JPWO2007111003A1 - Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board - Google Patents

Abstract

The present invention provides a photosensitive composition, a photosensitive film, and a high-definition permanent pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.) in the semiconductor field that have good sensitivity and excellent raw storage and handling properties. ) In high definition and efficiently, and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method. Therefore, (A) a polybasic compound containing either a saturated group or an unsaturated group in a reaction product of an epoxy compound (a) having a bisphenol skeleton in a partial structure and an unsaturated group-containing monocarboxylic acid (b) A photosensitive composition containing at least a binder obtained by reacting the acid compound (c), (B) a polymerizable compound, and (C) any of an acylphosphine oxide compound and an oxime derivative as a photopolymerization initiator; provide.

Description

  The present invention relates to a photosensitive composition having high sensitivity and excellent storage stability and handleability of a photosensitive laminate, a photosensitive film using the photosensitive composition, and a high-definition permanent pattern (protection) in the semiconductor field. The present invention relates to a permanent pattern forming method capable of forming a film, an interlayer insulating film, a solder resist pattern, etc.) with high definition and efficiency, and a printed board on which a permanent pattern is formed by the permanent pattern forming method.

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

In order to obtain the permanent pattern with high definition and efficiency, it is required to improve sensitivity. Therefore, for the purpose of improving the sensitivity, the photosensitive layer includes an α-aminoalkylphenone compound (Irgacure 907) as a photopolymerization initiator and a thioxanthone compound (Kayacure DETX-S) as a sensitizer. A photosensitive film has been proposed (see Patent Document 1).
However, since the α-aminoalkylphenone compound has an amine structure, when a thermal cross-linking agent is used, the reaction of the thermal cross-linking agent is gradually induced even near room temperature, and the sensitivity of the photosensitive film over time is stable. In some cases, the raw storability of the food was reduced.
Here, when the photosensitive composition solution for forming the photosensitive layer is applied directly on the substrate (hereinafter referred to as “liquid registration type”), a dispersion in which components other than the thermal crosslinking agent are dispersed, A solution in which a crosslinking agent is dispersed or dissolved is prepared and then mixed to prepare a so-called two-component type. However, after the mixing operation, the layered state on the substrate gradually proceeds with the curing reaction. Thus, exposure and development may not be possible, and improvement in storage stability in a laminated state is desired.
In the case where a film in which a photosensitive layer made of the photosensitive composition is formed on a support and the film is laminated on a substrate such as a printed board (hereinafter referred to as “film type”). Since it is required to be easy to handle, it is difficult to adopt an embodiment like the above liquid register type.

On the other hand, an alkali-soluble binder having an unsaturated double bond, a photopolymerizable oxime compound, a sensitizer thioxanthone compound, a polymerizable compound and an epoxy compound containing two or more epoxy groups are included. A photosensitive composition has been proposed (see Patent Documents 2 and 3).
However, the use of these also increases the sensitivity, but there is still a problem that the raw storage stability such as the stability of sensitivity over time is lowered.

On the other hand, as a binder used in the photosensitive layer, a solder resist pattern forming material using an epoxy acrylate compound having a bisphenol skeleton in a partial structure as a binder has been proposed (see Patent Document 4).
However, the material of Patent Document 4 has a low sensitivity, and particularly when laser exposure is performed, the exposure tact is slow, which is a problem. Moreover, there is no description about the compatibility between the stability after application of the liquid solder resist and the enhancement of sensitivity.
Therefore, a photosensitive composition, a photosensitive film, a photosensitive film using the photosensitive composition, and a permanent pattern such as a protective film and an insulating film, which are highly sensitive and have excellent raw storage stability in a laminate. A permanent pattern forming method that can be formed with high definition and efficiency, and a printed circuit board on which a pattern is formed by the permanent pattern forming method have not yet been provided, and further improvement and development are desired at present. is there.

JP 2000-232264 A JP 2002-519732 A JP 2005-182004 A International Publication No. 04/34147 Pamphlet

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention relates to a photosensitive composition having high sensitivity and excellent raw storage stability of a laminate, a photosensitive film using the photosensitive composition, and a high-definition permanent pattern (protective film, interlayer) in the semiconductor field. It is an object of the present invention to provide a permanent pattern forming method capable of forming an insulating film, a solder resist pattern, etc.) with high definition and efficiency, and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.

