufacturing methods, For example, a phenol novolak resin and a cresol novolak Examples include a method of reacting epichlorohydrin with any of the resins.

As the bisphenol type epoxy resin represented by the general formula (A-2), for example, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable.
When X in the bisphenol type epoxy resin represented by the general formula (A-2) is a glycidyl group represented by the following structural formula (5), the bisphenol type epoxy represented by the general formula (A-2) The method for producing the resin is not particularly limited and may be appropriately selected from known methods. For example, any one of the hydroxyl groups of the bisphenol-type epoxy resin represented by the following general formula (6), epichlorohydrin, The method of reacting is preferred.
As reaction conditions for promoting the reaction between the hydroxyl group and the epichlorohydrin, for example, the reaction temperature is 50 to 120 ° C., and the reaction is preferably performed in a polar organic solvent in the presence of an alkali metal hydroxide. When the reaction temperature is less than 50 ° C, the reaction may be slow, and when it exceeds 120 ° C, many side reactions may occur.
Examples of the polar organic solvent include methylformamide, dimethylacetamide, dimethylsulfoxide, and the like.
When X in the bisphenol type epoxy resin represented by the general formula (A-2) is a hydrogen atom, the production method of the bisphenol type epoxy resin represented by the general formula (A-2) is not particularly limited. However, it can be appropriately selected from known methods, for example, a method of producing from bisphenol and epichlorohydrin.
However, in said general formula (6), R represents either a hydrogen atom or a methyl group, and n represents an integer greater than or equal to 1.

Examples of the salicylaldehyde type epoxy resin represented by the general formula (A-3) include a polycondensate of cresol and salicylaldehyde.
A commercial item can be used as a salicylaldehyde type | mold epoxy resin represented by the said general formula (A-3). Examples of the commercial products include F 日本 E-2500, EPPN-501H, and EPPN-502H manufactured by Nippon Kayaku Co., Ltd.

  Examples of the vinyl group-containing monocarboxylic acid include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid, And half ester compounds. These may be used individually by 1 type and may use 2 or more types together.

Examples of the half-ester compound include a reaction product of a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride.
As a method for producing the half ester compound, for example, any one of a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether, and a vinyl group-containing monoglycidyl ester and a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. The method of making it react is mentioned.

  Examples of the hydroxyl group-containing acrylate, the vinyl group-containing monoglycidyl ether, and the vinyl group-containing monoglycidyl ester include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, Polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, group Glycidyl methacrylate, and the like.

  Examples of the saturated or unsaturated dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Examples include methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like.

  The reaction amount of the vinyl group-containing monocarboxylic acid in the reaction between the epoxy resin and the vinyl group-containing monocarboxylic acid is, for example, 0.8 to 1.05 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. Is preferable, and 0.9-1.0 equivalent is more preferable. When the reaction amount is less than 0.8 equivalent, the introduction rate of the vinyl group may decrease, and when it is 1.05 equivalent, the vinyl group-containing monocarboxylic acid remains and the peelability decreases. There is.

The epoxy resin and the vinyl group-containing monocarboxylic acid are preferably dissolved in an organic solvent and reacted.
Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, esters, aliphatic hydrocarbons, petroleum solvents, and the like.
Examples of the ketones include ethyl methyl ketone and cyclohexanone.
Examples of the aromatic hydrocarbons include toluene, xylene, tetramethylbenzene, and the like.
Examples of the glycol ethers include methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, and the like. It is done.
Examples of the esters include ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and the like.
Examples of the aliphatic hydrocarbons include octane and decane.
Examples of the petroleum solvent include petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

The epoxy resin and the vinyl group-containing monocarboxylic acid are preferably reacted using a catalyst.
Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like.
As the usage-amount of the said catalyst, 0.1-10 mass parts is preferable with respect to the total amount (100 mass parts) of the said epoxy resin and the said vinyl group containing monocarboxylic acid.

The epoxy resin and the vinyl group-containing monocarboxylic acid are preferably reacted using a polymerization inhibitor. The polymerization inhibitor can prevent polymerization during the reaction between the epoxy resin and the vinyl group-containing monocarboxylic acid.
Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like.
As the usage-amount of the said polymerization inhibitor, 0.01-1 mass part is preferable with respect to the total amount (100 mass parts) of the said epoxy resin and the said vinyl group containing monocarboxylic acid.
The reaction temperature between the epoxy resin and the vinyl group-containing monocarboxylic acid when the polymerization inhibitor is used is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

Examples of the epoxy resin containing an acid-modified vinyl group include, for example, a reaction product of the epoxy resin and the vinyl group-containing monocarboxylic acid, and a polybasic acid further containing either a saturated group or an unsaturated group. Examples thereof include an epoxy resin obtained by reacting an anhydride.
Specifically, a hydroxyl group is formed by an addition reaction between the epoxy group of the epoxy resin and a carboxyl group of the vinyl group-containing monocarboxylic acid, and then a hydroxyl group formed by the addition reaction (originally in the epoxy resin). And those obtained by a half ester reaction between an acid anhydride group of a polybasic acid anhydride containing one of the saturated group and the unsaturated group.

  Examples of the polybasic acid anhydride containing any one of the saturated group and the unsaturated group include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Examples include acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like.

A reaction amount of the polybasic acid anhydride containing either the saturated group or the unsaturated group in the reaction between the reaction product and the polybasic acid anhydride containing either the saturated group or the unsaturated group. As, for example, it is preferable that it is 0.1-1.0 equivalent with respect to 1 equivalent of hydroxyl groups in the said reaction product. When the reaction amount is in the range of 0.1 to 1.0 equivalent, the acid value of the epoxy resin containing the acid-modified vinyl group can be adjusted.
The acid value of the epoxy resin containing the acid-modified vinyl group is preferably, for example, 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the photosensitive resin composition in a dilute alkali solution may be reduced. When the acid value exceeds 150 mgKOH / g, the curing made of the photosensitive resin composition may occur. The electrical properties of the film may be degraded.
There is no restriction | limiting in particular as the measuring method of the said acid value, It can select suitably from well-known methods, For example, the titration method etc. are mentioned.
The reaction temperature between the reaction product and the polybasic acid anhydride containing any one of the saturated group and the unsaturated group is preferably 60 to 120 ° C.

The epoxy resin containing the acid-modified vinyl group is preferably used in combination with a flexible elastomer, if necessary.
The epoxy resin containing an acid-modified vinyl group undergoes a crosslinking reaction (curing reaction) by ultraviolet light or heat, and cures and contracts, causing distortion (internal stress) inside the resin, resulting in flexibility and adhesiveness. However, when the elastomer is used in combination, the stress of the cured film of the epoxy resin containing the acid-modified vinyl group can be relieved and the cured coating film can be modified. Furthermore, by using the above elastomer together with the epoxy resin containing the acid-modified vinyl group and polymer-alloying, the cured shrinkage and flexibility of the cured film are modified, and the elastic modulus can be reduced to 1 to 100 MPa. Further, the shear adhesiveness with the sealing material can be improved. If the elastic modulus is less than 1 MPa, the mechanical strength may decrease, and if it exceeds 100 MPa, the shear adhesive force may decrease.
The elastic modulus is a value obtained by measuring dynamic viscoelasticity in a temperature range of 200 to 220 ° C., which is a temperature during reflow.
Examples of the elastomer include styrene butadiene rubber.

In the method for producing an epoxy resin containing an acid-modified vinyl group, the vinyl group-containing monocarboxylic acid can be used in combination with a polybasic acid anhydride as necessary.
Examples of the polybasic acid anhydride include trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydride, and the like.

  In the method for producing an epoxy resin containing an acid-modified vinyl group, the epoxy resin can be used in combination with a hydrogenated bisphenol A type epoxy resin, if necessary.

  The solid content of the epoxy resin containing the acid-modified vinyl group is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total solid content of the photosensitive resin composition. -60 mass% is particularly preferred. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 80% by mass, the exposure sensitivity is increased. May decrease.

-Other binders-
Examples of the other binder include styrene maleic resins such as hydroxyethyl acrylate modified products of styrene-maleic anhydride copolymers, hydroxyethyl methacrylate modified products of styrene-maleic anhydride copolymers, and the like.
As solid content of the said other binder, 5-30 mass% is preferable with respect to the solid content whole quantity of the said photosensitive resin composition.

<Photopolymerization initiator>
The said photoinitiator contains the compound represented by following General formula (1), and contains another photopolymerizable initiator as needed.

-Compound represented by the general formula (1)-
When the photopolymerization initiator contains a photopolymerization initiator represented by the following general formula (1), it is possible to improve the curing sensitivity and the cured film strength.
In general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents an alkyl group, and R ³ represents a naphthyl group. R ¹ , R ² , and R ³ may be further substituted with a substituent.

As a photoinitiator represented by the said General formula (1), it is preferable that it is a photoinitiator represented by either the following general formula (2) and (3), for example.
When the photopolymerization initiator represented by the general formula (1) is a photopolymerization initiator represented by any one of the following general formulas (2) and (3), the curing sensitivity can be further improved. it can.
However, in general formula (2) and (3), R < ¹ > represents either an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > represents an alkyl group. R ¹ and R ² may be further substituted with a substituent.

In the general formulas (1), (2), and (3), examples of the acyl group for R ¹ include aliphatic, aromatic, and heterocyclic rings.
The acyl group may be further substituted with a substituent. Examples of the substituent include an alkoxy group, an aryloxy group, and a halogen atom.
As a total carbon number of the said acyl group, 2-30 are preferable, for example, 2-20 are more preferable, and 2-16 are especially preferable.
Specific examples of the acyl group include, for example, acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzyl Carbonyl group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, furanoyl group Thiophenoyl group, methacryloyl group, acryloyl group, and the like.

In the general formulas (1), (2), and (3), the total number of carbon atoms of the alkoxycarbonyl group in R ¹ is preferably 2 to 30, more preferably 2 to 20, and particularly preferably 2 to 16.
The alkoxycarbonyl group may be further substituted with a substituent.
Specific examples of the alkoxycarbonyl group include, for example, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl Group, and the like.

In the general formulas (1), (2) and (3), the total carbon number of the aryloxycarbonyl group in R ¹ is preferably 7 to 30, more preferably 7 to 20, and particularly preferably 7 to 16.
The aryloxycarbonyl group may be further substituted with a substituent.
Specific examples of the aryloxycarbonyl group include, for example, phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl. Group, paracyanophenoxycarbonyl group, and the like.

In the general formulas (1), (2) and (3), specific examples of the alkyl group in R ² include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and s-butyl group, n-heptyl group, and benzyl group.
The alkyl group may be further substituted with a substituent. Examples of the substituent include an alkoxy group, an aryloxy group, and a halogen atom.
Specific examples of the alkyl group further substituted with the substituent include, for example, an alkoxymethyl group, a phenoxymethyl group, a chloromethyl group, and the like.

