JP2007262224A - Photo-polymerization initiator, photosensitive composition, photosensitive film, photosensitive layered product, permanent pattern forming method, and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-polymerization initiator that can further improve sensitivity of a photosensitive composition in order to correspond to laser light exposure, and can keep resolution, preservation stability, surface hardness, and dielectric properties in a good state, to provide a photosensitive composition using the same, a photosensitive film, and a photosensitive layered product, to provide a method for forming highly detailed permanent patterns such as a protective film, an interlayer insulation film, a solder resist pattern, etc., using the photosensitive layered product and to provide a printed wiring board whose pattern is formed by using the method for forming highly detailed permanent patterns. <P>SOLUTION: The photoinitiator comprises a compound represented by one of general formulae (1)-(5), more desirable is the case when the formula (1) is represented by formula (6). The photosensitive composition, a photosensitive film, and a photosensitive layered product containing the photoinitiator, etc., the method for forming a permanent pattern using the photosensitive layered product, and the printed wiring board whose pattern is formed by the method for forming the permanent pattern are disclosed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photopolymerization initiator capable of further improving sensitivity in a photosensitive composition so as to be compatible with laser exposure, a photosensitive composition using the same, a photosensitive film, and a photosensitive laminate. The present invention relates to a method for forming a body, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern), and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.

  In the field of printed wiring boards, components such as semiconductors, capacitors and resistors are soldered onto the printed wiring board. In this case, for example, in a soldering process such as IR reflow, in order to prevent the solder from adhering to an unnecessary part of soldering, a permanent pattern corresponding to the unnecessary part of soldering is used as a protective film and an insulating film. The method of forming is adopted. A solder resist is preferably used as the permanent pattern of the protective film.

  Here, in the formation of a permanent pattern, laser exposure is considered to be an excellent method for digitization and pattern miniaturization in recent years. However, in order to cope with laser exposure, the current liquid type is required to have higher sensitivity than the mainstream solder resist.

On the other hand, oxime esters are conventionally known as photopolymerization initiators and have been used in photosensitive compositions (see Patent Documents 1 to 4).
However, by simply replacing the oxime ester used in these conventional photosensitive compositions with a photosensitive composition for solder resist, a photosensitive composition having high sensitivity and high resolution and desired storage stability. Could not get. It is also necessary to maintain good surface hardness and dielectric properties of the formed pattern.

  Therefore, in order to be compatible with laser exposure, the oxime ester can be used to further improve the sensitivity of the photosensitive composition, and the resolution, storage stability, surface hardness, and dielectric properties are good. Photopolymerization initiator, photosensitive composition using the same, photosensitive film, photosensitive laminate, and high-definition permanent pattern using the photosensitive laminate (protective film, interlayer insulating film, and A method for forming a solder resist pattern and the like, and a printed board on which a pattern is formed by the permanent pattern forming method have not yet been provided, and further improvements are desired.

JP 60-166306 A JP 2001-233842 A International Publication No. 05/080337 Pamphlet JP 2000-80068 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can further improve the sensitivity of the photosensitive composition so as to be compatible with laser exposure, and maintain good resolution, storage stability, surface hardness, and dielectric properties. Photopolymerization initiator, photosensitive composition using the same, photosensitive film, photosensitive laminate, high-definition permanent pattern using the photosensitive laminate (protective film, interlayer insulating film, and solder resist) It is an object of the present invention to provide a method for forming a pattern and the like, and a printed circuit board on which a pattern is formed by the permanent pattern forming method.

  As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, the sensitivity of the photosensitive composition can be further improved so that the compound represented by any one of the following general formulas (1) to (5) can cope with laser exposure, and resolution, This is a finding that the surface hardness and dielectric properties can be kept good, and a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) can be formed.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> A photopolymerization initiator characterized by being a compound represented by any one of the following general formulas (1) to (5).
However, in the general formulas (1) to (5), the dotted double line represents either a single bond or a double bond. R ¹ represents any ^one of a hydrogen atom, an aliphatic group which may have a substituent, and an aryl group which may have a substituent, and R ² represents a hydrogen atom, ═O, ═NOCOY, a substituent. It represents either an aliphatic group which may have an aryl group which may have a substituent. R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , and R ²⁰ are the same as R ^1. , R ⁵ , R ⁸ , R ¹³ , and R ¹⁷ represent the same meaning as R ² . At least ^one of R ¹ and R ² and R ³ , R ⁴ and R ⁵ and R ⁶ , and R ⁷ and R ⁸ and R ⁹ may be bonded to form a ring, and R ¹² and R ¹³ R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring. A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , and A ⁸ independently represent any of a single bond, an oxygen atom, a sulfur atom, NHCO, and CONH. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ independently represent a hydrogen atom or any of the groups shown below, and X ¹ , X ² and X ^3, and X ⁴ and X ⁵ are all Except when it is a hydrogen atom. Y ¹ , Y ² , and Y ³ independently represent any of the groups shown below. G represents either an aliphatic group which may have a substituent or an aryl group which may have a substituent. J represents the same meaning as R ¹ .
<2> The photopolymerization initiator according to <1>, which is a compound represented by the general formula (1).
<3> The photopolymerization initiator according to any one of <1> to <2>, wherein the compound represented by the general formula (1) is further represented by the following general formula (6).
However, in said general formula (6), R <^21> , R <^22> , R <^23> , R <^24> , R <^25> and R < ²⁶ > represent the same meaning as R < ¹ > in general formulas (1) to (5), and A < ⁸ > represents the same meaning as ^{a 1} in the general formula (1) to (5), ^{Y 4} represents the same meaning as ^{Y 1} in the general formula (1) to (5). R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ²⁶ may be bonded to each other to form a ring.

<4> comprising (A) a binder, (B) a polymerizable compound, (C) the photopolymerization initiator according to any one of <1> to <3>, and (D) a thermal crosslinking agent. It is a photosensitive composition.
<5> (C) The photosensitive composition according to <4>, wherein the content of the photopolymerization initiator is 0.1 to 15% by mass.
<6> (A) The photosensitive composition according to any one of <4> to <5>, wherein the binder is an epoxy acrylate compound.
<7> The photosensitive composition according to any one of <4> to <5>, wherein (A) the binder contains at least one vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain. It is a thing.
<8> Any one of <4> to <5>, wherein (A) the binder includes at least one of an epoxy acrylate compound and a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. It is a photosensitive composition of description.
<9> The photosensitive composition according to any one of <4> to <8>, wherein the polymerizable compound (B) includes at least one selected from monomers having a (meth) acryl group.
<10> (D) The above <4, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. > To <9>.
<11> (E) The photosensitive composition according to any one of <4> to <10>, including a thermosetting accelerator.

<12> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of <4> to <11> on the support.
<13> When 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 0.1 to 500 mJ / cm ² . It is the photosensitive film as described in said <12>.
<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>, which has a protective film on the photosensitive layer.

<18> A photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of <4> to <11> on a substrate.
<19> The photosensitive laminate according to <18>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <12> to <17>.
<20> The photosensitive laminate according to any one of <18> to <19>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<21> A photosensitive layer in the photosensitive laminate according to any one of <18> to <20>,
A pattern forming apparatus comprising: a light irradiating unit capable of irradiating light; and a light modulating unit configured to modulate light from the light irradiating unit and to expose a photosensitive layer in the photosensitive laminate. It is. In the pattern forming apparatus according to <21>, 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.
<22> 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 <21> modulated according to. In the pattern forming apparatus according to <22>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit corresponds to a control signal generated by the pattern signal generation unit. Modulated.
<23> The light modulation means includes n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts. The pattern forming apparatus according to any one of <21> to <22>, which is controllable according to pattern information. In the pattern forming apparatus according to <23>, any less than n pixel parts arranged continuously from the n pixel parts in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<24> The pattern forming apparatus according to any one of <21> to <23>, wherein the light modulation unit is a spatial light modulation element.
<25> The pattern forming apparatus according to <24>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<26> The pattern forming apparatus according to any one of <23> to <25>, wherein the picture element portion is a micromirror.
<27> The pattern forming apparatus according to any one of <21> to <26>, wherein the light irradiation unit is capable of combining and irradiating two or more lights. In the pattern forming apparatus according to <27>, 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.
<28> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects laser beams irradiated from the plurality of lasers and couples them to the multimode optical fiber. <21> to the pattern forming apparatus according to any one of <27>. In the pattern forming apparatus according to <28>, 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.

<29> A method for forming a permanent pattern, comprising exposing the photosensitive layer in the photosensitive laminate according to any one of <18> to <20>.
<30> The method for forming a permanent pattern according to <29>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<31> The method for forming a permanent pattern according to any one of <29> to <30>, wherein the exposure is performed imagewise based on pattern information to be formed.

<32> 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 forming method according to any one of <29> to <31>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the permanent pattern forming method according to <32>, 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.
<33> The exposure is performed by a plurality of exposure heads, and the drawing element specifying unit is related to the exposure of the head-to-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 the above <32>, wherein among the element parts, the image element part used for realizing N double exposure in the inter-head connecting region is designated. In the permanent pattern forming method according to the above <33>, the exposure is performed by a plurality of exposure heads, and the used image element designating unit is an overlapping exposure region on the 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.
<34> 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 <33>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area in the image element area is designated. In the method for forming a permanent pattern according to <34>, 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.
<35> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel parts in the column direction, the interval p of the pixel parts in the column direction, 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 spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal <32> to <34>.
<36> The permanent pattern forming method according to any one of <32> to <35>, wherein N in N-fold exposure is a natural number of 3 or more. In the permanent pattern forming method according to <36>, multiple drawing is performed when N in N-fold 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.

<37> 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;
<32> to <36>, 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.
<38> The permanent pattern forming method according to any one of <32> to <37>, wherein the used pixel part specifying unit specifies, in line units, the used pixel part to be used for realizing N double exposure. It is.

<39> Based on at least two light spot positions detected by the light spot position detection means, an actual direction formed by 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. The inclination angle θ ′ is specified, and the picture element selection means selects the use picture element part 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.
<40> The actual 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 permanent pattern forming method according to <39>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<41> The pixel part selection means derives a natural number T close to t satisfying a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <37> to <40> in which the pixel elements in the first to the Tth rows are selected as the used pixel elements in a line element (where m represents a natural number of 2 or more). The permanent pattern forming method according to any one of the above.
<42> The pixel part selection means derives a natural number T close to t satisfying a 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 from line (T + 1) to 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 <37> to <41>, wherein the pixel part excluding the element part is selected as a use pixel part.

<43> In a region including at least an overlapped exposure region 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 <37>, which is one of means for selecting a used pixel portion so that the area of the underexposed region is minimized and no overexposed region is generated with respect to typical N double exposure <42> The permanent pattern forming method according to any one of the above.
<44> In the joint 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 <37> to <43>.
<45> The permanent pattern forming method according to <44>, wherein the unused pixel parts are specified in units of rows.

<46> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel elements, N (N-1) pixel element columns for N multiple exposures The permanent pattern forming method according to any one of <37> to <45>, wherein the reference exposure is performed using only the picture element portion that constitutes. In the permanent pattern forming method according to <46>, in order to specify the used pixel part in the used pixel part specifying unit, among 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.
<47> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, a pixel part row is formed every 1 / N lines for N of N multiple exposures. The permanent pattern forming method according to any one of <37> to <46>, wherein the reference exposure is performed by using only the pixel part. In the permanent pattern forming method according to <47>, 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. / A 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.