Means for solving the problems are as follows. That is,
<1> (A) Polybase containing either a saturated group or an unsaturated group in a reaction product of an epoxy compound (a) having a bisphenol skeleton in a partial structure and an unsaturated group-containing monocarboxylic acid (b) A photosensitive material comprising at least a binder obtained by reacting an acid compound (c), (B) a polymerizable compound, and (C) any of an acylphosphine oxide compound and an oxime derivative as a photopolymerization initiator. Sex composition.
<2> (A) The binder is a reaction product of the epoxy compound (a) represented by any one of the following general formula (1) and general formula (2) and the unsaturated group-containing monocarboxylic acid (b). The photosensitive composition according to <1>, which is a photocurable resin obtained by reacting a polybasic acid compound (c) containing any of a saturated group and an unsaturated group.
However, in said general formula (1), X represents either a hydrogen atom or a glycidyl group, and R represents either a methylene group or an isopropylidene group. n represents an integer of 1 or more.
However, In the general formula (2), ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} and ^{R 3} represents an alkylene group, m and n are positive m + n is 2 to 50 P represents a positive integer.
<3> The photosensitive composition according to any one of <1> to <2>, wherein the sensitivity is 0.1 to 200 mJ / cm ² .
<4> The photosensitive composition according to any one of <1> to <3>, further including (D) a thermal crosslinking agent.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the oxime derivative has a partial structure represented by any one of the following general formula (3) and general formula (4). .
In the general formula (3) and (4), Ar represents an aromatic group, or a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ are an aliphatic group, It represents either an aromatic group or a heterocyclic group, and m represents an integer of 1 or more.
<6> (D) The ratio of the crosslinking group of the thermal crosslinking agent and the acidic group of the (A) binder is thermal crosslinking group / acidic group = 0.3 to 3.0. It is the photosensitive composition in any one.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the polymerizable compound (B) includes at least one selected from monomers having a (meth) acryl group.
<8> (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 <7>.
<9> The photosensitive composition according to any one of <1> to <8>, further including (E) an elastomer.
<10> The photosensitive composition according to any one of <1> to <9>, further including (F) a phenoxy resin.
<11> (G) The photosensitive composition according to any one of <1> to <10>, further including a sensitizer.
<12> The photosensitive composition according to <11>, wherein the (G) sensitizer includes a hetero-fused ring-type compound.
<13> The photosensitive composition according to <12>, wherein the hetero-fused ring compound is a thioxanthone compound.

<14> A photosensitive film comprising at least a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <13> on the support. It is.
<15> The photosensitive film according to <14>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<16> The photosensitive film according to any one of <14> to <15>, wherein the support includes a synthetic resin and is transparent.
<17> The photosensitive film according to any one of <14> to <16>, wherein the support has a long shape.
<18> The photosensitive film according to any one of <14> to <17>, which is long and wound in a roll shape.
<19> The photosensitive film according to any one of <14> to <18>, having a protective film on the photosensitive layer.

<20> A photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <13> on a substrate.
<21> The photosensitive laminate according to <20>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <14> to <19>.

<22> Light irradiation means capable of irradiating light, and modulating light from the light irradiation means, and exposing the photosensitive layer in the photosensitive laminate according to any one of <20> to <21>. A pattern forming apparatus including at least an optical modulation unit for performing the patterning. In the pattern forming apparatus according to <22>, 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.
<23> 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 <22> modulated according to. In the pattern forming apparatus according to <23>, 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.
<24> The light modulation means has 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 <22> to <23>, which can be controlled according to pattern information. In the pattern forming apparatus according to <24>, an arbitrary less than n pixel portions arranged continuously from n pixel portions in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<25> The pattern forming apparatus according to any one of <22> to <24>, wherein the light modulation unit is a spatial light modulation element.
<26> The pattern forming apparatus according to <25>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<27> The pattern forming apparatus according to any one of <24> to <26>, wherein the picture element portion is a micromirror.
<28> The pattern forming apparatus according to any one of <22> to <27>, wherein the light irradiation unit is capable of combining and irradiating two or more lights. In the pattern forming apparatus according to <28>, 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.
<29> The light irradiation unit 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 the laser beams to the multimode optical fiber. The pattern forming apparatus according to any one of <22> to <28>. In the pattern forming apparatus according to <29>, 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.

<30> A method for forming a permanent pattern, comprising exposing the photosensitive layer in the photosensitive laminate according to any one of <20> to <21>.
<31> The method for forming a permanent pattern according to <30>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<32> The method for forming a permanent pattern according to any one of <30> to <31>, wherein the exposure is performed imagewise based on pattern information to be formed.

<33> 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 <30> to <32>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the method for forming a permanent pattern according to <33>, the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part specifying means. 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.
<34> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the joint area between the heads, which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to <33>, wherein among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the method for forming a permanent pattern according to <34>, 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. 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.
<35> 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 the above <34>, wherein the drawing element portion used for realizing N double exposure in an area other than the inter-head connection area among the drawing element parts is designated. In the method for forming a permanent pattern according to <35>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating means is an overlapping exposure region on the 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.
<36> When the set inclination angle θ is N, the number of N exposures, the number s of pixel parts in the column direction, the interval p 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 <33> to <35>.
<37> The method for forming a permanent pattern according to any one of <33> to <36>, wherein N in N-fold exposure is a natural number of 3 or more. In the method for forming a permanent pattern described in <37>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<38> 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;
<33> to <37>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing the N-fold exposure based on a detection result by the light spot position detection unit. This is a permanent pattern forming method.
<39> The permanent pattern forming method according to any one of <33> to <38>, 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.