  The solid content of the compound represented by the general formula (1) is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition, and is 0.5 to 7% by mass. % Is more preferable. If the content is less than 0.1% by mass, satisfactory curing sensitivity cannot be obtained, and if it exceeds 10% by mass, the cured film may become brittle.

-Other photopolymerization initiators-
The photopolymerization initiator can include other photopolymerization initiators other than the photopolymerization initiator represented by the general formula (1).
Examples of the other photopolymerization initiators include camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, α-hydroxycycloalkyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, dialkoxy. Acetophenone, α-hydroxy- or α-amino-acetophenone, (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4-aroyl- 1,3-dioxolane, benzoin alkyl ethers and benzyl ketals (eg dimethylbenzyl ketal), phenylglyoxal esters and derivatives thereof, dimeric phenylglyoxal esters, diacetyl Peresters (for example, benzophenone tetracarboxylic acid peresters described in, for example, European Patent 126,541), monoacylphosphine oxides (for example, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, bisacylphosphine Oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxide), halomethyltriazine (eg, 2- [2- (4-methoxyphenyl) vinyl] -4,6-bistrichloromethyl [1,3 , 5] triazine, 2 (4-methoxyphenyl) -4,6-bistrichloromethyl [1,3,5] triazine, 2- (3,4-dimethoxyphenyl) -4,6-bistrichloromethyl [1,3,5] triazine, 2-methyl-4,6-bistrichloromethyl [1,3,5] triazine, 2- (4-N, N-di (ethoxycarbonylmethylaminophenyl) -4,6-bis (trichloromethyl) [1, 3,5] triazine, 2- (4-methoxynaphthyl) -4,6-bistrichloromethyl [1,3,5] triazine, 2- (1,3-benzodioxol-5-yl) -4,6-bis Trichloromethyl [1,3,5] triazine, 2- [2- [4- (pentyloxy) phenyl] ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- ( 3- Methyl-2-furanyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (5-methyl-2-furanyl) ethenyl] -4,6-bistrichloromethyl [ 1,3,5] triazine, 2- [2- (2,4-dimethoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (2-methoxyphenyl) ) Ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (4-isopropyloxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine 2- [2- (3-chloro-4-methoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2-bromo-4-N, N-di ( Ethoxycal Nylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2-chloro-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6-bis Trichloromethyl [1,3,5] triazine, 2- [3-bromo-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [3-Chloro-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine), other halomethyltriazines (for example, G.I. Buhr, R.A. Dammel and C.D. Lindley, Polym. Mater. Sci. Eng. 61,269 (1989), and compounds described in European Patent No. 022788), halomethyloxazole photoinitiators (eg, US Pat. Nos. 4,371,606 and 4,371,607). ), 1,2-disulfone hexaarylbisimidazole, and hexaarylbisimidazole (for example, compounds described in EA Bartmann, Synthesis 5,490 (1993)), coinitiators O-chlorohexaphenyl-bisimidazole in combination with systems (eg 2-mercaptobenzthiazole, ferrocenium compounds), titanocene (eg bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyrylphenyl) titanium) And a mixture thereof.

  The solid content of the photopolymerization initiator (the compound represented by the general formula (1) and other photopolymerization initiators) is preferably 0.1 to 10% by mass in the photosensitive resin composition, 0.5-7 mass% is more preferable, and 1-5 mass% is especially preferable.

<Polymerizable compound>
The polymerizable compound is a photosensitive compound used to improve the workability by adjusting the viscosity of the photosensitive resin composition, increase the crosslinking density, and obtain a coating film having adhesion and the like.
The polymerizable compound preferably has one or more unsaturated double bonds in one molecule, and is preferably a liquid photosensitive compound. When the polymerizable compound has one or more unsaturated double bonds in one molecule and is a liquid photosensitive compound, the curing sensitivity and the strength of the cured film may be improved.
The liquid photosensitive compound represents a compound having a viscosity of 3000 mpa or less at room temperature.
There is no restriction | limiting in particular as a measuring method of the said viscosity, Although it can select suitably from well-known things, For example, the measuring method by a viscometer etc. are mentioned.

  Examples of the polymerizable compound include a compound obtained by adding an α, β-unsaturated carboxylic acid to a polyhydric alcohol, a compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound, Other polyfunctional monomers are exemplified.

  Examples of the compound obtained by adding an α, β-unsaturated carboxylic acid to the polyhydric alcohol include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene. Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) Examples thereof include acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  Examples of the compound obtained by adding an α, β-unsaturated carboxylic acid to the glycidyl group-containing compound include ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, and trimethylolpropane. Examples thereof include triglycidyl ether triacrylate, bisphenol A glycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and glycerin polyglycidyl ether poly (meth) acrylate.

Examples of the other polyfunctional monomers include 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis- (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, and the like.
These may be used alone or in combination of two or more.

The polymerizable compound may be used in combination with the monofunctional monomer.
Examples of the monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2 -(Meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, half of phthalic acid derivative ( And (meth) acrylate, N-methylol (meth) acrylamide, and the like.

  The solid content of the polymerizable compound is preferably 2 to 50% by mass and more preferably 10 to 40% by mass with respect to the total solid content of the acid-modified vinyl group-containing epoxy resin. If the solid content is less than 2% by mass, the coating film may be poorly cured, the flexibility may be lowered, and the development speed may be delayed. If it exceeds 50% by mass, cold flow may occur. The peeling speed of the cured resist may be reduced.

<Thermal crosslinking agent>
The thermal crosslinking agent includes at least an epoxy compound having two or more epoxy groups in one molecule, and includes other thermal crosslinking agent as necessary.
When the thermal crosslinking agent contains an epoxy compound having two or more epoxy groups in one molecule, plating resistance can be improved.

-Epoxy compound having two or more epoxy groups in the molecule-
Examples of the epoxy compound having two or more epoxy groups in one molecule include a bixylenol-type or biphenol-type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, an isocyanurate skeleton, and the like. Heterocyclic epoxy resins (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated Bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, brominated fluorine resin) Nord novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP -7200H; manufactured by Dainippon Ink and Chemicals, Ltd.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (phthalic acid diglycidyl ester, Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4-epoxy) Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. ), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (Naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP 4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), a reaction between a phenol compound and a polyphenol compound obtained by an addition reaction of a diolefin compound such as divinylbenzene or dicyclopentadiene with epichlorohydrin , Epoxidized ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid, etc., epoxy resin having linear phosphorus structure, epoxy resin having cyclic phosphorus structure, α-methylstilbene type liquid crystal Epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resins, bis (glycidyloxyphenyl) adamantane type epoxy resins, and the like. It is done. The said epoxy compound used for this invention is not restricted to these. These may be used alone or in combination of two or more.

  The solid content of the epoxy compound having two or more epoxy groups in one molecule is preferably 1 to 40% by mass with respect to the total solid content of the photosensitive resin composition, and is preferably 5 to 30% by mass. % Is more preferable. When the content is less than 1% by mass, sufficient plating resistance cannot be obtained, and when it exceeds 40% by mass, development failure may occur.

-Other thermal crosslinking agents-
There is no restriction | limiting in particular as another thermal crosslinking agent, According to the objective, it can select suitably, For example, the epoxy compound which has two or more epoxy groups which have an alkyl group in beta-position, at least 2 in 1 molecule And an oxetane compound having an oxetanyl group.

--Epoxy compound having two or more epoxy groups having an alkyl group at the β-position--
As the epoxy group having an alkyl group at the β-position, for example, a β-alkyl-substituted glycidyl group is preferable.
As the epoxy compound having two or more epoxy groups having an alkyl group at the β-position, for example, all of the two or more epoxy groups may be β-alkyl-substituted glycidyl groups, and at least one epoxy group is β -Alkyl substituted glycidyl group may be sufficient.

The proportion of β-alkyl-substituted glycidyl groups in all epoxy groups in the epoxy compound having two or more epoxy groups having an alkyl group at the β-position is, for example, preferably 30% or more and 40% or more. Is more preferable, and 50% or more is particularly preferable. When the ratio of the β-alkyl-substituted glycidyl group is 30% or more, storage stability at room temperature may be excellent.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected from known ones. For example, β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butyl And a glycidyl group. Among these, a β-methylglycidyl group is preferable from the viewpoint of improving the storage stability of the photosensitive resin composition and the viewpoint of ease of synthesis.

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

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

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

Examples of the epoxy compound containing two or more epoxy groups having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as alkyl glycidyl ethers; di-β-alkyl glycidyl ethers of biphenol compounds such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol A β-alkyl glycidyl ether of a naphthol compound such as a di-β-alkyl glycidyl ether of dihydroxynaphthalene or a di-β-alkyl glycidyl ether of binaphthol; a phenol-formaldehyde polycondensate Poly-β-alkyl glycidyl ethers; poly-β-alkyl glycidyl ethers of monoalkyl substituted phenol-formaldehyde polycondensates of 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ethers of cresol-formaldehyde polycondensates; xylenol -C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of formaldehyde polycondensate; poly-β- of bisphenol A-formaldehyde polycondensate Bisphenol compounds such as alkyl glycidyl ether-poly-β-alkyl glycidyl ether of formaldehyde polycondensate; poly-β-alkyl glycidyl ether of polyaddition product of phenol compound and divinylbenzene; Can be mentioned.
Among these, a bisphenol compound represented by the following structural formula (iii), a β-alkyl glycidyl ether derived from a polymer obtained from this and epichlorohydrin, and the following structural formula (iv) Phenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether is preferred.
However, in said structural formula (iii), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
In the Structural Formula (iv), R represents any of an alkyl group having 1 to 6 carbon hydrogen and carbon, R "represents either hydrogen atoms, and CH _3, n is from 0 to 20 Represents an integer.

  These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more.

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

--Oxetane compound having at least two oxetanyl groups in the molecule--
Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, and compounds having an oxetane group , Novolac resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds such as silsesquioxane and other hydroxyl-containing resins, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

  Further, the epoxy compound (the epoxy compound having two or more epoxy groups in one molecule and the epoxy compound having two or more epoxy groups having an alkyl group at the β-position) or the oxetane compound is accelerated. Thus, for example, amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N- Dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, imidazole, 2-methyl) Imidazole, 2-ethyl Midazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus Compounds (for example, triphenylphosphine), guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid Additives etc.) wear. These may be used individually by 1 type and may use 2 or more types together.

  There is no particular limitation as long as it can accelerate the reaction between the epoxy resin compound and the oxetane compound, or the reaction of these with a carboxyl group, and compounds other than those described above that can promote thermal curing can be used. Good.

  The solid content of the epoxy compound having two or more epoxy groups having an alkyl group at the β-position, the oxetane compound, and a compound capable of accelerating thermal curing between these and the carboxylic acid is the total content of the photosensitive resin composition. It is preferable that it is 0.01-15 mass% with respect to solid content.