<48> From the above <32> to <47>, the used pixel part specifying unit includes a slit and a photodetector as a light spot position detecting unit, and an arithmetic unit connected to the photodetector as a pixel unit selecting unit. The permanent pattern forming method according to any one of the above.
<49> The method for forming a permanent pattern according to any one of <32> to <48>, wherein N in N-exposure is a natural number of 3 or more and 7 or less.

<50> The light modulation means further includes a 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. The method for forming a permanent pattern according to any one of <32> to <49>, wherein modulation is performed according to the method. In the pattern forming apparatus according to <50>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit corresponds to a control signal generated by the pattern signal generation unit. Modulated.
<51> The method for forming a permanent pattern according to any one of <32> to <50>, wherein the light modulator is a spatial light modulator.
<52> The method for forming a permanent pattern according to <51>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<53> The permanent pattern forming method according to any one of <32> to <52>, wherein the picture element portion is a micromirror.
<54> From the above <32> to <32> having conversion means for converting the pattern information so that the dimension of the predetermined part of the pattern represented by the pattern information matches the dimension of the corresponding part that can be realized by the designated used pixel part 53>. The method for forming a permanent pattern according to any one of No. 53>.

<55> The method for forming a permanent pattern according to any one of <32> to <54>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the permanent pattern forming method according to the above <55>, the light irradiation unit can synthesize and irradiate two or more lights, so that the 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.
<56> 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. <32> to the permanent pattern formation method according to any one of <55>. In the method for forming a permanent pattern according to <56>, the light irradiation 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.

<57> The method for forming a permanent pattern according to any one of <29> to <56>, wherein the photosensitive layer is developed after the exposure. In the method for forming a permanent pattern according to <57>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<58> The method for forming a permanent pattern according to <57>, wherein the permanent pattern is formed after the development.
<59> The method for forming a permanent pattern according to <58>, wherein after the development, the photosensitive layer is cured.
<60> The method for forming a permanent pattern according to <59>, 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.

<61> A permanent pattern formed by the pattern forming method according to any one of <29> to <60>. Since the permanent pattern according to <61> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition, and is a multilayer wiring board for semiconductors and components. This is useful for high-density mounting on PCBs and build-up wiring boards.
<62> The pattern according to <61>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in <62> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring may be subjected to an impact or bending from the outside due to the insulation property, heat resistance, etc. of the film. Protected from.

  <63> A printed circuit board wherein a permanent pattern is formed by the permanent pattern forming method according to any one of <29> to <60>.

  According to the present invention, the conventional problems can be solved and the sensitivity in the photosensitive composition can be further improved in order to be compatible with laser exposure, and the resolution, storage stability, surface can be improved. Photopolymerization initiator capable of maintaining good hardness and dielectric properties, photosensitive composition using the same, photosensitive film, photosensitive laminate, and high-definition permanent pattern using the photosensitive laminate (protection) Film, interlayer insulating film, solder resist pattern, etc.) and a printed circuit board on which a pattern is formed by the permanent pattern forming method can be provided.

(Photopolymerization initiator)
The photopolymerization initiator of the present invention is a compound represented by any one of the following general formulas (1) to (5).
However, in the general formulas (1) to (5), the dotted double line represents either a single bond or a double bond. R ¹ represents any ^one of a hydrogen atom, an aliphatic group which may have a substituent, and an aryl group which may have a substituent, and R ² represents a hydrogen atom, ═O, ═NOCOY, a substituent. It represents either an aliphatic group that may have an aryl group that may have a substituent. R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , and R ²⁰ are the same as R ^1. , R ⁵ , R ⁸ , R ¹³ , and R ¹⁷ represent the same meaning as R ² . At least ^one of R ¹ and R ² and R ³ , R ⁴ and R ⁵ and R ⁶ , and R ⁷ and R ⁸ and R ⁹ may be bonded to form a ring, and R ¹² and R ¹³ R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring. A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , and A ⁸ independently represent any of a single bond, an oxygen atom, a sulfur atom, NHCO, and CONH. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ independently represent a hydrogen atom or any of the groups shown below, and X ¹ , X ² and X ^3, and X ⁴ and X ⁵ are all Except when it is a hydrogen atom. Y ¹ , Y ² , and Y ³ independently represent any of the groups shown below. G represents either an aliphatic group which may have a substituent or an aryl group which may have a substituent. J represents the same meaning as R ¹ .

In the compounds represented by the general formulas (1) to (5), the aliphatic groups that may have a substituent represented by R ¹ , R ² , or G each have a substituent. And an alkyl group, an alkenyl group, and an alkynyl group.
Examples of the alkyl group that may have a substituent include linear, branched, and cyclic alkyl groups having 1 to 30 carbon atoms.
Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. .

Examples of the substituent of the alkyl group that may have a substituent include a substituent composed of a monovalent nonmetallic atom excluding a hydrogen atom.
Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy Group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group , Acylamino group, N-alkyl acyla Group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′- Alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl -N-alkylureido group, N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl -N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl- -Arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-ary carbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group _(-SO 3 H) And its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinaimoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonato group), dialkylphosphono group (— PO ₃ (alkyl) ₂ ) “alkyl = alkyl group, hereinafter the same”, diarylphospho Group (—PO ₃ (aryl) ₂ ) “aryl = aryl group, hereinafter the same”, alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ (alkyl)) ) And its conjugate base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H) ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono group _(-OPO 3 H _(alky )) And its conjugated base group (referred to as alkylphosphonato group), referred to as monoarylphosphono group (-OPO 3 H _(aryl)) and its conjugated base group (aryl phosphite Hona preparative group), a cyano group, Examples thereof include a nitro group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, and a silyl group.

  Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups. Specific examples of the aryl group in the substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxy Carbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulphonatophenyl group, phosphonopheny Groups, phosphonium Hona preparative phenyl group.

Examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like.
Examples of the alkynyl group in the substituent include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of the aryl group represented by R ¹ , R ² , or G include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring Is mentioned.
Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. In these, a phenyl group and a naphthyl group are more preferable.
In the aryl group, examples of the aryl group having a substituent include those having a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group.
Examples of preferred substituents include the alkyl groups described above and those previously shown as substituents in the substituted alkyl group.

  Preferable specific examples of the aryl group having a substituent include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and a trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Boxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonopheny Group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like.

  Among the compounds represented by the general formulas (1) to (5), the third to fifth atoms counted from the nitrogen atom constituting the bond between the nitrogen atom and the oxygen atom that are cleaved by light to form a free radical However, the compound represented by General formula (1) is preferable from the viewpoint of having an unsaturated bond with an atom adjacent to the side different from the nitrogen atom.

Moreover, as a compound represented by the said General formula (1), what forms a 5-7 membered ring with the said produced | generated free radical and the said unsaturated bond, for example is preferable, and this formed ring is adjacent. In the case where a ring structure is present at the position, it is more preferable that the number of the ring and the formed ring are different from the viewpoint of making it difficult to cause distortion in both.
The unsaturated bond is preferably at least one of an ethylenically unsaturated bond and an acetylenic unsaturated bond, excluding the carbonyl bond and the unsaturated bond that the aromatic group may have.

Here, “the third to fifth atoms counted from the nitrogen atom constituting a bond that is cleaved by light to generate a free radical” means a bond that is cleaved by light having a wavelength of 300 to 700 nm to generate a free radical. It means the 3rd to 5th atoms when counted from the constituent nitrogen atoms. The wavelength is preferably 350 to 600 nm.
It is generally known that a bond between a nitrogen atom and an oxygen atom is cleaved by light having a wavelength of 300 to 700 nm to generate a free radical. Forming the ring is, for example, irradiating the photosensitive layer obtained from the photosensitive composition containing the photopolymerization initiator with light having a wavelength of 300 to 700 nm, and the cyclized product is formed in the decomposition product. I can confirm that there is.

Among the compounds represented by the general formula (1), for example, a compound represented by the following general formula (6) is more preferable.
However, in said general formula (6), R <^21> , R <^22> , R <^23> , R <^24> , R <^25> and R < ²⁶ > represent the same meaning as R < ¹ > in general formulas (1) to (5), and A < ⁸ > represents the same meaning as ^{a 1} in the general formula (1) to (5), ^{Y 4} represents the same meaning as ^{Y 1} in the general formula (1) to (5). R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ²⁶ may be bonded to each other to form a ring.

Although there is no restriction | limiting in particular as a photoinitiator represented by the said General formula (6), For example, what is represented by the following compound examples 1-52 is mentioned suitably.

-Synthesis method-
Although there is no restriction | limiting in particular as a synthesis method of the said photoinitiator, For example, the method etc. which synthesize | combine in the order of the following (1) to (3) are mentioned.

(1) Put sodium hydride from which mineral oil has been removed into a three-necked flask, change to a nitrogen atmosphere, add a solution containing tetrahydrofuran (THF) from a dropping funnel, and then stir. At this time, diethyl carbonate may be added.
(2) After adding a solution of allyl bromide or propal bromide and tetodahydrofuran (THF) from a dropping funnel, stirring, adding water, extracting with ethyl acetate, and removing the solvent of the organic layer under reduced pressure The corresponding intermediate product of the compound of the present invention is obtained by purification by silica gel chromatography. At this time, sodium hydroxide, ethanol and water were added to the oily substance obtained by distillation under reduced pressure, the external temperature was set to about 75 ° C., and after stirring, hydrochloric acid was added and water was added. Also good.
(3) The intermediate product, hydroxyamine hydrochloride, potassium acetate and ethanol are placed in a recovery flask and refluxed. After completion of the reaction, water is added, the mixture is extracted with ethyl acetate, the organic layer is dried over magnesium sulfate, and evaporated under reduced pressure. Next, pyridine and acetonitrile are added to set the external temperature to about 0 ° C., and a solution of acetyl chloride and acetonitrile is added with a dropping funnel, followed by stirring. I) Water is added, and the mixture is extracted with ethyl acetate and organically extracted. The layer is dried over magnesium sulfate and evaporated under reduced pressure to obtain an oily compound of the present invention, or ii) crystals obtained by adding ice water are recrystallized from acetonitrile to give a white color of the compound of the present invention. Obtain crystals.
Moreover, you may perform the following reaction (0) before said (1).
(0) 1-naphthylaldehyde, malonic acid, piperidine, and pyridine are placed in a three-necked flask, refluxed, the reaction solution is placed in ice water, and the white solid is filtered. Next, this white solid is dissolved in methanol and ethyl acetate, palladium carbon is added, and the reaction is performed in a hydrogen atmosphere. After completion of the reaction, the reaction solution is filtered through Celite, and the solvent is distilled off under reduced pressure. Next, chlorobenzene and aluminum chloride are added, the external temperature is set to 0 ° C., the white solid and chlorobenzene are dropped from the dropping funnel, reacted, and ice water is added. The obtained white crystals are recrystallized from methanol to obtain an intermediate product corresponding to the intermediate product.

  The photopolymerization initiator of the present invention can further improve sensitivity so as to be compatible with laser exposure, and can maintain good resolution, storage stability, surface hardness, and dielectric properties. For this reason, protective films for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, color filters, pillar materials, rib materials, spacers, display members such as spacers, holograms, It can be widely used for forming permanent patterns such as micromachines, proofs, and adhesives, and can be particularly suitably used for the photosensitive composition, photosensitive film, photosensitive laminate, and permanent pattern forming method of the present invention.

(Photosensitive composition)
The photosensitive composition of the present invention comprises (A) a binder, (B) a polymerizable compound, (C) the photopolymerization initiator according to any one of claims 1 to 4, and (D) a thermal crosslinking agent. Preferably, it contains (E) a thermosetting accelerator, and further contains other components such as a color pigment, extender pigment, thermal polymerization inhibitor, and surfactant, if necessary.

[(A) Binder (polymer)]
As the binder, a compound exhibiting swelling property with respect to an alkaline aqueous solution is preferable, and a compound that is soluble in an alkaline aqueous solution is more preferable.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound. Compound (epoxy acrylate compound), vinyl copolymer having (meth) acryloyl group and acidic group in side chain, epoxy acrylate compound and vinyl copolymer having (meth) acryloyl group and acidic group in side chain And a mixture of maleamic acid and the like.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

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

  Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; NISSAN CHEMICAL INDUSTRY CO., LTD. "ALALDITE PT810; Ciba Specialty Chemicals" etc.), bisphenol A 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 phenol novolak type epoxy resin, glycidylamine type epoxy resin (eg, tetraglycidyldiaminodiphenylmethane), hydantoin Epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin ( “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink and Chemicals”, etc.), epoxy resins having a dicyclopentadiene skeleton (“HP -7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.); condensation of phenolic compounds such as phenol, o-cresol, naphthol and the like with aromatic aldehydes having a phenolic hydroxyl group (for example, p-hydroxybenzaldehyde) Anti Reaction product of polyphenol compound and epichlorohydrin obtained by the above; reaction product of polyphenol compound obtained by addition reaction of phenol compound and diolefin compound such as divinylbenzene and dicyclopentadiene and epichlorohydrin; 4-vinylcyclohexene-1- Epoxide of ring-opening polymer of oxide with peracetic acid or the like; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; NOF Corporation) And the like, and a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano. Cinnamic acid, acrylic acid dimer; in addition, addition reaction between a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride A reaction product with a halogen-containing carboxylic acid compound, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Furthermore, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1. Kyoeisha Yushi Chemical Co., Ltd. HOA-MP and HOA-MS, Osaka Organic Chemical Industry Co., Ltd. biscoat # 2100, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, and nonenyl succinic anhydride. , Maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot anhydride Acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylene Tetrahydro anhydride Dibasic acid anhydrides such as phosphoric acid, chlorendic anhydride and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, anhydrous Polybasic acid anhydrides such as pyromellitic acid and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid can also be used. These may be used individually by 1 type and may use 2 or more types together.
Each of them is reacted in order to obtain an epoxy acrylate, and the ratio of reacting them is preferably 0.8 to 1.2 equivalents of carboxyl groups of the carboxyl group-containing monomer with respect to 1 equivalent of epoxy groups of the polyfunctional epoxy compound. Is 0.9-1.1 equivalent, 0.1-1.0 equivalent of polybasic acid anhydride, preferably 0.3-1.0 equivalent.

  In addition, compounds obtained by adding the polybasic acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 are also used as the epoxy acrylate of the present invention. Available.

Among the compounds obtained by introducing an ethylenically unsaturated double bond and an acidic group into the epoxy compound, epoxy acrylate compounds represented by the following structural formulas (1) and (2) are preferable.
However, in said structural formula (1), X represents either a hydrogen atom and the substituent containing an acidic group at least, Y represents either a methylene group, an isopropylidene group, and a sulfonyl group, and n is The integer of 1-20 is represented.

However, in said structural formula (2), n represents the integer of 1-20.

The epoxy acrylate compound represented by the structural formula (1) is specifically represented by the bisphenol F-type epoxy acrylate compound represented by the following structural formula (3) and the following structural formula (4). Bisphenol A type epoxy acrylate compounds are more preferred.

  The mass average molecular weight of the epoxy acrylate compound is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. When the mass average molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may deteriorate. If it exceeds 100,000, the developability may deteriorate. Also, synthesis of the resin becomes difficult.

<Vinyl copolymer having (meth) acryloyl group and acid group in side chain>
Examples of the vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain include (1) a vinyl monomer having an acidic group, and (2) a function that can be used for a polymer reaction described later, if necessary. A (co) polymer obtained by vinyl (co) polymerization of a vinyl monomer having a group and (3) other copolymerizable vinyl monomer if necessary, and (4) the (co) polymer It is obtained by polymer-reacting a compound having a (meth) acryloyl group with a functional group having reactivity with at least one of an acidic group in the coalescence or a functional group available for polymer reaction.
There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has said (1) acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, These Among these, a carboxyl group is preferable. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and a monomer having a hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono ( And (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.
In the vinyl monomer having a functional group usable for the polymer reaction of (2), the functional group usable for the polymer reaction is a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. Moreover, the carboxyl group and acid anhydride group of the above-mentioned (1) are also mentioned as usable functional groups.

  Examples of the vinyl monomer having a hydroxyl group include compounds represented by the following structural formulas (5) to (13).

However, in the structural formulas (5) to (13), R ₁ represents a hydrogen atom or a methyl group, and n, n1, and n2 represent an integer of 1 or more.

  Examples of the vinyl monomer having an amino group include vinyl benzylamine and aminoethyl methacrylate.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (14) to (16).

However, in the structural formulas (14) to (16), R ¹ represents a hydrogen atom or a methyl group.

  Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (17).

However, in said structural formula (17), R represents either H or Me.

Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
As these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “Cyclomer (CYCLOMER) M-” 200; manufactured by Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; manufactured by Showa High Polymer Co., Ltd. "can be used.
Moreover, each said monomer may be used individually by 1 type, and may use 2 or more types together.

  The other copolymerizable monomer used as necessary in (3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters and crotonic acid. Esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes (eg, styrene, styrene derivatives, etc.), (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamide-2 -Methylpropanesulfonic acid, Vinyl monomers having mono (2-acryloyloxyethyl ester) acid, mono (1-methyl-2-acryloyloxyethyl ester) phosphate, and functional groups (for example, urethane group, urea group, sulfonamide group, imide group) Etc.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene Glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, dis Clopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, And tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include the styrene, the styrene derivatives (for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, Bromostyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like).

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing a vinyl monomer having a urethane group or a urea group as the functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group. Specifically, a monomer having an isocyanate group, and a hydroxyl group An addition reaction with a compound containing 1 or a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate. .

Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (14) to (16), as in the above-described (2).
Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.
Examples of the monomer having a hydroxyl group include compounds represented by the structural formulas (5) to (13) in the same manner as shown in (2) above.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamino) , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
By vinyl (co) polymerizing these, an (co) polymer containing an acid group, an acid anhydride group and, if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. can get. The vinyl (co) polymer can be prepared by copolymerizing corresponding monomers according to a conventional method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.
With respect to the (co) polymer thus obtained, as the above (4), an acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It is obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) acryloyl group.

As the compound having a (meth) acryloyl group and a functional group reactive to at least one of the acidic group in the (co) polymer of the above (4) or a functional group available for polymer reaction The compounds shown in (2) above can be used.
Examples of combinations of functional groups for performing these polymer reactions include, for example, a copolymer having an acidic group (such as a carboxyl group) and a vinyl monomer having an epoxy group, and a copolymer having an amino group Combination of vinyl monomer having epoxy group, combination of copolymer having amino group and vinyl monomer having isocyanate group, combination of copolymer having hydroxyl group and vinyl monomer having isocyanate group, copolymer having hydroxyl group and acid Combination of vinyl monomer having halide group, combination of copolymer having amino group and vinyl monomer having active halide group, combination of copolymer having acid anhydride group and vinyl monomer having hydroxyl group, having isocyanate group Combination of copolymer and vinyl monomer having amino group, isocyanate Combinations of vinyl monomer having a copolymer and a hydroxyl group with the combination of the vinyl monomer having a copolymer and an amino group having an active halide groups, and the like. Two or more of these combinations may be used in combination.

<Maleamic acid copolymer>
The maleamic acid-based copolymer is a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer. The copolymer is a maleamic acid copolymer having at least a maleamic acid unit B having a maleic acid half amide structure and a unit A having no maleic acid half amide structure, represented by the following structural formula (17). It is preferably a coalescence.
The unit A may be one type or two or more types. For example, assuming that the unit B is one type, when the unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit A is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
The unit A is an aryl group which may have a substituent and a vinyl monomer described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with the vinyl monomer (c) is preferred.

In the Structural Formula (17), R ³ and R ⁴ represents a hydrogen atom or a lower alkyl group. x and y represent the mole fraction of the repeating unit. For example, when the unit A is one, x is 85 to 50 mol%, and y is 15 to 50 mol%.

In the structural formula (17), as R ¹ , for example, (—COOR ¹⁰ ), (—CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (—OCOR ¹³ ), (—OR ¹⁴ ), substituents such as (—COR ¹⁵ ). Here, said R < ¹⁰ > -R < ¹⁵ > represents either a hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{10 to} R ¹⁵ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, and cyclohexyl. 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.
Specific examples of R ¹ include, for example, benzene derivatives such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl; n-propyloxycarbonyl, Examples include n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

Examples of R ² include an alkyl group, an aryl group, and an aralkyl group that may have a substituent. These may have a cyclic structure or a branched structure. Specific examples of R ² include, for example, benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, and α-methyl. Benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) Ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) Til, 4-fluoro-α, α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl, Ethyl, propyl, i-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3 -Methoxypropyl, 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropylamine and the like.

  The binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the glass transition temperature (Tg) of the homopolymer of the vinyl monomer. ) Is preferably a copolymer obtained by reacting a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a temperature of less than 80 ° C. A copolymer comprising the component (a) and the component (b) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties. Moreover, in the copolymer which consists of this (a) component and this (c) component, although lamination property can be ensured, it may become difficult to ensure the said surface hardness.

-(B) Aromatic vinyl monomer-
The aromatic vinyl monomer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the surface hardness of the photosensitive layer formed using the photosensitive composition of the present invention may be increased. A compound having a homopolymer glass transition temperature (Tg) of 80 ° C. or higher is preferable, and a compound having a temperature of 100 ° C. or higher is more preferable.
Specific examples of the aromatic vinyl monomer include, for example, styrene (homopolymer Tg = 100 ° C.), α-methylstyrene (homopolymer Tg = 168 ° C.), 2-methylstyrene (homopolymer Tg = 136 ° C.), 3-methylstyrene (homopolymer Tg = 97 ° C.), 4-methylstyrene (homopolymer Tg = 93 ° C.), 2,4-dimethylstyrene (homopolymer Tg = 112 ° C.) Preferred examples include derivatives. These may be used individually by 1 type and may use 2 or more types together.

-(C) Vinyl monomer--
The vinyl monomer is required to have a glass transition temperature (Tg) of a homopolymer of the vinyl monomer of less than 80 ° C., preferably 40 ° C. or less, and more preferably 0 ° C. or less.
Examples of the vinyl monomer include n-propyl acrylate (homopolymer Tg = −37 ° C.), n-butyl acrylate (homopolymer Tg = −54 ° C.), pentyl acrylate, or hexyl acrylate (homopolymer acrylate). Tg = −57 ° C.), n-butyl methacrylate (Tg of homopolymer = −24 ° C.), n-hexyl methacrylate (Tg of homopolymer = −5 ° C.), and the like. These may be used individually by 1 type and may use 2 or more types together.