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

Furthermore, for the purpose of improving the storage stability of the photosensitive film of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec). -Butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, Methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, a melamine derivative can be used as said other thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  As the solid content of the thermal crosslinking agent (the epoxy compound having two or more epoxy groups in one molecule and the other thermal crosslinking agent) in the total amount, with respect to the total solid content of the photosensitive resin composition, 1-50 mass% is preferable and 3-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, the developability and the exposure sensitivity may be lowered.

<Other ingredients>
Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, dyes (pigments and discoloring agents), adhesion imparting agents, antioxidants, solvents, surface tension modifiers, stabilizers, and chains. Examples thereof include additives such as a transfer agent, an antifoaming agent, an inorganic filler, and an organic filler.

-Sensitizer-
The sensitizer is used in combination when the photosensitive layer is exposed and developed to improve the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferred.
The sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.).
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of
The sensitizer is preferably an aromatic compound, for example. Specifically, benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, coumarin and derivatives thereof, phenothiazine and derivatives thereof, 3- (aroylmethylene) thiazoline, rhodanine, camphorquinone, eosin, rhodamine, erythrosine, Xanthene, thioxanthene, acridine (for example, 9-phenylacridine), 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, cyanine, merocyanine dye, other compounds, etc. Can be mentioned.

  Examples of the thioxanthone include thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxy. Carbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3- (2-methoxyethoxycarbonyl) thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl- 3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl Bonyl-3-phenylsulfylthioxanthone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonyl] thioxanthone, 1,3-dimethyl-2-hydroxy-9H-thioxanthen-9-one 2-ethylhexyl ether 1-ethoxycarbonyl-3- (1-methyl-1-morpholinoethyl) thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6- (1,1-dimethoxybenzyl) thioxanthone, 2-morpholinomethyl Thioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N- (1,1,3,3-tetra Methylbutyl) thioxanthone-3,4 Dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylic acid polyethylene glycol ester, 2-hydroxy-3- (3,4- Dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, and the like.

  Examples of the benzophenone include benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bis ( Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (methylethylamino) benzophenone, 4,4′-bis (p-isopropylphenoxy) benzophenone, 4-methylbenzophenone, 2, 4,6-trimethylbenzophenone, 4- (4-methylthiophenyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate, 4- (2-hydroxyethylthio) benzophenone, 4- 4-Tolylthio) benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (toluene-4-sulfonyl) propan-1-one, 4-benzoyl-N, N, N- Trimethylbenzenemethananium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanaminium chloride monohydrate, 4- (13-acryloyl-1,4, 7,10,13-pentaoxatridecyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethylbenzenemethananium chloride, and the like.

  Examples of the coumarin include coumarin 1, coumarin 2, coumarin 6, coumarin 7, coumarin 30, coumarin 102, coumarin 106, coumarin 138, coumarin 152, coumarin 153, coumarin 307, coumarin 314, coumarin 314T, coumarin 334, coumarin. 337, coumarin 500, 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-dipropoxycoumarin, 3-benzoyl-6,8- Dichlorocoumarin, 3-benzoyl-6-chlorocoumarin, 3,3′-carbonyl-bis [5,7-di (propoxy) coumarin], 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-iso Butyroylcoumarin, 3-benzoyl- , 7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di (methoxyethoxy) coumarin, 3-benzoyl-5 , 7-di (allyloxy) coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3- (1-naphthoyl) ) Coumarin, 5,7-diethoxy-3- (1-naphthoyl) coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3- (4-cyanobenzoyl) -5,7- Dimethoxycoumarin, 3- (4-cyanobenzoyl) -5,7-dipropoxycoumarin, 7- Methylamino-3-phenylcoumarin, 7-diethylamino-3-phenylcoumarin, coumarin derivatives disclosed in JP-A-9-179,299 and 9-325,209 (for example, 7-[{4-chloro- 6- (diethylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin), and the like.

  Examples of the 3- (aroylmethylene) thiazoline include 3-methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β. -Naphthiazoline and the like.

  Examples of the rhodanine include 4-dimethylaminobenzalrhodanine, 4-diethylaminobenzalrhodanine, 3-ethyl-5- (3-octyl-2-benzothiazolinylidene) rhodanine, and JP-A-8-305. , 019, rhodanine derivatives represented by any of the formulas [1], [2], and [7].

Examples of the other compounds include acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 4,4′-bis (dimethylamino) benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, dansylic acid derivative, 9 , 10-anthraquinone, anthracene, pyrene, aminopyrene, perylene, phenatrene, phentolenquinone, 9-fluorenone, dibenzosuberone, curcumin, xanthone, thiomichler ketone, α- (4-dimethylaminobenzylidene) ketone, 2,5 -Bis (4-diethylaminobenzylidenecyclopentanone, 2- (4-dimethylaminobenzylidene) indan-1-one, 3- (4-dimethylaminophenyl) -1-indan-5-ylpropenone, 3-phenylthiophthal N-methyl-3,5-di (ethylthio) phthalimide, N-methyl-3,5-di (ethylthio) phthalimide, phenothiazine, methylphenothiazine, amine, N-phenylglycine, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid butoxyethyl, 4-dimethylaminoacetophenone, triethanolamine, methyldiethanolamine, dimethylaminoethanol, 2- (dimethylamino) ethylbenzoate, poly (propylene glycol) -4- (dimethylamino) benzoate , Etc.
The said sensitizer may be used individually by 1 type and may use 2 or more types together.

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

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the photosensitive resin composition.
Specific examples of the thermal polymerization inhibitor include, for example, the thermal polymerization inhibitor described in paragraph “0316” of the specification of JP-A-2005-258431.
The solid content of the thermal polymerization inhibitor is preferably 0.001 to 5 mass% with respect to the total solid content of the photosensitive resin composition. When the solid content is less than 0.001% by mass, stability during storage may be lowered, and when it is 5% by mass or more, sensitivity may be lowered.

-Plasticizer-
The plasticizer is added to control film physical properties.
Specific examples of the plasticizer include plasticizers described in paragraphs “0318” to “0319” of the specification of JP-A-2005-258431.
As solid content of the said plasticizer, 0.1-50 mass% is preferable with respect to the said photosensitive resin composition total solid. When the solid content is less than 0.1% by mass, the cured film may be fragile, and when it is 5% by mass or more, the film strength may be reduced.

-Dye-
Examples of the pigment include dyes described in paragraph “0323” of the specification of JP-A-2005-258431.
As solid content of the said pigment | dye, 0.01-10 mass% is preferable with respect to the said photosensitive resin composition total solid. When the solid content is less than 0.1% by mass, coloring is weak, and when it is 10% by mass or more, coloring may be too dark.

-Discoloring agent-
The said color change agent is added in the photosensitive resin composition so that a visible image can be given by exposure.
Examples of the color changing agent include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4′-biphenyldiamine, o-chloroaniline, in addition to the dye. Examples include leuco crystal violet, leucomalachite green, leucoaniline, and leucomethyl violet.
As solid content of the said color change agent, 0.001-10 mass% is preferable with respect to the said photosensitive resin composition total solid. If the solid content is less than 0.001% by mass, the effect may not be sufficiently exhibited, and if it is 10% by mass or more, the curing sensitivity may be affected.

-Adhesion promoter-
Examples of the adhesion promoter include adhesion promoters described in paragraph “0326” of the specification of JP-A-2005-258431.
As solid content of the said adhesion promoter, 0.001-20 mass% is preferable with respect to the said photosensitive resin composition total solid. If the solid content is less than 0.001% by mass, the effect may not be sufficiently exhibited, and if it is 10% by mass or more, developability may be affected.

-Inorganic filler-
By adding the inorganic filler, the cured film strength can be improved.
Examples of the inorganic filler include barium sulfate, titanium oxide, and silica gel.
As solid content of the said inorganic filler, 1-50 mass% is preferable with respect to the said photosensitive resin composition total solid. If the solid content is less than 1% by mass, the effect may not be sufficiently exhibited, and if it is 50% by mass or more, the curing sensitivity and developability may be affected.

-Organic filler-
By adding the organic filler, the cured film strength can be improved.
Examples of the organic filler include anthracene and perylene.
As solid content of the said organic filler, 1-50 mass% is preferable with respect to the said photosensitive resin composition total solid. If the solid content is less than 1% by mass, the effect may not be sufficiently exhibited, and if it is 50% by mass or more, the curing sensitivity and developability may be affected.

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer made of the photosensitive resin composition of the present invention formed on the support, and optionally has other layers as necessary. It is preferable.

  The said photosensitive film is used for the permanent pattern formation method mentioned later, This permanent pattern formation method is performed by laminating | stacking the photosensitive layer of the said photosensitive film on a base material.

Further, in the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is preferably 100 mJ / cm ² or less. .
In the case of exposing and developing the photosensitive layer, the minimum energy of light that does not change the thickness of the exposed portion of the photosensitive layer before and after the exposure and development is particularly limited as long as it is 100 mJ / cm ² or less. rather, may be appropriately selected depending on the intended purpose, for example, preferably 0.1~80mJ / cm ^2, more preferably 0.5~70mJ / cm ^2, more preferably 1~50mJ / cm ^2, 1 5-30 mJ / cm ² is particularly preferable.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 100 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

Here, “the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development” is so-called development sensitivity, for example, when the photosensitive layer is exposed. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure and the thickness of the cured layer generated by the development process following the exposure.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
The method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the purpose. (Manufactured by Tokyo Seimitsu Co., Ltd.)).

In the photosensitive film of the present invention, a sample cut into a width of 4.5 cm and a length of 8 cm is fixed on a pedestal so that the support is on the surface side, and the support is pulled from the sample at a speed of 160 cm / min. The peeling force between the photosensitive layer and the support when peeled in the length direction is preferably 500 g or less, more preferably 1 to 300 g, and more preferably 1 to 50 g per 4.5 cm length of the sample. Is particularly preferred.
When the peeling force between the photosensitive layer and the support is more than 500 g, the peelability between the photosensitive layer and the support is inferior, and the tackiness of the surface of the photosensitive layer may increase, and is less than 1 g. The protective film and the support may be peeled off during storage of the photosensitive film.

<Photosensitive layer>
The photosensitive layer in the photosensitive film is formed of the photosensitive resin composition of the present invention.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body.
The photosensitive layer can be formed by applying the photosensitive resin composition of the present invention on a support described later and drying. A detailed description of the method for forming the photosensitive layer will be described in the description of the method for producing a photosensitive film described later.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable. The support may be a single layer or may have a multilayer structure.