-Primary amine compound-
Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1-hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2-chloro Benzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- ( 3-Chlorophenyl) ethyla Min, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, propylamine, 1 -Propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylaniline, anisi Gin, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3- Examples thereof include propoxypropylamine and 3-isopropoxypropylamine. Among these, benzylamine and phenethylamine are particularly preferable.
The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.

  The reaction amount of the primary amine compound needs to be 0.1 to 1.2 equivalents relative to the anhydride group, and preferably 0.1 to 1.0 equivalents. When the reaction amount exceeds 1.2 equivalents, the solubility may be significantly deteriorated when one or more primary amine compounds are reacted.

  The content of the (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, particularly preferably 20 to 40 mol%. When the content is less than 15 mol%, alkali developability cannot be imparted, and when it exceeds 50 mol%, alkali resistance deteriorates and synthesis of the copolymer becomes difficult, resulting in a normal permanent pattern. Formation may not be possible. In this case, the content of (b) the aromatic vinyl monomer and (c) the vinyl monomer having a glass transition temperature (Tg) of the homopolymer of less than 80 ° C. in the binder is 20 respectively. -60 mol% and 15-40 mol% are preferable. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.

  The molecular weight of the maleamic acid copolymer is preferably 3,000 to 500,000, more preferably 8,000 to 150,000. When the molecular weight is less than 3,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later. When the molecular weight exceeds 500,000, the photosensitive composition is heated and laminated. The fluidity of the resin tends to be low, and it may be difficult to ensure proper laminating properties, and the developability may deteriorate.

<Other binders>
As the other binder, a polyamide (imide) resin described in JP-A-11-288087, a polyimide precursor described in JP-A-11-282155, or the like can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

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

  The solid content in the solid content of the photosensitive composition of the binder is preferably 5 to 70% by mass, and more preferably 10 to 50% by mass. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. Sensitivity may decrease.

[(B) Polymerizable compound]
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, the polymerizable compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. A compound is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

[(C) Photopolymerization initiator]
The photopolymerization initiator includes the photopolymerization initiator of the present invention. Moreover, you may contain another photoinitiator as needed.

-Other photopolymerization initiators-
The other photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. It is preferable that it has photosensitivity to visible light, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and initiates cationic polymerization depending on the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 to 800 nm. The wavelength is more preferably 330 to 500 nm.

  Examples of other photopolymerization initiators include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thio compounds, ketones. Examples thereof include compounds and metallocenes. Among these, halogenated hydrocarbons having a triazine skeleton, ketone compounds, and hexaarylbiimidazole compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) 1,3,5-triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.
Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4 -Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compounds described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenyl) Ethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) Le) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2, 6-difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1, 3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) Examples include -4,6-bis (tribromomethyl) -s-triazine.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4 Oxadiazole and the like).

  Examples of the phosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, and the like. Is mentioned.

Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (3-methoxyphenyl) ) Biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4-methoxyphenyl) -4 , 4 ', 5,5'-tetraphenylbi Dazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-trifluoromethylphenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, compounds described in WO00 / 52529, and the like.
The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

Examples of the organic peroxide include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone.
Examples of the thio compound include 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-benzoylmethylene-3-methylnaphthothiazoline, and the like.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bis (dicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Benzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-dimethyl Amino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1 -Methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, Jill dimethyl ketal), and the like.

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

  Further, as photopolymerization initiators other than the above, N-phenylglycine and other polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethyl ketone, etc.), amines (for example, 4-dimethylamino) Ethyl benzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2-phthalimidoethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4 -Dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-di- Tilaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N- Methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, crystal violet lactone, leuco crystal violet, etc.), JP-A-53-133428, JP-B-57-1819, Examples thereof include compounds described in JP-A-57-6096 and US Pat. No. 3,615,455.

  The content of all the photopolymerization initiators including the oxime ester in the photosensitive layer is preferably 0.05 to 30% by mass, more preferably 0.1 to 15% by mass, and 0.1 to 10% by mass. Particularly preferred.

-Sensitizer-
In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means described later.
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
These compounds not only improve the sensitivity of the photosensitive layer, but also have a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation.

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. Examples thereof include a condensed ring compound, and at least two aromatic hydrocarbon rings and aromatic heterocycles. And at least one selected from amine-based compounds substituted with any of the above. Here, the condensed ring compound means a compound in which an aromatic ring or a heterocyclic ring is condensed.

Although there is no restriction | limiting in particular as said condensed ring type compound, For example, a hetero condensed ring type ketone compound and an acridine type compound are more preferable.
Examples of the hetero-fused ring compound include an acridone compound, a thioxanthone compound, and a coumarin compound.

Examples of the acridone compounds include acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (for example, 2-chloro-10-butylacridone) and the like. Can be mentioned.
Examples of the thioxanthone compound include thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, 2-chlorothioxanthone, Quantacure QTX, and the like.
Examples of the coumarin compound include 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- ( 2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 ′ -Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy -3- (3-pyridylcarbonyl) coumarin, 3-benzoyl- , 7-dipropoxycoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc. Examples include coumarin compounds described in each publication.

  Examples of the acridine compound include acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, and the like.

  Among the hetero-fused compounds, acridone compounds and thioxanthone compounds are particularly preferable.

  The amine compound substituted with any one of the at least two aromatic hydrocarbon rings and aromatic heterocycles is not particularly limited, but for example, at least represented by the following general formulas (I) to (III): Examples include compounds having a structure in which two aromatic rings are bonded to a nitrogen atom, and among these, triarylamine compounds are preferred.

However, in the general formulas (I) to (III), the rings A to G each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and the rings A and B , Ring D and Ring E, Ring F and Ring G may be bonded to each other to form a bonded ring containing N.
In the general formula (II), the linking group L represents a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the linking groups L and N are the aromatic hydrocarbon ring and aromatic group. And n represents an integer of 2 or more.
In the general formula (III), R represents an alkyl group which may have a substituent.
The rings A to G and the linking group L may have a substituent, and these substituents may be bonded to each other to form a ring.

In the general formulas (I) to (III), examples of the aromatic hydrocarbon ring represented by the rings A to G include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, and Indene rings and the like can be mentioned. Among these, a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable.
Examples of the aromatic heterocycle represented by rings A to G include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole. Ring, pyran ring, thiadizole ring, oxadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, etc., among which furan ring, thiophene ring, pyrrole ring, pyridine ring, oxazole ring, thiazole ring A furan ring, a thiophene ring, and a pyrrole ring are more preferable.

  Rings included in ring A, ring B, ring D, ring E, ring F, ring G, and linking group L may be bonded to each other to form a condensed ring containing N. In this case, An example is given of forming a carbazole ring containing an N atom to which the ring is attached. When a carbazole ring is formed, any of the rings A to G is exceptionally not a ring structure and may be an arbitrary substituent. In this case, the substituent has a substituent. An alkyl group which may be present is preferred.

Each of the rings A to G may have an arbitrary substituent at an arbitrary position, and these substituents may be bonded to each other to form a ring.
In the general formula (II), the linking group L is a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and N is an aromatic group of the linking group L. It is directly bonded to a hydrocarbon ring or aromatic heterocycle.

Examples of the aromatic hydrocarbon ring and aromatic heterocyclic ring contained in the linking group L include the same as those exemplified as the aromatic hydrocarbon ring and aromatic heterocyclic ring of rings A to G.
As the aromatic hydrocarbon ring contained in the linking group L, a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable.
The aromatic heterocyclic ring contained in the linking group L is preferably a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, an oxazole ring, a thiazole ring, a thiadizole ring, or an oxadiazole ring, a furan ring, a thiophene ring, or a pyrrole. A ring is more preferred.

  When the linking group L contains two or more of at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, these rings may be directly connected, or a divalent or higher valent linking group ( The linking group is not limited to a divalent or higher valent group but may include a divalent or higher valent atom). In this case, examples of the divalent or higher valent linking group include known alkylene groups such as an alkylene group represented by the following formula (a), an acetylene group represented by the following formula (b), an amine group, an O atom, S atom, ketone group, thioketone group, -C (= O) O-, amide group, Se, Te, P, As, Sb, Bi, Si, B and other metal atoms, aromatic hydrocarbon ring group, aromatic Examples include a heterocyclic group (unsaturated heterocyclic group), a non-aromatic heterocyclic group (saturated heterocyclic group), and any combination thereof.

However, m < ₃ > represents an integer greater than or equal to 1 in said Formula (a) and (b).

Examples of the linking group that can be sandwiched between at least one of the aromatic hydrocarbon ring and the aromatic heterocycle included in the linking group L include an alkylene group represented by the following formula (a) and a formula represented by the following formula (b). Acetylene group, amine group, O atom, S atom, ketone group, -C (= O) O-, amide group, aromatic hydrocarbon ring group, aromatic heterocyclic group, -C = N-, -C = N—N =, a saturated or unsaturated heterocyclic group is preferred, an alkylene group having 1 to 3 carbon atoms, —OCH ₂ O—, —OCH ₂ CH ₂ O—, —O—, a ketone group, a benzene ring A group, a furan ring group, a thiophene ring group, and a pyrrole ring group are more preferable.

  Moreover, in the said general formula (II), it is preferable that n is 2-5.

In the linking group L, it is desirable to provide an absorption maximum and appropriate absorption in the wavelength region of 350 to 430 nm by adjusting the combination of the aromatic hydrocarbon ring or aromatic heterocyclic ring and the unsaturated linking group.
The ring contained in the linking group L and the linking group for linking the rings may have an arbitrary substituent at an arbitrary position, and these substituents may be linked to each other to form a ring.

Examples of the optional substituent that the rings A to G and the linking group L may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a nitro group; a cyano group; Examples of the monovalent organic group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, a linear or branched alkyl group having 1 to 18 carbon atoms such as n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group A cycloalkyl group having 3 to 18 carbon atoms such as a straight chain or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cyclopentenyl A cycloalkenyl group having 3 to 18 carbon atoms such as cyclohexenyl group; methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, amyloxy group, a linear or branched alkoxy group having 1 to 18 carbon atoms such as a tert-amyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, a tert-octyloxy group; a methylthio group, an ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, amylthio group, tert-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, tert- C1-C18 linear or branched alkyl such as octylthio group O group; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; vinyloxy group, propenyloxy group, hexenyloxy Table with -COR ^11; linear or branched alkenyloxy group having 2 to 18 carbon atoms group or the like; alkenylthio group vinylthio group, propenylthio group, having 2 to 18 carbon atoms such as hexenyl thio group linear or branched Carboxyl group; acyloxy group represented by —OCOR ¹² ; amino group represented by —NR ¹³ R ¹⁴ ; acylamino group represented by —NHCOR ¹⁵ ; carbamate group represented by —NHCOOR ¹⁶ ; A carbamoyl group represented by —CONR ¹⁷ R ¹⁸ ; a carboxylic acid ester group represented by —COOR ¹⁹ ; —SO ₃ A sulfamoyl group represented by NR ²⁰ R ²¹ ; a sulfonic acid ester group represented by —SO ₃ R ²² ; a group represented by —C═NR ²³ ; a group represented by —C═N—NR ²⁴ R ^25. A saturated or unsaturated heterocyclic group such as a 2-thienyl group, a 2-pyridyl group, a furyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, or a tetrahydrothiophene dioxide group. It is done.