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

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

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

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

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Method for producing photosensitive laminate]
As a manufacturing method of the said photosensitive laminated body, the method of apply | coating the said photosensitive resin composition to the surface of the said base | substrate and drying is mentioned as a 1st aspect, In the photosensitive film of this invention as a 2nd aspect. Examples include a method of transferring and laminating at least one of the photosensitive layer while performing at least one of heating and pressurization.

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

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

In the method for producing a photosensitive laminate according to the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the 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 any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

  Since the photosensitive film of the present invention and the photosensitive laminate use the photosensitive resin composition of the present invention, it has excellent characteristics such as pattern formability, plating resistance, and peelability, high sensitivity, and resolution. Is good, and it is possible to form a pattern with high definition, for forming various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, It can be suitably used for the production of liquid crystal structural members such as barrier ribs, pattern formation for holograms, micromachines, proofs, etc., and particularly suitable for the permanent pattern formation of printed wiring boards.

  In particular, since the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned, the high acceleration test is performed. In (HAST), there is no occurrence of ion migration and a high-definition permanent pattern is obtained, so that the lamination to the substrate is performed more finely.

(Permanent pattern forming method, permanent pattern, and printed wiring board)
The permanent pattern forming method of the present invention preferably includes at least an exposure step and further includes other steps such as a development step and a curing treatment step.
The permanent pattern and printed wiring board of the present invention are obtained by the permanent pattern forming method of the present invention.
Hereinafter, the details of the permanent pattern and the printed wiring board of the present invention will be clarified through the description of the method for forming a permanent pattern of the present invention.

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

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

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

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is used. For example, the photosensitive layer is arranged in a two-dimensional array of n (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means and the light irradiation means. An exposure head provided with a light modulation unit capable of controlling the drawing unit according to pattern information, wherein the column direction of the drawing unit is relative to the scanning direction of the exposure head. An exposure head arranged so as to form a predetermined set inclination angle θ is used, and the exposure head is subjected to N double exposure (where N is 2) among the usable pixel parts by the use pixel part specifying means. The natural number above) Designate the element part, and control the element part for the exposure head so that only the element part specified by the element part for specifying the used element part is involved in the exposure by the element part controlling unit. A method is preferred in which the exposure head is moved relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit. Refers to a sequence of Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms. Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Further, in the following description, “N multiple drawing” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is 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 flat bed type exposure apparatus is used. As shown in FIG. The plate-shaped moving stage 14 is provided that adsorbs and holds the photosensitive layer 12 on the surface. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The pattern forming apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is provided at the center of the installation base 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is provided on one side across the gate 22, and a plurality of (for example, two) sensors 26 that detect the front and rear ends of the photosensitive material 12 are provided on the other side. The scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14. The scanner 24 and the sensor 26 are connected to a controller (not shown) that controls them.

  Here, for explanation, an X axis and a Y axis orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.

  A slit formed in a “<” shape that opens in the direction of the X-axis at the upstream edge (hereinafter sometimes simply referred to as “upstream”) along the scanning direction of the stage 14. 10 are formed at equal intervals. Each slit 28 includes a slit 28 a located on the upstream side and a slit 28 b located on the downstream side. The slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of −45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.

  The position of the slit 28 is substantially coincident with the center of the exposure head 30. In addition, the size of each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30. Further, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34. In this case, the size of each slit 28 is set so as to sufficiently cover the width of the overlapping portion between the exposed regions 34.

  In the position below each slit 28 inside the stage 14, single cell type light detection as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part designation process described later. A vessel (not shown) is incorporated. In addition, each photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in the used pixel part specifying process described later.

  The operation form of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while constantly moving the exposure head, or each movement destination position while the exposure head is moved stepwise. The exposure head may be stationary to perform the exposure operation.

<< Exposure head >>
Each exposure head 30 is connected to the scanner 24 so that each pixel portion (micromirror) row direction of an internal digital micromirror device (DMD) 36 described later forms a predetermined set inclination angle θ with the scanning direction. It is attached. For this reason, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed in the photosensitive layer 12 for each exposure head 30. In the example shown in FIGS. 2 and 3B, the scanner 24 includes ten exposure heads arranged in a substantially matrix of 2 rows and 5 columns.
In the following description, when the individual exposure heads arranged in the mth row and the nth column are indicated, the exposure head 30 _mn is indicated, and exposure by the individual exposure heads arranged in the mth row and the nth column is performed. When an area is indicated, it is expressed as an exposure area 32 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads 30 in each row arranged in a line so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34 is In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice in this embodiment). Therefore, can not be exposed portion between the exposure area _{32 11} in the first row and the exposure area _{32 12,} it can be exposed by the second row of the exposure area _{32 21.}

  As shown in FIGS. 4, 5A, and 5B, each of the exposure heads 30 includes a light modulation unit that modulates incident light for each pixel part according to image data (spatial light that modulates each pixel part). As a modulation element, a DMD 36 (manufactured by Texas Instruments Inc., USA) is provided. The DMD 36 is connected to a controller serving as a pixel part control unit including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the use area on the DMD 36 for each exposure head 30 based on the input image data. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.

  As shown in FIG. 4, on the light incident side of the DMD 36, there is provided a laser emitting portion in which the emission end portion (light emitting point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32. A fiber array light source 38, a lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and a mirror 42 for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 Arranged in order. In FIG. 4, the lens system 40 is schematically shown.

  As shown in detail in FIGS. 5A and 5B, the lens system 40 includes a pair of combination lenses 44 that convert the laser light emitted from the fiber array light source 38 into parallel light, and a light quantity distribution of the parallel laser light. A pair of combination lenses 46 that are corrected so as to be uniform, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36 are configured.

  Further, on the light reflection side of the DMD 36, a lens system 50 that images the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed. The lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.

  In the present embodiment, the laser light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is reduced to about 5 μm by the lens system 50. Is set to

-Light modulation means-
The light modulating means has n (where n is a natural number of 2 or more) two-dimensionally arranged image elements, and can control the image elements according to the pattern information. If it is, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, a spatial light modulation element is preferable.

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

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

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 6, the DMD 36 is a mirror device in which a large number of micromirrors 58 are arranged in a lattice pattern on a SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). . In this embodiment, a DMD 36 in which 1024 columns × 768 rows of micromirrors 58 are arranged is used. Among these, the micromirrors 58 that can be driven by a controller connected to the DMD 36, that is, usable micromirrors 58 are 1024 columns × 256 rows. Suppose only. The data processing speed of the DMD 36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors to be used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (integrated).

  When an image signal representing the density of each point constituting a desired two-dimensional pattern in binary is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the column is centered on the diagonal line. As shown in FIG. 1, the inclination is inclined to ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed. FIG. 7A shows a state in which the micromirror 58 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 58 is tilted to −α degrees in the off state. In this way, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 as shown in FIG. 6 in accordance with the image signal, the laser light B incident on the DMD 36 moves in the inclination direction of each micromirror 58. Reflected.

  FIG. 6 shows an example in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + α degrees or α degrees. The on / off control of each micromirror 58 is performed by the controller connected to the DMD 36. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

-Light irradiation means-
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beam, X-ray, laser beam, and the like are mentioned. Of these, laser beam is preferable, and a laser combining two or more lights (hereinafter, referred to as “combined laser”). More preferred. Even when light irradiation is performed after the support is peeled off, the same light can be used.

The wavelength of ultraviolet to visible light is preferably, for example, 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.
For example, the wavelength of the laser beam is preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 400 to 450 nm.

  Examples of means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and collective optics for condensing the laser beams respectively emitted from the plurality of lasers and coupling them to the multimode optical fiber. Means having a system are preferred.

  Hereinafter, examples of the means (fiber array light source) capable of irradiating the combined laser include the methods described in paragraphs “0109” to “0146” of the specification of JP-A-2005-258431.

<< Used pixel part designation means >>
The used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot on a surface to be exposed as a pixel unit, and N-fold exposure based on a detection result by the light spot position detecting means. It is preferable to include at least a pixel part selection unit that selects a pixel part to be used for the realization.
Hereinafter, an example of a method for designating a pixel part used for N-exposure by the used pixel part designation unit will be described.

(1) Method for Specifying Picture Element Portions Used in Single Exposure Head In the present embodiment (1), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and each exposure head 30. A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the mounting angle error and realizing ideal double exposure.

The set inclination angle θ in the column direction of the image element (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 and the like. It is assumed that an angle slightly larger than the angle θ _ideal, which is a double exposure using 256 lines of pixel parts, is adopted.
This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 degrees according to Equation 3. Therefore, for example, an angle of about 0.50 degrees may be adopted as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

  FIG. 10 illustrates an example of unevenness in a pattern on an exposed surface due to the influence of an attachment angle error of one exposure head 30 and pattern distortion in the pattern forming apparatus 10 that is initially adjusted as described above. FIG. In the following drawings and description, the light spot in the m-th row is represented by r (m) with respect to the light spot generated by each pixel part (micromirror) and constituting the exposure area on the exposed surface. ), The light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

The upper part of FIG. 10 shows a pattern of light spot groups from the usable micromirrors 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is the upper part. 2 shows the state of the exposure pattern formed on the surface to be exposed when the stage 14 is moved and continuous exposure is performed in the state where the pattern of light spots as shown in FIG.
In FIG. 10, for convenience of explanation, the exposure pattern of the odd-numbered columns of the usable micromirrors 58 and the exposure pattern of the even-numbered columns are shown separately. However, the actual exposure patterns on the exposed surface are shown in FIG. Two exposure patterns are superimposed.

In the example of FIG. 10, as a result of adopting the set inclination angle θ slightly larger than the angle θ _ideal , and because it is difficult to finely adjust the mounting angle of the exposure head 30, the actual mounting angle and the above As a result of the error in the set inclination angle θ, density unevenness occurs in any region on the exposed surface. Specifically, in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, it is ideal in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows. Overexposure occurs with respect to double exposure, resulting in a redundant drawing area and uneven density.

Furthermore, the example of FIG. 10 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” occurs in which the inclination angle of each pixel row projected on the surface to be exposed is not uniform. Causes of such angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, micromirror placement errors, and the like.
The angular distortion appearing in the example of FIG. 10 is a distortion in which the tilt angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

In order to reduce the density unevenness in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows as described above, a set of the slit 28 and the photodetector is used as the light spot position detecting means. The actual inclination angle θ ′ is specified for each exposure head 30, and based on the actual inclination angle θ ′, the arithmetic unit connected to the photodetector as the pixel portion selection unit is used for actual exposure. A process of selecting a micromirror to be used is performed.
The actual inclination angle θ ′ is based on at least two light spot positions detected by the light spot position detection means, and the light spot column direction on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. It is specified by the angle formed by.
Hereinafter, the specification of the actual inclination angle θ ′ and the used pixel selection process will be described with reference to FIGS.

-Specification of actual inclination angle θ'-
FIG. 11 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
In the example of the present embodiment (1), the angle formed by the 512th light spot row positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle θ ′. . Specifically, the micromirror 58 in the first row and the 512th column and the micromirror 58 in the 256th row and the 512th column on the DMD 36 are turned on, and the light spots on the exposure surface corresponding to each of the micromirrors 58 are turned on. The positions of P (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 θ ′.

FIG. 12 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
First, in a state where the micromirror 58 in the 256th row and the 512th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is changed. The slit 28 is positioned at an arbitrary position so as to be between the upstream slit 28a and the downstream slit 28b. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 512) on the surface to be exposed are X = X0 + (Y1-Y2) / 2, Y = (Y1 + Y2) / 2. Determine by calculation. By the same measurement, coordinates indicating the position of P (1,512) are also determined, an inclination angle formed by a straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is obtained as an actual inclination angle θ ′. As specified.

-Selection of used pixel part-
Using the actual inclination angle θ ′ thus specified, the arithmetic unit connected to the photodetector is expressed by the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived, and the first to T-th row micromirrors on the DMD 36 are selected as micromirrors that are actually used during the main exposure. In this way, in the exposure region near the 512th column, a micromirror that minimizes the total area of the overexposed region and the underexposed region with respect to the ideal double exposure is actually obtained. It can be selected as a micromirror to be used for.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the overexposed region and does not produce an underexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.
It is also possible to derive the maximum natural number equal to or less than the value t. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the underexposed region and does not produce an overexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.

FIG. 13 shows how the unevenness on the exposed surface shown in FIG. 10 is improved in the exposure performed using only the light spot generated by the micromirror selected as the micromirror to be actually used as described above. It is explanatory drawing which showed what was done.
In this example, it is assumed that T = 253 is derived as the natural number T and the micromirrors in the first row to the 253rd row are selected. For the micromirrors in the 254th to 256th rows that are not selected, the pixel part control means sends a signal to set the angle of the always-off state, and these micromirrors are substantially Not involved in exposure. As shown in FIG. 13, in the exposure region near the 512th column, overexposure and underexposure are almost completely eliminated, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 13 (near c (1) in the figure), the inclination angle of the light spot sequence on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. This is smaller than the inclination angle of the light beam row in the region. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, the ideal double pattern is used for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. An area that is underexposed with respect to the exposure is slightly generated.
However, in the actual exposure pattern formed by overlaying the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the regions where the exposure amount is insufficient are complemented with each other, and the exposure unevenness due to the angular distortion is double-exposed. The effect of offsetting can be minimized.

Further, in the region on the right side of FIG. 13 (near c (1024) in the figure), the inclination angle of the light beam on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is larger than the inclination angle of the light beam row in the region. Therefore, in the exposure with the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, as shown in the figure, there is an overexposed region with respect to the ideal double exposure. It will occur slightly.
However, in the actual exposure pattern formed by superimposing the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the overexposed regions are complemented with each other, and the density unevenness due to the angular distortion is caused by the double exposure. The effect of offsetting can be minimized.

In the present embodiment (1), as described above, the actual inclination angle θ ′ of the 512th ray array is measured, and based on the T derived from the equation (4) using the actual inclination angle θ ′. The micro-mirror 58 to be used is selected. However, as a method of specifying the actual inclination angle θ ′, a plurality of actual directions formed by the column direction (light spot column) of the plurality of image elements and the scanning direction of the exposure head are used. Each of the tilt angles is measured, and any one of the average value, median value, maximum value, and minimum value is specified as an actual tilt angle θ ′. It is good also as a form to select.
When the average value or the median value is set to the actual inclination angle θ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure. For example, the total area of the overexposed region and the underexposed region is minimized, and the number of pixel units (number of light spots) in the overexposed region and the underexposed region are drawn. It is possible to realize exposure such that the number of prime units (number of light spots) is equal.
Further, if the maximum value is set to the actual inclination angle θ ′, it is possible to realize an exposure that places more importance on eliminating an overexposed region with respect to an ideal N double exposure, for example, an underexposure. It is possible to realize exposure that minimizes the area of the region and does not generate an overexposed region.
Further, if the minimum value is set to the actual inclination angle θ ′, it is possible to realize exposure that places more importance on eliminating underexposed areas with respect to ideal N-fold exposure, for example, overexposure. It is possible to realize exposure that minimizes the area of the region and does not cause a region that is underexposed.

On the other hand, the specification of the actual inclination angle θ ′ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row). For example, the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in the row near the c (n), The actual inclination angle θ ′ may be specified.
Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on a straight line and in the vicinity along the scanning direction of the exposure head are detected. The actual inclination angle θ ′ can be obtained from the position information. Further, the angle obtained based on the positions of at least two light spots (for example, two light spots arranged so as to straddle c (n)) in the light spot array in the vicinity of the c (n) line is an actual inclination. The angle θ ′ may be specified.

  As described above, according to the specification method of the used picture element portion of the present embodiment (1) using the pattern forming apparatus 10, resolution variation and density unevenness due to the influence of the mounting angle error of each exposure head and pattern distortion are eliminated. It is possible to reduce and realize an ideal N double exposure.

(2) Method for designating used pixel parts between a plurality of exposure heads <1>
In the present embodiment (2), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads 30. In the intermittent region, the variation in resolution and density unevenness due to the deviation from the ideal state of the relative position of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction are reduced; A description will be given of a method for designating a used pixel portion for realizing ideal double exposure.

As the set inclination angle θ of each exposure head 30, that is, each DMD 36, the usable pixel portion micromirror 58 of 1024 columns × 256 rows is used if there is no ideal mounting angle error of the exposure head 30. Then, it is assumed that an angle θ _ideal that is exactly double exposure is adopted.
This angle θ _ideal is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1). In the present embodiment (2), it is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 becomes this angle θ _ideal .

FIG. 14 shows the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which showed the example of the density nonuniformity which arises in the pattern on a to-be-exposed surface by the influence. The displacement of the relative position of each exposure head in the X-axis direction can occur because it is difficult to finely adjust the relative position between the exposure heads.

14 is projected onto the exposed surface of the photosensitive material 12 in a state where the stage 14 is stationary, the light spot group from the usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 _21. It is the figure which showed these patterns. The lower part of FIG. 14 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing. The state is shown for exposure areas 32 ₁₂ and 32 ₂₁ .
In FIG. 14, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

In the example of FIG. 14, the exposure pattern by the pixel column group A and the pixel column group B as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction from the ideal state. In both of the above exposure patterns, a portion where the exposure amount is larger than the ideal double exposure state occurs in the connection area between the heads in the exposure areas 32 ₁₂ and 32 ₂₁ .

In order to reduce density unevenness appearing in the inter-head connecting region formed on the exposed surface by the plurality of exposure heads as described above, in this embodiment (2), a slit is used as the light spot position detecting means. 28 and a set of photodetectors, the positions of some of the light spots constituting the connecting area between the heads formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 _21. Detect (coordinates). Based on the position (coordinates), processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel portion selection means.

-Detection of position (coordinates)-
FIG. 15 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to those in FIG. 14 and the corresponding slits 28. The size of the slit 28 is large enough to cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ , that is, the slit 28 is formed on the exposed surface by the exposure heads 30 ₁₂ and 30 _21. The size is sufficient to cover the connection area between the heads.

Figure 16 is a top view for explaining a detection method of detecting the position of a point P of the exposure area _{32 21} as an example (256, 1024).
First, with the micromirror in the 256th row and the 1024th column turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream. The slit 28 is positioned at an arbitrary position so as to be between the slit 28a on the side and the slit 28b on the downstream side. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 16 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 16 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 1024) on the exposed surface are calculated as X = X0 + (Y1−Y2) / 2, Y = (Y1 + Y2) / 2. Determined by

-Identification of unused pixel parts-
In the example of FIG. 14, first, the position of the point P of the exposure area _{32 12} (256,1) is detected by a set of slits 28 and a photodetector as the light spot position detecting unit. Subsequently, the position of each light spot on the 256 line of light spots row r of the exposure area _{32 21 (256), P (} 256,1024), to detect the P (256,1023) ··· and order periodically, where the exposure area _{32 21} of point P indicating the exposure area _{32 12} point P (256,1) larger X coordinate than the (256, n) is detected, and terminates the detecting operation. Then, the micro mirrors corresponding to light spots constituting the c (1024) from the light spot column c of the exposure area 32 ₂₁ (n + 1), specifies as a micro-mirror is not used during the exposure (unused pixel parts).
For example, in FIG. 14, the exposure area _{32 21} point P (256,1020) is shows a larger X coordinate than the point P of the exposure area _{32 12} (256,1) of the exposure area _{32 21} spot If P (256,1020) is that the detection operation at the detected ended, the light spots constituting the first 1024 lines from the 1021 line of exposure area _{32 21,} corresponding to the portion 70 covered with hatched in FIG. 17 The corresponding micromirror is identified as a micromirror that is not used during the main exposure.

Next, the number N of the N multiple exposure, the position of the point P of the exposure area _{32 12} (256, N) is detected. In this embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.
Then, among the light spot columns of the exposure area 32 _21, except those identified as light spots string corresponding to the micromirrors is not used during the exposure in the above, the position of the light spot constituting the rightmost 1020 column a, P (1,1020) in order from P (1,1020), P (2,1020 ) ··· and continue to detection, greater than the point P of the exposure area _{32 12} (256,2) X When the light spot P (m, 1020) indicating the coordinates is detected, the detection operation is terminated.
Thereafter, the connected operational devices to said light detector, and X-coordinate of the exposure area _{32 12} of the light spot P (256, two), point P of the exposure area _{32 21} (m, 1020) and P (m- and X-coordinate of 1,1020) are compared, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m, 1020) is closer to the X coordinate of the point P in the exposure area _{32 12} (256, 2) a micro mirror corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020) is identified as a micro-mirror is not used during the exposure.
Also, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m-1,1020) is close to the X-coordinate of the point P in the exposure area _{32 12} (256, 2), the light of the exposure area _{32 21} Micromirrors corresponding to points P (1, 1020) to P (m−2, 1020) are specified as micromirrors that are not used for the main exposure.
Furthermore, the position of the point P of the exposure area _{32 12 (256, N-1} ) That point P (256,1), the position of each point constituting the first 1019 column is the next row of the exposure area _{32 21} The same detection process and identification of micromirrors that are not used are also performed.

  As a result, for example, micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 17 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set the micromirror angle to the off-state angle, and these micromirrors are substantially not used for exposure.

As described above, the micromirrors that are not used at the time of actual exposure are identified, and the micromirrors that are not used at the time of actual exposure are selected as the micromirrors that are used at the time of actual exposure, whereby the exposure areas 32 ₁₂ and 32 ₂₁ In the connecting area between the heads, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure can be minimized. As shown in the lower part of FIG. Uniform exposure extremely close to double exposure can be realized.