R ^{11 to} R ²⁵ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. Represents a group. In these substituent groups, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, alkylthio group, aryl group, aralkyl group, alkenyloxy group, and alkenylthio group are further substituted with a substituent. May be.

There are no particular restrictions on the substitution positions of these substituents in the rings A to G and the linking group L, and when there are a plurality of substituents, these may be the same or different. Also good.
Rings A to G and linking group L are unsubstituted or substituted as a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituted group. An optionally substituted alkenyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkenyloxy group, an optionally substituted alkenylthio group, an optionally substituted amino group, an optionally substituted acyl group, a carboxyl group, a group represented by -C = ^{NR 23,} the group represented by ^{-C = N-NR 24 R 25} , saturated Alternatively, it is preferably substituted with an unsaturated heterocyclic group. In the case of having a substituent, examples of the substituent include a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, and an optionally substituted group. A good alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted amino group, a group represented by —C═NR ²³ , —C═N—NR ²⁴ R; ^The group represented by ²⁵ and a saturated or unsaturated heterocyclic group are preferred.

  When the above optional substituents that the rings A to G and the linking group L may have are further substituted with arbitrary substituents, the substituents include methoxy group, ethoxy group, n-propoxy group, C1-C10 alkoxy groups such as iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group; methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, C2-C12 alkoxyalkoxy groups such as methoxybutoxy group; C3-C15 alkoxyalkoxyalkoxy such as methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, ethoxymethoxymethoxy group, and ethoxyethoxymethoxy group Group: 6 carbon atoms such as phenyl group, tolyl group, xylyl group 12 aryl groups (these may be further substituted with a substituent); aryloxy groups having 6 to 12 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group; vinyloxy group, allyloxy group, etc. C2-C12 alkenyloxy group; acyl group such as acetyl group, propionyl group; cyano group; nitro group; hydroxyl group; tetrahydrofuryl group; amino group; N, N-dimethylamino group, N, N-diethylamino An alkylamino group having 1 to 10 carbon atoms such as a group; an alkylsulfonylamino group having 1 to 6 carbon atoms such as a methylsulfonylamino group, an ethylsulfonylamino group and an n-propylsulfonylamino group; a fluorine atom, a chlorine atom and a bromine atom Halogen atoms such as methoxycarbonyl group, ethoxycarbonyl group, n-propo A C2-C7 alkoxycarbonyl group such as a sicarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group An alkylcarbonyloxy group having 2 to 7 carbon atoms such as n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group, n-butoxycarbonyloxy group And an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as tert-butoxycarbonyloxy group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as vinyl group, propenyl group and hexenyl group;

  The sensitizers represented by the general formulas (I) to (III) preferably have an appropriate absorption in the wavelength range of 390 to 430 nm, and preferably have an absorption maximum in the wavelength range of 330 to 450 nm. More preferably, it has an absorption maximum in the wavelength region of 430 nm. Therefore, the molecule preferably has at least one of four or more aromatic hydrocarbon rings and aromatic heterocycles, and has at least one of five or more aromatic hydrocarbon rings and aromatic heterocycles. It is more preferable.

  Specific examples of the compounds represented by the general formulas (I) to (III) are shown below, but are not limited thereto.

However, in said formula (I-1), R < ^{31 >} , R <^32> , R < ³³ > represents either of the following groups each independently.

However, in the formula (II-g), the bonding position is on any two benzene rings of the two terminal phenyl groups or the two terminal tolyl groups.

However, in said formula (II-j), R <^41> , R < ^{42 >} , R < ⁴³ > represents either of the following groups each independently.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  The content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and preferably 0.2 to 10% by mass with respect to all components in the photosensitive composition. Particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

[(D) Thermal crosslinking agent]
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used within a range that does not adversely affect the like.
Examples of the epoxy compound having at least two oxirane groups in one molecule include a bixylenol type or biphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) 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, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated Bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak Epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA”) -4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), epoxy resins having a dicyclopentadiene skeleton ("HP-7200, HP-7200H; manufactured by Dainippon Ink &Chemicals", etc.), glycidyl methacrylate Examples include, but are not limited to, copolymer epoxy resins (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and the like. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position in one molecule can be used. A compound containing an epoxy group substituted with a group (more specifically, a β-alkyl-substituted glycidyl group or the like) is particularly preferable.
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 70% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive resin composition and the ease of synthesis.

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

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

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

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; di-β-alkyl glycidyl ethers of biphenols such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol; Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ethers of binaphthol, di-β-alkyl glycidyl ethers of binaphthol; poly- of phenol-formaldehyde polycondensates β-alkyl glycidyl ether; poly-β-alkyl glycidyl ether of monoalkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ether of cresol-formaldehyde polycondensate; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of condensate; poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate Bisphenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether; phenol compound-divinylbenzene polyaddition product poly-β-alkyl glycidyl ether; The
Among these, β-alkyl glycidyl ether derived from a bisphenol compound and a polymer obtained from this and epichlorohydrin, and poly-β-alkyl glycidyl ether of a phenol compound-formaldehyde polycondensate are preferable.

  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 or oligomers or copolymers thereof, oxetane groups and novolak resins , Poly (p-hydroxystyrene), cardo-type bisphe And ether compounds with hydroxyl groups, such as siloles, calixarenes, calixresorcinarenes, silsesquioxanes, and the like, as well as unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. And a copolymer thereof.

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

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

[Thermosetting accelerator]
In order to accelerate the thermal curing of the epoxy acrylate compound in the binder, a conventionally known thermal curing accelerator can be blended. Examples of the thermosetting accelerator include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N. -Amine compounds such as dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzylammonium chloride; Block isocyanate compounds blocked with dimethylamine or the like; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4- Imidazole derivatives such as methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and the like, and bicyclic amidine compounds Salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine derivatives such as S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct; Etc. can be used. These may be used alone or in combination of two or more.
The thermosetting accelerator is not particularly limited as long as it can accelerate the thermosetting of the epoxy acrylate compound, and compounds other than those described above that can promote thermosetting may be used.

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

[Other ingredients]
Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other auxiliary agents ( For example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.

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

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

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

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

-Extender pigment-
If necessary, the photosensitive composition may be inorganic for the purpose of improving the surface hardness of the permanent pattern or keeping the linear expansion coefficient low, or keeping the dielectric constant or dielectric loss tangent of the cured film low. Pigments and organic fine particles can be added.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  The amount of the extender is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the photosensitive layer surface, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

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

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

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

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer made of the above-described photosensitive composition of the present invention on the support. These layers are laminated.

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

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

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable.

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

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention.
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 0.1 to 500 mJ / cm ² . preferably there, more preferably 0.1~100mJ / cm ^2, and particularly preferably 1~80mJ / cm ^2.
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 thickness of the cured layer and the thickness of the photosensitive layer before the exposure are within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring machine (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

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

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

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, 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. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator on the end face, and it is also preferable to use a material with low moisture permeability for packaging. The separator is particularly preferably a moisture-proof one or a desiccant-containing one.

  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 easily peeled off, and includes 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 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 alone or in combination of two or more. Moreover, you may add a well-known surfactant.

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

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

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

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

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

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

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

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

In the method for producing a photosensitive laminate 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 composition, photosensitive film, and photosensitive laminate of the present invention use the photopolymerization initiator of the present invention, sensitivity can be further improved, and resolution, storage stability, surface Hardness and dielectric properties can be kept good. For this reason, protective films for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, color filters, column materials, rib materials, spacers, display members such as partition walls, holograms, It can be widely used for forming a permanent pattern such as a micromachine or a proof, and can be particularly suitably used for forming a permanent pattern on a printed circuit board.

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

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

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer 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 analog exposure is not particularly limited and may be appropriately selected depending on the purpose.For example, a method of performing exposure with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like through a negative mask having a predetermined pattern. Can be mentioned.

  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.

For example, the wavelength of ultraviolet to visible light is preferably 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, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.
As shown in FIG. 8, the fiber array light source 38 includes a plurality of (for example, 14) laser modules 60, and one end of a multimode optical fiber 62 is coupled to each laser module 60. An optical fiber 64 having a cladding diameter smaller than that of the multimode optical fiber 62 is coupled to the other end of the multimode optical fiber 62. As shown in detail in FIG. 9, seven ends of the optical fiber 64 opposite to the multimode optical fiber 62 are arranged along the direction orthogonal to the scanning direction, and these are arranged in two rows to form the laser emitting unit 66. Is configured.

  As shown in FIG. 9, the laser emitting portion 66 constituted by the end portion of the optical fiber 64 is sandwiched and fixed between two support plates 68 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the optical fiber 64 for protection. The light exit end face of the optical fiber 64 has a high light density and is likely to collect dust and easily deteriorate. However, by arranging the protective plate as described above, it is possible to prevent the dust from adhering to the end face and to delay the deterioration. Can do.

  For example, as shown in FIG. 25, such an optical fiber is formed by coaxially connecting an optical fiber 64 having a length of 1 to 30 cm with a small cladding diameter at the tip portion on the laser light emission side of a multimode optical fiber 62 having a large cladding diameter. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 64 is fused and joined to the outgoing end face of the multimode optical fiber 62 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 64 a of the optical fiber 64 is the same as the diameter of the core 62 a of the multimode optical fiber 62.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused with an optical fiber having a small cladding diameter may be coupled to the output end of the multimode optical fiber 62 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 64 may be referred to as an emission end portion of the multimode optical fiber 62.

  The multimode optical fiber 62 and the optical fiber 64 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 62 and the optical fiber 64 are step index type optical fibers, and the multimode optical fiber 62 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 64 has a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

  In general, in the laser light in the infrared region, the propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm. However, the smaller the clad diameter, the deeper the focal depth, so the clad diameter of the optical fiber is preferably 80 μm or less, more preferably 60 μm or less. 40 μm or less is more preferable. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 64 is preferably 10 μm or more.

  The laser module 60 is composed of a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 arranged on the heat block 110, And LD7, collimator lenses L1, L2, L3, L4, L5, L6, and L7 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 200, and one multimode. And an optical fiber 62. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and the maximum output is also all the same (for example, 100 mW for the multimode laser and 30 mW for the single mode laser). As the GaN semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 to 450 nm may be used.

  As shown in FIGS. 27 and 28, the combined laser light source is housed in a box-shaped package 400 having an upper opening together with other optical elements. The package 400 includes a package lid 410 created so as to close the opening. After the degassing process, a sealing gas is introduced, and the package 400 and the package lid are closed by closing the opening of the package 400 with the package lid 410. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the reference numeral 410.

  A base plate 420 is fixed to the bottom surface of the package 400, and the heat block 110, a condensing lens holder 450 that holds the condensing lens 200, and the multimode optical fiber 62 are disposed on the top surface of the base plate 420. A fiber holder 460 that holds the incident end is attached. The exit end of the multimode optical fiber 62 is drawn out of the package from an opening formed in the wall surface of the package 400.

  A collimator lens holder 440 is attached to the side surface of the heat block 110, and the collimator lenses L1 to L7 are held. An opening is formed in the lateral wall surface of the package 400, and a wiring 470 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 28, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens L7 is numbered among the plurality of collimator lenses. is doing.