In the above example, upon the particular light spots constituting the regions 72 covered with hatched in FIG. 17, the X coordinate of the point P in the exposure area _{32 12} (256, 2), the exposure area _{32 21} of the light spot P (m, 1020) and P (m-1,1020) without comparison of the X-coordinate of the immediately, P from point P of the exposure area _{32 21 (1,1020) (m-} 2 , 1020) may be specified as a micromirror that is not used during the main exposure. In that case, in the connecting area between the heads, a micromirror is actually used that minimizes the area of an overexposed area with respect to an ideal double exposure and does not cause an underexposed area. It can be selected as a micromirror.
Further, the micro-mirrors corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020), it may be specified as micro mirrors not used in this exposure. In that case, in the connecting region between the heads, a micromirror is actually used in which the area of the region that is underexposed with respect to the ideal double exposure is minimized and the region that is not overexposed does not occur. It can be selected as a micromirror.
Further, in the connecting area between the heads, the number of pixel units (the number of light spots) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light spots) in an area that is underexposed. It is good also as selecting the micromirror actually used so that it may become equal.

  As described above, according to the specification method of the used pixel part of the present embodiment (2) using the pattern forming apparatus 10, the resolution variation caused by the relative position shift in the X-axis direction of the plurality of exposure heads Density unevenness can be reduced, and ideal N-fold exposure can be realized.

(3) Specification method of used pixel parts between a plurality of exposure heads <2>
In this embodiment (3), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30. In the intermittent region, the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state, the mounting angle error of each exposure head, and the two exposures A description will be given of a method for designating a pixel part to be used in order to reduce resolution variations and density unevenness due to relative mounting angle errors between the heads and realize ideal double exposure.

As the set tilt angle of each exposure head 30, that is, each DMD 36, in an ideal state where there is no mounting angle error of the exposure head 30, a usable 1024 column × 256 row pixel element (micromirror 58) is provided. It is assumed that an angle slightly larger than the angle θ _ideal that is used for exactly double exposure is adopted.
This angle θ _ideal is a value obtained in the same manner as the above embodiment (1) using the above equations 1 to 3, and in this embodiment, s = 256 and N = 2 as described above. The angle θ _ideal is about 0.45 degrees. Therefore, for example, an angle of about 0.50 degrees may be adopted as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

FIG. 18 shows a mounting angle error of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 in which the mounting angle of each exposure head 30, that is, each DMD 36 is initially adjusted as described above, FIG. 11 is an explanatory diagram showing an example of unevenness that occurs in a pattern on an exposed surface due to the influence of a relative mounting angle error between each of the exposure heads 30 ₁₂ and 30 ₂₁ and a relative position shift.

In the example of FIG. 18, as in the example of FIG. 14, as a result of the shift of the relative positions of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction, exposure by every other light spot group (pixel column groups A and B) is performed. In both exposure patterns 32 ₁₂ and 32 ₂₁ , the exposure amount overlaps on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface of the exposure areas 32 ₁₂ and 32 ₂₁ , which is more than the ideal double exposure state. A region 74 is generated, which causes uneven density.
Further, in the example of FIG. 18, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head slightly larger than the angle θ _ideal satisfying the formula (1) and the mounting angle of each exposure head. Therefore, as a result of the actual mounting angle deviating from the set inclination angle θ, even in regions other than the exposure region overlapping on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface, In the connection region between the pixel part columns, which is an overlapped exposure region on the exposed surface, formed by a plurality of pixel part columns, both in the exposure pattern by every other light spot group (pixel column group A and B). A region 76 that is overexposed than the ideal double exposure state is generated, and this causes further density unevenness.

In this embodiment (3), first, the use pixel selection process for reducing the uneven density due to the influence of the deviation of the mounting angle error and relative mounting angle of the exposure heads 30 ₁₂ and 30 _21.
Specifically, a set of a slit 28 and a photodetector is used as the light spot position detecting means, and an actual inclination angle θ ′ is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual inclination angle θ ′ is set. Based on this, it is assumed that processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel part selection means.

-Specification of actual inclination angle θ'-
The actual inclination angle θ ′ is specified with respect to the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ for the exposure head 30 _{12 and in the} exposure area 32 ₂₁ for the exposure head 30 ₂₁ . The positions of the light spots P (1,1024) and P (256,1024) are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), and the inclination angle of the straight line connecting them. And the angle formed by the scanning direction of the exposure head.

-Identification of unused pixel parts-
The arithmetic device connected to the photodetector using the actual inclination angle θ ′ thus specified is similar to the following equation 4 similar to the arithmetic device in the embodiment (1) described above.
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirrors in the (T + 1) th to 256th rows on the DMD 36 are not used for the main exposure. Processing to identify as a micromirror is performed.
For example, T = 254 for the exposure head _{30 12,} when T = 255 was derived for the exposure head _3O21, micro mirrors corresponding to light spots constituting the parts 78 and 80 covered with hatched in FIG. 19 These are specified as micromirrors that are not used for the main exposure. As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure is minimized. be able to.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area where the amount is excessive and to prevent an area where the exposure amount is insufficient.
Or it is good also as deriving the maximum natural number below value t. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area of the insufficient region and prevent the region from being overexposed.
In each area other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads, the number of pixel units (light It is also possible to identify micromirrors that are not used during the main exposure so that the number of pixel units (the number of light points) in the underexposed region is equal to the number of points.

Thereafter, with respect to the micromirror corresponding to the light spot other than the light spots constituting the regions 78 and 80 covered with diagonal lines in FIG. In FIG. 19, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are specified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. Not involved.

  As described above, according to the method for designating the used picture element portion of the present embodiment (3) using the pattern forming apparatus 10, the relative position shift in the X-axis direction of the plurality of exposure heads, as well as the Variation in resolution and density unevenness due to the mounting angle error and the relative mounting angle error between the exposure heads can be reduced, and ideal N-fold exposure can be realized.

  As described above, the method for designating the used pixel portion by the pattern forming apparatus 10 has been described in detail. However, the above-described embodiments (1) to (3) are merely examples, and various modifications can be made without departing from the scope of the present invention. It is.

  In the above embodiments (1) to (3), as a means for detecting the position of the light spot on the exposed surface, a set of the slit 28 and the single cell type photodetector is used. The present invention is not limited to this, and any form may be used. For example, a two-dimensional detector may be used.

  Further, in the above embodiments (1) to (3), the actual inclination angle θ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle θ ′ is obtained. The micromirrors to be used are selected based on the above, but a usable micromirror may be selected without the derivation of the actual inclination angle θ ′. Furthermore, for example, the reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by checking the resolution and density unevenness by visual observation of the reference exposure results. It is included in the scope of the invention.

In addition to the angular distortion described in the above example, there are various forms of pattern distortion that can occur on the exposed surface.
As an example, as shown in FIG. 20A, there is a form of magnification distortion in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.
As another example, as shown in FIG. 20B, there is a form of beam diameter distortion in which the light from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposed surface with a different beam diameter. . These magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposed surface.
As yet another example, there is a form of light amount distortion in which light beams from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposed surface with different light amounts. In addition to various aberrations and misalignment, the light amount distortion includes the positional dependence of the transmittance of optical elements between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIGS. 5A and 5B which are single lenses) This is caused by unevenness in the amount of light due to the DMD 36 itself. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.

  According to the above embodiments (1) to (3), the residual elements of pattern distortion in these forms after selecting the micromirrors actually used for the main exposure are the same as the residual elements of angular distortion described above. It is possible to level out by the effect of filling by multiple exposure, and the unevenness of resolution and density can be reduced over the entire exposure area of each exposure head.

<< Reference exposure >>
As a modified example of the above embodiments (1) to (3), among available micromirrors, it corresponds to (N-1) every micromirror column or 1 / N rows of all light spot rows. A reference exposure is performed using only a group of micromirrors constituting an adjacent row, and among the micromirrors used for the reference exposure, micromirrors that are not used at the time of actual exposure are specified so that uniform exposure can be realized. It is good as well.
The result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is analyzed to confirm resolution variation and density unevenness and to estimate the actual inclination angle. The analysis of the result of the reference exposure may be a visual analysis by an operator.

FIG. 21A and FIG. 21B are explanatory views showing an example of a form in which reference exposure is performed using only (N-1) rows of micromirrors using a single exposure head.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot arrays indicated by the solid lines in FIG. 21A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and density unevenness, or estimating an actual inclination angle.
For example, micromirrors other than the micromirror corresponding to the light spot array shown by hatching in FIG. 21B are designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. . For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and the micromirror used during the main exposure may be designated, or the same pattern as that for the odd-numbered light spot arrays may be applied. Good.
By specifying the micromirrors used in the main exposure as described above, in the main exposure using both the odd-numbered and even-numbered micromirrors, a state close to ideal double exposure can be realized.

FIG. 22 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference is made using only the micromirrors corresponding to the odd-numbered light spot rows of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction, which are indicated by solid lines in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the area 86 shown by hatching in FIG. 22 and the shaded area 88 are among the micromirrors constituting the odd-numbered light spots, during the main exposure. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

FIG. 23A and FIG. 23B show an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total number of light spot rows. FIG.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows indicated by the solid line in FIG. 23A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, a micromirror to be used in the main exposure can be designated.
For example, a micromirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 23B is designated as actually used in the main exposure among the micromirrors in the first to 128th rows. Can be done. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used in the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
By designating the micromirror to be used at the time of the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using the entire micromirror.

FIG. 24 uses a plurality of exposure heads, and two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction are adjacent to each other corresponding to 1 / N rows of the total number of light spots. It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises a line.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows indicated by solid lines in FIG. 24, and the reference exposure results are output as samples. . Based on the reference exposure result outputted from the sample, it is possible to realize the main exposure in which the variation in resolution and the density unevenness in the region other than the joint region between the heads formed on the exposed surface by the two exposure heads are minimized. In addition, it is possible to designate a micromirror to be used during the main exposure.
For example, micromirrors other than the micromirrors corresponding to the light spot arrays in the region 90 shown by hatching in FIG. 24 and the region 92 shown by shading are included in the micromirrors in the first to 128th rows. Designated as actually used at the time of exposure. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used for the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
In this way, by specifying the micromirror to be used during the main exposure, a state close to ideal double exposure is realized in an area other than the inter-head connecting area formed on the exposed surface by two exposure heads. it can.

  In the above embodiments (1) to (3) and the modified examples, the case where the main exposure is the double exposure has been described. However, the present invention is not limited to this, and any multiple exposure more than the double exposure may be used. . In particular, by setting the exposure to about 3 to 7 exposures, high resolution can be secured, and exposure with reduced variations in resolution and density unevenness can be realized.