  FIG. 29 shows a front shape of a mounting portion of the collimator lenses L1 to L7. Each of the collimator lenses L <b> 1 to L <b> 7 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses L1 to L7 are closely arranged in the light emitting point arrangement direction so that the length direction is orthogonal to the light emitting point arrangement direction of the GaN-based semiconductor lasers LD1 to LD7 (left-right direction in FIG. 29).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each has a divergence angle in a direction parallel to or perpendicular to the active layer, for example, 10 ° or 30 °. Lasers that emit beams B1 to B7 are used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses L1 to L7 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses L1 to L7 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. In addition, each of the collimator lenses L1 to L7 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 200 is formed by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane in parallel planes, and is long in the arrangement direction of the collimator lenses L1 to L7, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. The condenser lens 200 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 200 is also formed by molding resin or optical glass, for example.

  In addition, since the light emitting means for illuminating the DMD uses a high-intensity fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, it has a high output and a deep depth of focus. A pattern forming apparatus can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.

  In addition, since the cladding diameter at the exit end of the optical fiber is smaller than the cladding diameter at the entrance end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources, and for example, emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources including optical fibers are arrayed can be used.

  Moreover, as a light irradiation means provided with a plurality of light emitting points, for example, as shown in FIG. 30, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on a heat block 110. An array can be used. Further, a chip-shaped multi-cavity laser 110 shown in FIG. 31A in which a plurality of (for example, five) light emitting points 111a are arranged in a predetermined direction is known. Since the multicavity laser 111 can arrange the light emitting points with high positional accuracy as compared with the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multi-cavity laser 111 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 111a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 31B, a plurality of multi-cavity lasers 111 are arranged on the heat block 110 in the same direction as the arrangement direction of the light emitting points 111a of each chip. A multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 32, a combined laser light source including a chip-shaped multicavity laser 111 having a plurality of (for example, three) emission points 111a can be used. The combined laser light source includes a multi-cavity laser 111, a single multi-mode optical fiber 62, and a condenser lens 200. The multicavity laser 111 can be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the multicavity laser 111 is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 111 a of the multicavity laser 111 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 62, and a focal point substantially equal to the core diameter of the multimode optical fiber 62 is formed as the condenser lens 200. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multicavity laser 111 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode optical fiber 62 can be increased. it can.

  As shown in FIG. 33, a multi-cavity laser 111 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 111 are equidistant from each other on the heat block 110. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 111 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 111a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 111, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the plurality of multi-cavity lasers 111 is condensed in a predetermined direction by the rod lens 113 and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. As shown in FIGS. 34A and 34B, this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180 and is housed between two heat blocks. A space is formed. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 111 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 111a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 111, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 111a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the divergence angle of the laser beam is large (the fast axis direction), and the width direction of each collimating lens is the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser beam emitting side of the collimating lens array 184, there is one multimode optical fiber 62 and a condensing lens 200 that condenses and couples the laser beam to the incident end of the multimode optical fiber 62. Is arranged.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111a of the plurality of multi-cavity lasers 111 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and collected. The light is collected by the optical lens 200 and is incident on the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be configured, so that it is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.

  A laser module in which each of the combined laser light sources is housed in a casing and the emission end portion of the multimode optical fiber 62 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

<< 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, the set inclination angle θ may be an angle of about 0.50 degrees, for example. 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 exposure heads 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 relative mounting angle error between them and realizing 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, the set inclination angle θ may be an angle of about 0.50 degrees, for example. 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, the influence of the deviation of the relative mounting angle error and the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ is an explanatory view showing an example of unevenness that occurs in the pattern on the exposed surface.

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.
Furthermore, in the example of FIG. 18, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head to be 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 and the attachment of each exposure head Variations in resolution and density unevenness due to angle errors and relative mounting angle errors between 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.

[Curing process]
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a UV exposure machine such as an ultra-high pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine and the like are preferable. Listed. The exposure amount is usually 10 to 2,000 mJ / cm ² .

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

-Protective film, interlayer insulation film, solder resist pattern formation method-
When the pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, a permanent pattern is formed on a printed wiring board by the permanent pattern forming method. Then, soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern of the hardened layer functions as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

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

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

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Synthesis Example 1)
-Synthesis of Compound Example 1-
Into a 100 ml three-necked flask was added 2.2 parts by mass of sodium hydride (mineral oil removed), and after changing to a nitrogen atmosphere, 30 parts by mass of tetrahydrofuran (THF) was added. Next, a solution of 12 parts by mass of propiophenone and 30 parts by mass of THF was added from the dropping funnel over 1 hour. Then, it stirred for 1 hour. The intermediate product was obtained in an amount of 3.2 parts by mass by means of a liquid gel column chromatography (hexane / ethyl acetate = 9/1).
Next, a solution of 12 parts by mass of allyl bromide and 15 parts by mass of THF was added from the dropping funnel over 1 hour. Thereafter, the mixture was stirred for 1 hour, 150 parts by mass of water was added, and 50 parts by mass of ethyl acetate was added for extraction. The solvent of the organic layer was distilled off under reduced pressure and the residue was produced by silica gel column chromatography (hexane / ethyl acetate = 9/1) to obtain 5.2 parts by mass of the following intermediate product A.
5.2 parts by mass of this intermediate product, 4 parts by mass of hydroxyamine hydrochloride, 6 parts by mass of potassium acetate, and 30 parts by mass of ethanol were placed in a 100 ml eggplant flask and refluxed for 2 hours. After completion of the reaction, 150 parts by mass of water was added, the mixture was extracted with 50 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 6 parts by mass of pyridine and 30 parts by mass of acetonitrile were added to set the external temperature to 0 ° C., and a solution of 4 parts by mass of acetyl chloride and 20 parts by mass of acetonitrile was added using a dropping funnel over 30 minutes. The mixture was then stirred for 1 hour, 150 parts by mass of water was added, extraction was performed with 50 parts by mass of ethyl acetate, the organic layer was dried over magnesium sulfate, and evaporated under reduced pressure to obtain 2.8 parts of an oily compound (Compound Example 1). Part (yield 14%) was obtained.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 7.49-7.37 (m, 4H), 7.20-7.16 (m, 1H), 5.88-5.68 (m, 1H), 5.09-5.02 (m, 2H) ), 3.51-3.42, 3.00-2.92 (m, 1H), 2.52-2.38 (m, 1H), 2.33-2.08 (m, 2H), 2 .26 (s, 3H), 1.23 (dd, 1H)

(Synthesis Example 2)
-Synthesis of Compound Example 3-
Sodium hydride 2.6 parts by mass (mineral oil removed) was placed in a 100 ml three-necked flask, and after changing to a nitrogen atmosphere, 50 parts by mass of THF and 20 parts by mass of dimethylacetamide were added. Next, 8.3 parts by mass of diethyl carbonate was added.
The external temperature was set to 50 ° C., and a solution of 7 parts by mass of 1-indanone and 8 parts by mass of THF was added from the dropping funnel over 1 hour. Then, it stirred for 1 hour.
Next, a solution of 13 parts by mass of allyl bromide and 15 parts by mass of THF was added from the dropping funnel over 1 hour. Thereafter, the mixture was stirred for 1 hour, 150 parts by mass of water was added, and 50 parts by mass of ethyl acetate was added for extraction. To the oily substance obtained by distilling off the solvent of the organic layer under reduced pressure, 4.6 parts by mass of 48% aqueous sodium hydroxide solution, 20 parts by mass of ethanol and 20 parts by mass of water were added, and the external temperature was set to 75 ° C. And stirred for 2 hours. Then, after adding 7 mass parts of 12 N hydrochloric acid, 200 mass parts of water was added. Extraction was performed with 50 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 3.2 parts by mass of the following intermediate product B was obtained by producing by silica gel column chromatography (hexane / ethyl acetate = 9/1).
3.2 parts by mass of this intermediate product, 2 parts by mass of hydroxyamine hydrochloride, 3 parts by mass of potassium acetate and 50 parts by mass of ethanol were placed in a 100 ml eggplant flask and refluxed for 2 hours. After completion of the reaction, 150 parts by mass of water was added, the mixture was extracted with 50 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 2 parts by mass of pyridine and 30 parts by mass of acetonitrile were added to set the external temperature to 0 ° C., and a solution of 1.5 parts by mass of acetyl chloride and 20 parts by mass of acetonitrile was added using a dropping funnel over 30 minutes. Thereafter, the mixture was stirred for 1 hour, and 100 parts by mass of ice water was added. The crystals obtained were recrystallized and purified with acetonitrile to obtain 2.8 parts by mass (yield 23%) of white crystals (Compound Example 3).
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 8.25, 7.87 (dd, 1H), 7.50-7.30 (m, 3H), 5.89-5.68 (m, 1H), 5.14-5.03 (m, 2H) ), 3.62-3.54, 3.27-3.15 (m, 1H), 2.90-2.81 (m, 1H), 2.75-2.61 (m, 1H), 2 .31, 2.26 (s, 3H)

(Synthesis Example 3)
-Synthesis Example of Compound Example 4-
A 300 ml three-necked flask was charged with 30 parts by mass of 1-naphthylaldehyde, 30 parts by mass of malonic acid, 5 parts by mass of piperidine and 100 parts by mass of pyridine, and refluxed for 3 hours. The reaction solution was put into 1000 parts by mass of ice water to obtain a white solid by filtration. Next, this white solid was dissolved in 50 parts by mass of methanol and 50 parts by mass of ethyl acetate, 5 parts by mass of palladium carbon (Pd content 10%) was added, and the reaction was performed in a hydrogen atmosphere for 5 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. Next, 150 parts by mass of chlorobenzene and 40 parts by mass of aluminum chloride were added, the external temperature was set to 0 ° C., and the white solid obtained above and 50 parts by mass of chlorobenzene were added dropwise from the dropping funnel in 30 minutes. Then, it was made to react for 2 hours and 1000 mass parts of ice water was added. The obtained white crystals were recrystallized from methanol to obtain 25 parts by mass (yield 68%) of the following intermediate product C.
Sodium hydride 0.87 parts by mass (mineral oil removed) was placed in a 100 ml three-necked flask, and after changing to a nitrogen atmosphere, 10 parts by mass of THF and 5 parts by mass of dimethylacetamide were added. Next, 2.4 parts by mass of diethyl carbonate was added.
The external temperature was set to 50 ° C., and a solution of 3 parts by mass of α-tetralone and 10 parts by mass of THF was added from the dropping funnel over 1 hour. The mixture was then stirred for 1 hour.
Next, a solution of 3 parts by mass of allyl bromide and 10 parts by mass of THF was added from the dropping funnel over 1 hour. Thereafter, the mixture was stirred for 1 hour, 100 parts by mass of water was added, and 30 parts by mass of ethyl acetate was added for extraction. To the oily substance obtained by distilling off the solvent of the organic layer under reduced pressure, 2.5 parts by mass of 48% aqueous sodium hydroxide solution, 15 parts by mass of ethanol and 15 parts by mass of water were added, and the external temperature was set to 75 ° C. And stirred for 2 hours. Thereafter, 4 parts by mass of 12N hydrochloric acid was added, and then 100 parts by mass of water was added. Extraction was performed with 30 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and evaporated under reduced pressure. Next, the product was produced by silica gel column chromatography (hexane / ethyl acetate = 7/3) to obtain 2.2 parts by mass of the following intermediate product D.
2.2 parts by mass of this intermediate product, 0.7 parts by mass of hydroxyamine hydrochloride, 1.2 parts by mass of potassium acetate, and 20 parts by mass of ethanol were placed in a 100 ml eggplant flask and refluxed for 2 hours. After completion of the reaction, 100 parts by mass of water was added, extraction was performed with 80 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 0.5 parts by mass of pyridine and 20 parts by mass of acetonitrile were added to set the external temperature to 0 ° C., and a solution of 0.5 parts by mass of acetyl chloride and 5 parts by mass of acetonitrile was added with a dropping funnel over 10 minutes. . Thereafter, the mixture was stirred for 1 hour, 100 parts by mass of water was added and extracted with 30 parts by mass of ethyl acetate, and the solvent was distilled off under reduced pressure to obtain 0.84 parts by mass of an oily compound (Compound Example 4) (yield 18%). Got.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 9.05 (t, 1H), 7.92 (q, 2H), 7.71-7.62 (m, 1H), 7.58-7.50 (m, 1H), 7.45 (dd, 1H), 5.84-5.70 (m, 1H), 5.17-5.01 (m, 1H), 3.78-3.71, 3.58-3.49 (m, 1H), 3.32 (dd, 1H), 2.92 (dd, 1H), 2.77-2.66 (m, 1H), 2.36 (s, 3H), 2.34-2.27 (m, 1H)