  Further, in the exposure apparatus according to the embodiment and the modified example, the dimension of the predetermined part of the two-dimensional pattern represented by the image data is matched with the dimension of the corresponding part that can be realized by the selected use pixel. A mechanism for converting image data is preferably provided. By converting the image data in this way, a high-definition pattern according to a desired two-dimensional pattern can be formed on the exposed surface.

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

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

For example, the pH of the weakly alkaline aqueous solution is preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 to 40 ° C., for example.

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

  In the formation of the pattern, for example, a curing process, an etching process, a plating process, and the like may be included. These may be used individually by 1 type and may use 2 or more types together.

<Curing process>
When the pattern forming method is a permanent pattern forming method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter, the photosensitive layer is cured after the developing step. It is preferable to provide the hardening process process which processes.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. By the entire surface exposure, curing of the resin in the photosensitive resin composition forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected according to the purpose. It is mentioned in. The exposure amount is usually 10 to 2,000 mJ / cm ² .

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
120-250 degreeC is preferable and the heating temperature in the said whole surface heating has more preferable 120-200 degreeC. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive resin composition is decomposed, and the film quality is weak and brittle. May be.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

  In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern. When the pattern formed by the permanent pattern forming method is a permanent pattern such as the protective film, the interlayer insulating film, and the solder resist pattern, the wiring can be protected from external impact and bending. In the case of an interlayer insulating film, it is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board or a build-up wiring board.

  By using the photosensitive resin composition of the present invention, the permanent pattern forming method of the present invention is excellent in various characteristics such as pattern formability, plating resistance, and peelability, and has high sensitivity and good resolution. Yes, because the pattern can be formed with high definition and efficiency, the formation of various patterns such as protective patterns, interlayer insulating films, and solder resist patterns that require high-definition exposure, and color It can be suitably used for the production of liquid crystal structural members such as filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., and particularly suitable for the formation of permanent patterns on printed wiring boards. be able to.

[Method of manufacturing printed wiring board]
The said pattern formation method of this invention can be used suitably for manufacture of a printed wiring board, especially the manufacture of a printed wiring board which has hole parts, such as a through hole or a via hole. Hereinafter, an example of the manufacturing method of the printed wiring board using the pattern formation method of this invention is demonstrated.

  As a method for producing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the pattern forming material is formed on a printed wiring board forming substrate having a hole portion as the substrate, and the photosensitive layer is the substrate. (2) The photosensitive layer is irradiated with light from a side opposite to the base of the photosensitive laminate to cure the photosensitive layer, 3) removing the support in the pattern forming material from the photosensitive laminate, and (4) developing the photosensitive layer in the photosensitive laminate to remove the uncured portion in the photosensitive laminate. A pattern can be formed.

  The removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).

  Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate using the formed pattern (for example, a known subtractive method or additive method (for example, a semi-additive method) And the full additive method)). Among these, in order to form a printed wiring board by industrially advantageous tenting, the subtractive method is preferable. After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off. In the case of the semi-additive method, a desired printed wiring board can be manufactured by further etching the copper thin film portion after peeling. it can. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.

  Next, the manufacturing method of the printed wiring board which has a through hole using the said pattern formation material is further demonstrated.

  First, a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper-clad laminate substrate and a substrate in which a copper plating layer is formed on an insulating substrate such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer A substrate (laminated substrate) can be used.

Next, when a protective film is provided on the pattern forming material, the protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. Is used for pressure bonding (lamination process). Thereby, the photosensitive laminated body which has the said board | substrate for printed wiring board formation and the said photosensitive laminated body in this order is obtained.
There is no restriction | limiting in particular as lamination | stacking temperature of the said pattern formation material, For example, room temperature (15-30 degreeC) or under heating (30-180 degreeC) is mentioned, Among these, under heating (60-140 degreeC) Is preferred.
There is no restriction | limiting in particular as roll pressure of the said crimping | compression-bonding roll, For example, 0.1-1 Mpa is preferable.
There is no restriction | limiting in particular as the speed | rate of the said crimping | compression-bonding, and 1-3 m / min is preferable. The printed wiring board forming substrate may be preheated or laminated under reduced pressure.

  The formation of the photosensitive laminate may be performed by laminating the pattern forming material on the printed wiring board forming substrate, and the photosensitive resin composition solution for manufacturing the pattern forming material or the like may be used as the printed wiring board. The photosensitive layer and the support may be laminated on the printed wiring board forming substrate by applying directly to the surface of the forming substrate and drying.

  Next, light is irradiated from the surface of the photosensitive laminate opposite to the substrate to cure the photosensitive layer. At this time, exposure may be performed after peeling off the support as necessary (for example, when the light transmittance of the support is insufficient).

  At this time, if the support is not yet peeled, the support is peeled from the photosensitive laminate (peeling step).

  Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer to form a pattern of the cured layer for forming the wiring pattern and the cured layer for protecting the metal layer of the through hole. And a metal layer is exposed on the surface of the printed wiring board forming substrate (developing step).

  Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

  Next, the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal plating of the through hole is predetermined without etching liquid entering the through hole and corroding the metal plating in the through hole. It will remain in the shape. Thus, a wiring pattern is formed on the printed wiring board forming substrate.

  There is no restriction | limiting in particular as said etching liquid, According to the objective, it can select suitably, For example, when the said metal layer is formed with copper, a cupric chloride solution, a ferric chloride solution, Examples include alkaline etching solutions and hydrogen peroxide-based etching solutions. Among these, ferric chloride solutions are preferable from the viewpoint of etching factors.

Next, it removes from the said board | substrate for printed wiring board formation by making the said hardened layer into a peeling piece with strong alkaline aqueous solution etc. (hardened | cured material removal process).
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

  The printed wiring board may be a multilayer printed wiring board. The pattern forming material may be used not only for the above etching process but also for a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.

When the substrate is a printed wiring board such as a multilayer wiring board, a photosensitive layer made of a photosensitive resin composition as the solder resist is formed on the printed wiring board, and soldered as follows. It can be performed.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1
-Preparation of photosensitive resin composition-
Each component was mix | blended in the following quantity and the photosensitive resin composition solution was prepared.
[Each component amount of photosensitive resin composition solution]
---------------------------------------
・ Binder (Acid-modified vinyl group-containing epoxy resin obtained by the following production method 1) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ 40% by mass
-Photopolymerization initiator (compound represented by the following formula (B-1)) ... 3% by mass
-Polymerizable compound (dipentaerythritol hexaacrylate (DPHA), manufacturer: Nippon Kayaku Co., Ltd.) ... 12 mass %
-Thermal crosslinking agent (epoxy compound having two or more epoxy groups in one molecule, product name: EXA
-4750, manufacturer: Dainippon Ink & Chemicals, Inc.) ... 10% by mass
・ 1-Chloro-4-propyloxythioxanthone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.7% by mass
・ Methyl ethyl ketone (MEK) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 100% by mass
---------------------------------------

(Manufacturing method 1)
100 ° C. of 60% glycidyl-containing cresol novolak resin (mass average molecular weight: 15,000), 10 parts by mass of methacrylic acid, 1 part by mass of triethylamine, and 150 parts by mass of methylpropylene glycol acetate (MFG-Ac) The mixture was stirred for 2 hours to synthesize an acid-modified vinyl group-containing epoxy resin.

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

-Preparation of photosensitive laminate-
Next, as the base material, a surface of a copper-clad laminate (no through hole, copper thickness 12 μm) on which wiring was formed as a printed wiring board was prepared by chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order.
The pressure bonding conditions were as follows: a vacuuming time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

  The photosensitive laminate was evaluated for the shortest development time, sensitivity, resolution, peelability, plating resistance, and surface unevenness.

<Evaluation of the shortest development time>
The polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. The shortest development time was 15 seconds.

<Evaluation of sensitivity>
With respect to the photosensitive layer of the photosensitive film in the prepared photosensitive laminate, from the support side, using a pattern forming apparatus described below, 0.1 mJ / cm ² to 100 mJ / cm at ^2½ times intervals. by irradiating light of different amount of light energy to ² double exposure to cure the part of the area of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. And sprayed for twice the minimum development time to dissolve and remove the uncured area, and the thickness of the remaining cured area was measured. Next, a sensitivity curve was obtained by plotting the relationship between the amount of light irradiation and the thickness of the cured layer. From the sensitivity curve, the amount of light energy when the thickness of the cured region was 30 μm, the same as that of the photosensitive layer before exposure, was defined as the amount of light energy necessary for curing the photosensitive layer.

<< Pattern Forming Apparatus >>
As the light irradiating means, a combined laser light source described in paragraphs “0109” to “0146” of the specification of JP-A-2005-258431, and a main diagram schematically showing FIG. 6 as the light modulating means. 5A and 5B show a DMD 36 controlled to drive only 1024 × 256 rows out of 768 micromirror rows in which 1024 micromirrors 58 are arranged in the scanning direction. A pattern forming apparatus 10 provided with an exposure head 30 having an optical system for forming an image of the indicated light on the photosensitive film was used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _{ideal at} which double exposure is performed using a usable 1024 column × 256 row micromirror 58 was adopted. This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
Since s = 256 and N = 2, the angle θ _ideal is about 0.45 degrees. Therefore, for example, 0.50 degrees is adopted as the set inclination angle θ.

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 16, the light spot group from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive film 12 with the stage 14 being stationary. Showed the pattern. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 16, for convenience of explanation, every other column exposure pattern of the micromirror 58 that can be used is divided into an exposure pattern by the pixel column group A and an exposure pattern by the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 16, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

The use of a set of slits 28 and a photodetector as a light spot position detection means, the position of the point P of the exposure head _{30 12} For the exposure area _{32 12} (1,1) and P (256,1), the exposure head For 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 angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head is determined. It was measured.

Using the actual inclination angle θ ′, the following equation 4
ttanθ ′ = N (Formula 4)
The closest natural number T to the value t satisfying the relationship, derived for each of the exposure heads _{30 12} and _{30 21.} T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 17 were similarly covered with the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed 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. Thus, the total area of the overexposed region and the underexposed region can be minimized.

<Evaluation of resolution>
The laminate was prepared under the same method and conditions as the evaluation method for the shortest development time, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the laminate, exposure is performed for each line width in increments of 1 μm from line / space = 1/1 to a line width of 10 to 100 μm using the pattern forming apparatus. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate. A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove uncured areas. The surface of the copper-clad laminate with a permanent pattern obtained in this way is observed with an optical microscope, the line of the permanent pattern is free of irregularities such as rounding and twisting, and the minimum line width that can form a space is measured, This was the resolution. The smaller the numerical value, the better the resolution.