(Synthesis Example 4)
-Synthesis of Compound 7-
Into a 300 ml three-necked flask was added 11 parts by mass of sodium hydride (mineral oil removed), and after changing to a nitrogen atmosphere, 70 parts by mass of THF and 40 parts by mass of dimethylacetamide were added. Next, 48.5 parts by mass of diethyl carbonate was added.
The external temperature was set to 50 ° C., and a solution of 30 parts by mass of α-tetralone and 45 parts by mass of THF was added from the dropping funnel over 1 hour. The mixture was then stirred for 1 hour.
Next, a solution of 30.2 parts by mass of allyl bromide and 30 parts by mass of THF was added from the dropping funnel over 1 hour. Thereafter, the mixture was stirred for 1 hour, 300 parts by mass of water was added, and 100 parts by mass of ethyl acetate was added for extraction. To the oily substance obtained by distilling off the solvent of the organic layer under reduced pressure, 33 parts by mass of a 48% aqueous sodium hydroxide solution, 80 parts by mass of ethanol and 80 parts by mass of water were added, and the external temperature was set to 75 ° C. Stir for hours. Then, after adding 90 mass parts of 12 N hydrochloric acid, 1000 mass parts of water was added. Extraction was performed with 100 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and evaporated under reduced pressure. Next, the product was produced by silica gel column chromatography (hexane / ethyl acetate = 9/1) to obtain 17.5 parts by mass of the following intermediate product E1.
17.5 parts by mass of this intermediate product, 18 parts by mass of hydroxyamine hydrochloride, 27 parts by mass of potassium acetate and 80 parts by mass of ethanol were placed in a 200 ml eggplant flask and refluxed for 2 hours. After completion of the reaction, 300 parts by mass of water was added, extraction was performed with 80 parts by mass of ethyl acetate, the organic layer was dried over magnesium sulfate, and evaporated under reduced pressure. Next, 8 parts by mass of pyridine and 50 parts by mass of acetonitrile were added, the external temperature was set to 0 ° C., and a solution of 7 parts by mass of acetyl chloride and 30 parts by mass of acetonitrile was added using a dropping funnel over 30 minutes. Thereafter, the mixture was stirred for 1 hour, added with 500 parts by mass of water and extracted with 50 parts by mass of ethyl acetate, and the solvent was distilled off under reduced pressure to obtain 16 parts by mass (yield 48%) of an oily compound (Compound Example 7). It was.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 8.14 (d, 1H), 7.34 (t, 1H), 7.25 (d, 1H), 7.18 (t, 1H), 5.88-5.75 (m, 1H), 5 .07 (d, 2H), 3.63-3.55 (m, 1H), 3.01-2.90 (m, 1H), 2.74-2.69 (m, 1H), 2.41 -2.20 (m, 2H), 2.27 (s, 3H), 1.98-1.92 (m, 2H)

(Synthesis Example 5)
-Synthesis of Compound 9-
Into a 300 ml three-necked flask, 7.2 parts by mass of sodium hydride (mineral oil removed) was put, and after changing to a nitrogen atmosphere, 40 parts by mass of THF and 30 parts by mass of dimethylacetamide were added. Next, 26 parts by mass of diethyl carbonate was added.
The external temperature was set to 50 ° C., and a solution of 20 parts by mass of α-tetralone and 30 parts by mass of THF was added from the dropping funnel over 1 hour. The mixture was then stirred for 1 hour.
Next, a solution of 21 parts by mass of propargyl bromide and 20 parts by mass of THF was added from the dropping funnel over 1 hour. Thereafter, the mixture was stirred for 1 hour, 300 parts by mass of water was added, and 100 parts by mass of ethyl acetate was added for extraction. To the oily substance obtained by distilling off the solvent of the organic layer under reduced pressure, 24.1 parts by mass of 48% aqueous sodium hydroxide solution, 45 parts by mass of ethanol and 50 parts by mass of water were added, and the external temperature was set to 75 ° C. Stir for 2 hours. Thereafter, 30 parts by mass of 12N hydrochloric acid was added, and then 1000 parts by mass of water were added. Extraction was performed with 100 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and evaporated under reduced pressure. Next, by producing by silica gel column chromatography (hexane / ethyl acetate = 9/1), the following intermediate product F11 parts by mass was obtained.
11 parts by mass of this intermediate product, 7 parts by mass of hydroxyamine hydrochloride, 12 parts by mass of potassium acetate and 80 parts by mass of ethanol were placed in a 200 ml eggplant flask and refluxed for 2 hours. After completion of the reaction, 300 parts by mass of water was added, extraction was performed with 50 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 5.4 parts by mass of pyridine and 50 parts by mass of acetonitrile were added to set the external temperature to 0 ° C., and a solution of 4.7 parts by mass of acetyl chloride and 20 parts by mass of acetonitrile was added over 30 minutes with a dropping funnel. . Thereafter, the mixture was stirred for 1 hour, and 500 parts by mass of ice water was added, and the resulting crystals were recrystallized and purified with acetonitrile to obtain 9 parts by mass (yield 27%) of white crystals (Compound Example 9).
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 8.15 (d, 1H), 7.36 (t, 1H), 7.24-7.17 (m, 2H), 3.75-3.68 (m, 1H), 3.04-2. 92 (m, 1H), 2.81-2.71 (m, 1H), 2.60-2.51 (m, 1H), 2.60-2.51 (m, 1H), 2.44- 2.22 (m, 2H), 2.30 (s, 3H), 2.07-1.95 (m, 2H)

(Synthesis Example 6)
-Synthesis of acrylic resin (B)-
A mixed solution consisting of 45.1 parts by weight of methyl methacrylate, 47.3 parts by weight of methacrylic acid, 1 part by weight of azoisovaleronitrile, and 215 parts by weight of propylene glycol monomethyl ether was placed in a reaction vessel at 90 ° C. in a nitrogen gas atmosphere. It was added dropwise over time. Reaction was carried out for 4 hours after the dropwise addition to obtain acrylic resin (b).
Next, 35.9 parts by mass of glycidyl methacrylate, 0.2 part by mass of hydroquinone monomethyl ether and 1 part by mass of triphenylphosphine are added to the obtained acrylic resin (b) solution, and air is blown at 80 ° C. Reaction for 8 hours, an acrylic resin (B) solution having an unsaturated group as a binder (solid content acid value: 104, mass average molecular weight (Mw); 20,000, double bond equivalent 2.0
mmol / g, 37% by mass solution of propylene glycol monomethyl ether).

Example 1
-Preparation of photosensitive composition-
A photosensitive composition was prepared based on the following composition. In addition, it prepared by kneading | mixing with 3 rolls, using methyl ethyl ketone as a solvent and making solid content concentration 55 mass%.
[Composition of photosensitive composition solution]
Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) ... 33.4 parts by mass Binder represented by the following formula (A) ... 40.0 parts by mass 2,2-bis (4-glycidylphenyl) propane ( Thermal crosslinking agent) ... 15.7 parts by weight Dipentaerythritol hexaacrylate ... 16.0 parts by weight Compound Example 1 (photopolymerization initiator) ... 2.0 parts by weight Hydroquinone monomethyl ether ... 0. 056 parts by mass Dicyandiamide (amine-based thermosetting agent) 0.77 parts by mass 2MAOK (2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid Addendum, manufactured by Shikoku Chemicals Co., Ltd.) ... 0.47 parts by mass

However, in said formula (A), n is about 6-7.

-Production of photosensitive film-
The obtained photosensitive composition was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 μm as the support and dried to form a photosensitive layer having a thickness of 30 μm. Next, a 12 μm-thick polypropylene film was laminated as a protective film on the photosensitive layer to produce a photosensitive film.

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

--Exposure process--
With respect to the photosensitive layer in the prepared photosensitive laminate, from a polyethylene terephthalate film (support) side, a laser exposure apparatus is used to obtain a pattern in which holes having different diameters are formed using a laser beam of 405 nm. Were exposed to light, and a partial region of the photosensitive layer was cured.

--Development process--
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1% by mass aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Was used for shower development at 30 ° C. for 60 seconds to dissolve and remove uncured regions. Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the photosensitive laminate on which the permanent pattern was formed was heated at 160 ° C. for 60 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.

  The manufactured photosensitive film was evaluated for exposure sensitivity, resolution, and storage stability, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. The results are shown in Table 1.

<Measurement of the shortest development time>
In the produced photosensitive film, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is applied to the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying of the aqueous sodium hydrogen carbonate 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.

<Exposure sensitivity>
In the photosensitive film described above produced, the polyethylene terephthalate film from (support) side, the light energy different light at ^{2 1/2} times the interval from 0.1 mJ / cm ² using an exposure apparatus to 100 mJ / cm ² Were exposed to light to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive film, and an aqueous sodium hydrogen carbonate solution (30 ° C., 1% by mass) is applied to the entire photosensitive layer on the copper-clad laminate. Spraying was performed for twice the shortest development time determined by the above method, and the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was the same as that before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.
The amount of light energy necessary for curing the photosensitive layer obtained as a result is shown in Tables 3 to 9.

<Resolution>
The surface of the obtained printed circuit board on which the permanent pattern was formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. The smaller the numerical value, the better the resolution. As a result, the resolution was 70 μm.

<Storage stability>
After the forced aging of the produced photosensitive film at 40 ° C. for 3 days, the shortest development time of the unexposed film was measured, and the storage stability was evaluated based on the following criteria.
〔Evaluation criteria〕
A: Development time is within 30 seconds, and storage stability is extremely excellent.
○: The development time is more than 30 seconds and within 45 seconds, and the storage stability is excellent.
Δ: Development time exceeds 45 seconds and within 60 seconds, and storage stability is poor.
X: The development time exceeds 60 seconds, and the storage stability is extremely poor.

<Pencil hardness>
The printed wiring board on which the permanent pattern had been formed was subjected to gold plating according to a conventional method and then subjected to a water-soluble flux treatment. Subsequently, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JISK-5400.
As a result, the pencil hardness was 5H or more. Further, when visually observed, no peeling, blistering, or discoloration of the cured film in the permanent pattern was observed.