<Plating resistance>
The permanent pattern obtained in the evaluation of the resolution was degreased to roughen the surface, and then palladium sulfate was added to perform catalyst addition. Next, after immersing the permanent pattern in a nickel sulfate / dilute sulfuric acid solution at 70 ° C. for 40 minutes to perform plating, the cured film in the permanent pattern was visually turned up and peeled off, based on the following criteria: The plating resistance was evaluated.
〔Evaluation criteria〕
(Double-circle): It turns over to a cured film, there is no peeling, and it is very excellent in plating resistance.
○: Discoloration occurs in a part of the cured film, but this is not a problem for practical use and has excellent plating resistance.
Δ: The cured film is turned over and the plating resistance is poor.
X: Floating (peeling) is observed in the cured film, and the plating resistance is extremely poor.

<Peelability>
After preparing the photosensitive laminate, the polyethylene terephthalate film (support) was peeled off from the photosensitive film on the substrate, and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Peeled without resistance.
Δ: Some resistance unevenness was observed.
X: High resistance and a photosensitive layer adhered on the support.

<Surface unevenness>
Regarding the sample after the peelability test, the unevenness was visually observed on the surface of the photosensitive layer laminate (after peeling off the support).
When there was unevenness on the release surface, it was indicated as “Yes”, and when there was no unevenness on the release surface, it was indicated as “None”.

(Example 2)
In Example 1, the photosensitive film and the photosensitive laminated body were the same as in Example 1 except that the binder was changed from the binder obtained by the production method 1 to the binder obtained by the following production method 2. Manufactured.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Manufacturing method 2)
100 parts by mass of a bisphenol type epoxy resin (product name: ZX-1059, manufacturer: Toto Kasei Co., Ltd.), 5 parts by mass of methacrylic acid, 1 part by mass of triethylamine, and 150 parts by mass of methylpropylene glycol acetate (MFG-Ac) The mixture was stirred at 40 ° C. for 2 hours to synthesize an acid-modified vinyl group-containing epoxy resin.

(Example 3)
In Example 1, the photosensitive film and the photosensitive laminated body were the same as in Example 1 except that the binder was changed from the binder obtained by the production method 1 to the binder obtained by the following production method 3. Manufactured.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Manufacturing method 3)
Salicylaldehyde type epoxy resin (product name: FAE-2500, manufacturer: Nippon Kayaku Co., Ltd.) 100 parts by mass, acrylic acid 10 parts by mass, triethylamine 1 part by mass, methylpropylene glycol acetate (MFG-Ac) 150 parts by mass The mixture was stirred at 40 ° C. for 2 hours to synthesize an acid-modified vinyl group-containing epoxy resin.

Example 4
In Example 1, the photosensitive film and the photosensitive laminated body were the same as in Example 1 except that the binder was changed from the binder obtained by the production method 1 to the binder obtained by the following production method 4. Manufactured.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Manufacturing method 4)
60% glycidyl-containing cresol novolac resin (mass average molecular weight: 15,000) 100 parts by weight, acrylic acid 10 parts by weight, trimellitic anhydride 1 part by weight, triethylamine 1 part by weight, methylpropylene glycol acetate (MFG- Ac) 150 parts by mass was stirred at 40 ° C. for 2 hours to synthesize an acid-modified vinyl group-containing epoxy resin.

(Example 5)
In Example 1, the photopolymerization initiator was changed from the compound represented by the formula (B-1) to the compound represented by the formula (B-2) in the same manner as in Example 1. Thus, a photosensitive film and a photosensitive laminate were produced.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Example 6)
In Example 1, the photopolymerization initiator was changed from the compound represented by the formula (B-1) to the compound represented by the following formula (B-3) in the same manner as in Example 1. Thus, a photosensitive film and a photosensitive laminate were produced.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Example 7)
In Example 1, as the photopolymerization initiator, in addition to the compound represented by the formula (B-1), Irg. A photosensitive film and a photosensitive laminate were produced in the same manner as in Example 1 except that 1 mass% of 819 (manufacturer: Ciba Specialty Chemicals) was added.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Example 8)
A photosensitive film and a photosensitive laminate were produced in the same manner as in Example 1 except that 1-chloro-4-propyloxythioxanthone was changed to N-butylchloroacridone in Example 1.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

Example 9
In Example 1, as the photopolymerization initiator, in addition to the compound represented by the formula (B-1), Irg. A photosensitive film and a photosensitive laminate were produced in the same manner as in Example 1 except that 1% by mass of 369 (manufacturer: Ciba Specialty Chemicals) was added.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Example 10)
In Example 1, the photosensitive film and the photosensitive laminated body were manufactured like Example 1 except having changed the addition amount of the polymeric compound from 12 mass% to 25 mass%.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Example 11)
In Example 1, the photosensitive film and the photosensitive laminated body were manufactured like Example 1 except having added 30 mass% of barium sulfate as an inorganic filler.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Example 12)
In Example 1, a photosensitive film and a photosensitive laminate were produced in the same manner as in Example 1 except that 1-chloro-4-propyloxythioxanthone was not contained.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Example 13)
In Example 1, the photopolymerization initiator was changed from the compound represented by the formula (B-1) to the compound represented by the following formula (B-4) in the same manner as in Example 1. Thus, a photosensitive film and a photosensitive laminate were produced.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.
In the following formula (B-4), Me represents a methyl group.

(Example 14)
In Example 1, the photopolymerization initiator was changed from the compound represented by the formula (B-1) to the compound represented by the formula (B-5) in the same manner as in Example 1. Thus, a photosensitive film and a photosensitive laminate were produced.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.
In the following formula (B-5), Ph represents a phenyl group.

(Comparative Example 1)
In Example 1, the binder was changed from the binder obtained by the production method 1 to an acrylic acid-methyl methacrylate copolymer (copolymer composition (mass%): 30/70, mass average molecular weight: 25,000). The photosensitive film and the photosensitive laminated body were manufactured like Example 1 except having replaced with ().
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Comparative Example 2)
In Example 1, as the photopolymerization initiator, instead of the compound represented by the formula (B-1), Irg. A photosensitive film and a photosensitive laminate were produced in the same manner as in Example 1 except that 369 (manufacturer: Ciba Specialty Chemicals) was added.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

(Comparative Example 3)
In Example 1, the same procedure as in Example 1 except that phenyl glycidyl ether was added instead of EXA-4750 (an epoxy compound having two or more epoxy groups in one molecule) as the thermal crosslinking agent. A photosensitive film and a photosensitive laminate were produced.
Moreover, the same evaluation as Example 1 was performed about the said photosensitive film and the photosensitive laminated body.

From the result of Table 1, the photosensitive resin composition of Examples 1-14 is an acid-modified vinyl group containing epoxy resin, the compound represented by the said General formula (1), and two or more epoxy in the said molecule | numerator. Any one of an acid-modified vinyl group-containing epoxy resin, a compound represented by the general formula (1), and an epoxy compound having two or more epoxy groups in one molecule because it contains an epoxy compound having a group Compared to the photosensitive resin compositions of Comparative Examples 1 to 3 that do not contain any of the above, it was found that they were excellent in various properties such as plating resistance and peelability, and had good sensitivity and resolution.

The photosensitive resin composition and photosensitive film of the present invention are excellent in various properties such as pattern formability, plating resistance, peelability, high sensitivity, good resolution, and unexpectedly, Since the photosensitive laminate using the photosensitive resin composition of the present invention has good surface unevenness after peeling of the support, it is possible to form a pattern with high definition, a protective film, an interlayer insulating film, and It can be suitably used for various pattern formation such as a permanent pattern such as a solder resist pattern, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. In particular, it can be suitably used for forming a permanent pattern of a printed wiring board.
Since the method for forming a permanent pattern of the present invention uses the photosensitive resin composition of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, a color filter, and a column material. It can be suitably used for the production of liquid crystal structural members such as rib members, spacers, partition walls, holograms, micromachines, proofs, and the like, and particularly suitable for the formation of permanent patterns on printed wiring boards.
Further, since the printed wiring board of the present invention is obtained by the permanent pattern forming method of the present invention, it is possible to prevent external impact and conduction between adjacent electrodes, and a printed wiring board suitable for mounting precise electronic components. can get.

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 9 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 10 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 11 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 12 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 13 is a top view showing a positional relationship between an exposure area by two adjacent exposure heads and a corresponding slit. FIG. 14 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 15 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 12 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 16 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 17 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 18A is an explanatory diagram showing an example of magnification distortion. FIG. 18B is an explanatory diagram showing an example of beam diameter distortion. FIG. 19A is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 19B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 20 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 21A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 22 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads.

Explanation of symbols

10 Pattern forming device 12 Photosensitive layer (photosensitive material)
DESCRIPTION OF SYMBOLS 14 Moving stage 18 Installation stand 20 Guide 22 Gate 24 Scanner 26 Sensor 28 Slit 30 Exposure head 32 Exposure area 36 Digital micromirror device (DMD)
38 Fiber array light source 58 Micro mirror (picture element)
200 condenser lens

Claims (10)

It comprises a binder, a photopolymerization initiator, a thermal crosslinking agent, and a polymerizable compound, the binder contains an acid-modified vinyl group-containing epoxy resin, and the photopolymerization initiator is represented by the following general formula (1). The photosensitive resin composition characterized by containing the compound by which the said thermal crosslinking agent contains the epoxy compound which has a 2 or more epoxy group in 1 molecule.
In general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents an alkyl group, and R ³ represents a naphthyl group. R ¹ , R ² , and R ³ may be further substituted with a substituent. The acid-modified vinyl group-containing epoxy resin is a novolak type epoxy resin represented by the following general formula (A-1), a bisphenol type epoxy resin represented by the following general formula (A-2), and the following general formula (A- The photosensitive property according to claim 1, which is a resin obtained by reacting at least one epoxy resin selected from the group consisting of salicylaldehyde type epoxy resins represented by 3) with a vinyl group-containing monocarboxylic acid. Resin composition.


However, in general formula (A-1), (A-2), and (A-3), X represents either a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group ( The molar amount of the hydrogen atom / the molar amount of the glycidyl group represents 0/100 to 30/70, R represents one of a hydrogen atom and a methyl group, and n represents an integer of 1 or more. . The photosensitive resin composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by any one of the following general formulas (2) and (3).
However, in general formula (2) and (3), R < ¹ > represents either an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > represents an alkyl group. R ¹ and R ² may be further substituted with a substituent.   The photosensitive resin composition in any one of Claim 1 to 3 in which a photoinitiator contains photoinitiators other than the compound represented by General formula (1).   The photosensitive resin composition in any one of Claim 1 to 4 containing a sensitizer.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the solid content of the polymerizable compound is 2 to 50 mass% with respect to the total solid content of the acid-modified vinyl group-containing epoxy resin.   The photosensitive resin composition in any one of Claim 1 to 6 containing either an inorganic filler and an organic filler.   A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive resin composition according to claim 1 on the support.   A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive resin composition according to claim 1. A printed wiring board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 9.