<Measurement of dielectric properties>
The dielectric constant and dielectric loss tangent at 1 GHz were measured for the dielectric properties of the cured film having a thickness of 500 μm at 25 ° C. using an LCR meter manufactured by Agilent Technologies and a 4291A type solid electrode.

(Example 2)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 3, and in the same manner as in Example 1, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 1.

(Example 3)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 4, and in the same manner as in Example 1, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 1.

Example 4
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 7, and in the same manner as in Example 1, the photosensitive film and A photosensitive laminate was prepared to form a permanent pattern.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 1.
The photopolymerization initiator was irradiated with light having a wavelength of 405 nm on the resulting photosensitive layer, and it was confirmed that a 5-membered ring was present in the decomposition product.

(Example 5)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 9, and in the same manner as in Example 1, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 2.

(Example 6)
In Example 1, 40.0 parts by mass of the binder represented by the structural formula (A) in the photosensitive composition, 20.0 parts by mass of the binder represented by the structural formula (A), and the synthesis example A photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to 20 parts by mass of the acrylic resin (B) having an unsaturated group obtained in Step 6. The photosensitive film was prepared in the same manner as in Example 1. And the photosensitive laminated body was prepared and the permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 2.

(Example 7)
In Example 6, a photosensitive composition was prepared in the same manner as in Example 6 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 3, and in the same manner as in Example 6, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 6, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 2.

(Example 8)
In Example 6, a photosensitive composition was prepared in the same manner as in Example 6 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 4, and in the same manner as in Example 6, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 6, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 2.

Example 9
In Example 6, a photosensitive composition was prepared in the same manner as in Example 6 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 7, and in the same manner as in Example 6, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 6, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 3.

(Example 10)
In Example 6, a photosensitive composition was prepared in the same manner as in Example 6 except that the photopolymerization initiator was changed from Compound Example 1 to Compound Example 9, and in the same manner as in Example 6, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 6, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 3.

(Example 11)
The exposure sensitivity, resolution, and storage stability of the photosensitive composition and photosensitive film produced in the same manner as in Example 1 except that the exposure apparatus in Example 6 was replaced with the pattern forming apparatus described below. The pencil hardness and dielectric properties of the formed permanent pattern were evaluated. The results are shown in Table 3.

<< Pattern Forming Apparatus >>
8-9 and 25-29 as the light irradiating means, and 1024 micromirrors 58 arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. DMD 36 controlled to drive only 1024 × 256 rows among 768 pairs of mirror rows arranged in the sub-scanning direction, and optical for imaging the light shown in FIGS. 5A and 5B on the pattern forming material A pattern forming apparatus 10 including an exposure head 30 having a system 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. 18, 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 pattern forming material 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. 18, 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.

As shown in FIG. 18, 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 natural number T closest to the value t satisfying the relationship is 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. 19 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 by the oblique lines in FIG. 19 were similarly covered by 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.

(Example 12)
In Example 3, a photosensitive composition was prepared in the same manner as in Example 3 except that the addition amount of the photopolymerization initiator was changed to 0.08 parts by mass. In the same manner as in Example 3, the photosensitive film and A photosensitive laminate was prepared and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the produced photosensitive film were evaluated in the same manner as in Example 3, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. The results are shown in Table 3.

(Example 13)
The substrate was prepared by subjecting the surface of a copper-clad laminate (no through-hole, copper thickness 12 μm) on which wiring was formed as a printed circuit board to a chemical polishing treatment. On the copper clad laminate, the photosensitive composition of Example 1 was applied by screen printing using a 120 mesh Tetron screen so that the thickness after drying was 30 μm, and hot air was heated at 80 ° C. for 15 minutes. A photosensitive layer was formed by drying with a circulation dryer, and a photosensitive laminate in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared.

  The photosensitive laminate was subjected to laser exposure in the same manner as in Example 1 to evaluate exposure sensitivity, resolution, and storage stability, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 4.

(Example 14)
In Example 1, instead of the pattern forming apparatus, a glass negative mask having the same pattern as this was separately prepared, and this negative mask was brought into contact with the photosensitive laminate, and exposure was performed with an ultrahigh pressure mercury lamp at 26 mJ / cm ² . Exposed in quantity. Thereafter, development was carried out in the same manner as in Example 1, and the resolution and storage stability were evaluated in the same manner as in Example 1 except that the resolution was measured. Pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. The results are shown in Table 4.

(Comparative Example 1)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to Irgacure 819 (manufactured by Ciba Specialty Chemicals). A photosensitive film and a photosensitive laminate were prepared to form a permanent pattern.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 5.

(Comparative Example 2)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to CGI325 (manufactured by Ciba Specialty Chemicals). A photosensitive film and a photosensitive laminate were prepared to form a permanent pattern.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 5.

(Comparative Example 3)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to Reference Compound Example 1 represented by the following structural formula. In the same manner as above, a photosensitive film and a photosensitive laminate were prepared to form a permanent pattern.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 5.

(Comparative Example 4)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator was changed from Compound Example 1 to Irgacure OXE-01 (manufactured by Ciba Specialty Chemicals). Similarly, a photosensitive film and a photosensitive laminate were prepared, and a permanent pattern was formed.
In addition, exposure sensitivity, resolution, and storage stability of the manufactured photosensitive film were evaluated in the same manner as in Example 1, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. The results are shown in Table 5.

From the results of Tables 1 to 5, the photosensitive layers formed using the photosensitive compositions of Examples 1 to 14 using the photopolymerization initiator of the present invention are excellent in resolution and storage stability, and are cured in a permanent pattern. The surface hardness and dielectric properties of the layer were also found to be good. In particular, in Examples 1 to 12 in which a photosensitive film was prepared and laser exposure was performed, it was found that the exposure sensitivity was also excellent.
In contrast, the photosensitive composition of Comparative Examples 1 to 4 that did not use the photopolymerization initiator of the present invention and the photosensitive layer in the photosensitive film produced using this photosensitive composition had exposure sensitivity and resolution. And / or storage stability was inferior.

The photopolymerization initiator of the present invention can further improve sensitivity so as to be compatible with laser exposure, and can maintain good resolution, storage stability, surface hardness, and dielectric properties. , Protective films for printed wiring boards (multi-layer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, display members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, It can be suitably used for a micromachine, a proof, an adhesive, a thermosetting composition, a photosensitive composition for forming a permanent pattern, and the like.
The photosensitive composition of the present invention, the photosensitive film and the photosensitive laminate using the photosensitive composition use the photopolymerization initiator of the present invention, so that the sensitivity can be further improved, and The resolution, storage stability, surface hardness, and dielectric properties can be kept good. For this reason, protective films for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, and display members such as color filters, pillar materials, rib materials, spacers, partition walls, It can be widely used for forming permanent patterns such as holograms, micromachines, and proofs, and can be particularly suitably used for forming permanent patterns on printed circuit boards.
Since the permanent pattern method of the present invention uses the photosensitive laminate of the present invention, it is for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a column material, and a rib material. It can be suitably used for the production of liquid crystal structural members such as spacers and partition walls, and the production of holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of permanent patterns on printed boards.

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 a perspective view showing an example of the configuration of the fiber array light source. FIG. 9 is a front view showing an example of the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 10 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. 11 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 12 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 13 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. 14 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. 15 is a top view showing the positional relationship between the exposure areas by two adjacent exposure heads and the corresponding slits. FIG. 16 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 17 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 14 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 18 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. 19 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 20A is an explanatory diagram showing an example of magnification distortion. FIG. 20B is an explanatory diagram showing an example of beam diameter distortion. FIG. 21A is an explanatory view showing a first example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 22 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 23A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 23B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 24 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads. FIG. 25 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 26 is an example of a plan view showing the configuration of the combined laser light source. FIG. 27 is an example of a plan view showing the configuration of the laser module. FIG. 28 is an example of a side view showing the configuration of the laser module shown in FIG. FIG. 29 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 30 is an example of a perspective view showing a configuration of a laser array. FIG. 31A is an example of a perspective view showing a configuration of a multi-cavity laser. FIG. 31B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 31A are arranged in an array. FIG. 32 is an example of a plan view showing another configuration of the combined laser light source. FIG. 33 is an example of a plan view showing another configuration of the combined laser light source. FIG. 34A is an example of a plan view showing another configuration of the combined laser light source. FIG. 34B is an example of a cross-sectional view along the optical axis of FIG. 34A.

Explanation of symbols

B1 to B7 Laser beam L1 to L7 Collimator lens LD1 to LD7 GaN-based semiconductor laser 10 Pattern forming device 12 Photosensitive laminate (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)
Reference Signs List 60 laser module 62 multimode optical fiber 64 optical fiber 66 laser emitting unit 110 heat block 111 multicavity laser 113 rod lens 114 lens array 140 laser array 200 condenser lens

Claims (10)

A photopolymerization initiator, which is a compound represented by any one of the following general formulas (1) to (5).
However, in the general formulas (1) to (5), the dotted double line represents either a single bond or a double bond. R ¹ represents any ^one of a hydrogen atom, an aliphatic group which may have a substituent, and an aryl group which may have a substituent, and R ² represents a hydrogen atom, ═O, ═NOCOY, a substituent. It represents either an aliphatic group that may have an aryl group that may have a substituent. R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , and R ²⁰ are the same as R ^1. , R ⁵ , R ⁸ , R ¹³ , and R ¹⁷ represent the same meaning as R ² . At least ^one of R ¹ and R ² and R ³ , R ⁴ and R ⁵ and R ⁶ , and R ⁷ and R ⁸ and R ⁹ may be bonded to form a ring, and R ¹² and R ¹³ R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring. A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , and A ⁸ independently represent any of a single bond, an oxygen atom, a sulfur atom, NHCO, and CONH. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ independently represent a hydrogen atom or any of the groups shown below, and X ¹ , X ² and X ^3, and X ⁴ and X ⁵ are all Except when it is a hydrogen atom. Y ¹ , Y ² , and Y ³ independently represent any of the groups shown below. G represents either an aliphatic group which may have a substituent or an aryl group which may have a substituent. J represents the same meaning as R ¹ .
The photopolymerization initiator according to claim 1, wherein the compound represented by the general formula (1) is further represented by the following general formula (6).
However, in said general formula (6), R <^21> , R <^22> , R <^23> , R <^24> , R <^25> and R < ²⁶ > represent the same meaning as R < ¹ > in general formulas (1) to (5), and A < ⁸ > represents the same meaning as ^{a 1} in the general formula (1) to (5), ^{Y 4} represents the same meaning as ^{Y 1} in the general formula (1) to (5). R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ²⁶ may be bonded to each other to form a ring.   A photosensitive composition comprising (A) a binder, (B) a polymerizable compound, (C) the photopolymerization initiator according to claim 1, and (D) a thermal crosslinking agent.   (C) Content of a photoinitiator is 0.1-15 mass%, The photosensitive composition of Claim 3.   A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to claim 3 on the support.   A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition according to claim 3 on a substrate.   The photosensitive laminated body of Claim 6 in which the photosensitive layer was formed with the photosensitive film of Claim 5.   A method for forming a permanent pattern, comprising exposing the photosensitive layer in the photosensitive laminate according to claim 6.   The permanent pattern formation method according to claim 8, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm. A printed circuit board, wherein a permanent pattern is formed by the method for forming a permanent pattern according to claim 8.