<40> The fact that the light spot position detector detects the row direction of the light spot on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted based on the detected at least two light spot positions. The slope angle θ ′ is specified, and the picture element selection means selects the picture element part to be used so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. The permanent pattern forming method according to any one of the above.
<41> 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 <40>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<42> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <38> to <41>, in which the pixel elements in the first to the Tth rows are selected as used pixel elements in a row (where m represents a natural number of 2 or more). The permanent pattern forming method according to any one of the above.
<43> The pixel part selection means derives a natural number T close to t satisfying a relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part in the (T + 1) -th line to the m-th line is specified as an unused picture element part, and the unused picture element part is specified. The permanent pattern forming method according to any one of <38> to <42>, wherein the pixel part excluding the element part is selected as a use pixel part.

<44> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part rows, the pixel part selection unit,
(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 the above <38>, which is one of means for selecting a pixel part to be used so that the area of an underexposed area is minimized and an overexposed area does not occur with respect to typical N-exposure <43> The method for forming a permanent pattern according to <43>.
<45> In the connecting region between the heads, which is an overlapped 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 does not occur. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
<38> to <44> according to any one of <38> to <44>.
<46> The permanent pattern forming method according to <45>, wherein the unused pixel parts are specified in units of rows.

<47> In order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, N (N-1) pixel part columns for N multiple exposures. The permanent pattern forming method according to any one of <38> to <46>, wherein the reference exposure is performed using only the image element portion that constitutes. In the permanent pattern forming method according to <47>, in order to specify a 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.
<48> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, for each N-exposure N, a pixel part line is formed every 1 / N lines. The method for forming a permanent pattern according to any one of <38> to <47>, wherein the reference exposure is performed using only the picture element portion. In the permanent pattern forming method according to <48>, in order to designate the use pixel part in the use pixel part designating unit, among the usable picture element parts, N is set to 1 for N double exposure. / Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<49> From <33> to <48>, wherein the used pixel part specifying means includes a slit and a photodetector as a light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means. The permanent pattern forming method according to any one of the above.
<50> The method for forming a permanent pattern according to any one of <33> to <49>, wherein N in N-fold exposure is a natural number of 3 or more and 7 or less.

<51> 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. The method for forming a permanent pattern according to any one of <33> to <50>, wherein the modulation is performed according to the method. In the pattern forming apparatus according to <51>, 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.
<52> The method for forming a permanent pattern according to <51>, wherein the light modulator is a spatial light modulator.
<53> The method for forming a permanent pattern according to <52>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<54> The permanent pattern forming method according to any one of <33> to <53>, wherein the picture element portion is a micromirror.
<55> From the above <33> to <33> 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 54>.

<56> The permanent pattern forming method according to any one of <33> to <55>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <56>, the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<57> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses and couples the laser beams emitted from the plurality of lasers to the multimode optical fiber. <33> to <56> The method for forming a permanent pattern according to any one of <56>. In the method for forming a permanent pattern according to <57>, the light irradiating means may collect the laser light emitted from each of 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.

<58> The method for forming a permanent pattern according to any one of <30> to <57>, wherein the photosensitive layer is developed after the exposure. In the method for forming a permanent pattern according to <58>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<59> The method for forming a permanent pattern according to <58>, wherein the permanent pattern is formed after the development.

<60> A permanent pattern formed by the pattern forming method according to any one of <30> to <59>. Since the permanent pattern according to <60> 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. It is useful for high-density mounting on PCBs and build-up wiring boards.
<61> The permanent pattern according to <60>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern according to <61> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, due to the insulation and heat resistance of the film, the wiring may be subjected to an impact or bending from the outside. Protected from.

  <62> A printed circuit board wherein a permanent pattern is formed by the permanent pattern forming method according to any one of <30> to <59>.

  According to the present invention, it is possible to solve the conventional problems, and for the purpose of forming a permanent pattern such as a solder resist, the photosensitive composition has good sensitivity and excellent raw storage and handling properties even in the film type. , A photosensitive film, and a permanent pattern forming method capable of efficiently and efficiently forming a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) in the semiconductor field, and the permanent pattern A printed circuit board on which a permanent pattern is formed by the forming method can be provided.

FIG. 1A is a top view showing an example of a detailed configuration of the exposure head. FIG. 1B is a side view showing an example of a detailed configuration of the exposure head. FIG. 2 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus. FIG. 3 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. 4 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least (A) a binder, (B) a polymerizable compound, and (C) a photopolymerization initiator, and (D) a thermal crosslinking agent, if necessary. E) Elastomer, (F) Phenoxy resin, (G) Sensitizer, (H) Including other components.
As the sensitivity of the photosensitive composition, in the case where a photosensitive layer formed using the photosensitive composition is exposed and developed, the exposure in which the thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development. preferably, the minimum energy of light used for it is preferably from 0.1~200mJ / cm ^2, more preferably 0.2~100mJ / cm ^2, to be 0.5~50mJ / cm ² preferable.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 200 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.
Here, the “minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development” (hereinafter sometimes simply referred to as “minimum energy of light”) This is so-called development sensitivity. For example, the relationship between the amount of energy (exposure amount) of light used for the exposure when the photosensitive layer is exposed and the thickness of the cured layer generated by the development processing subsequent to the exposure. It can be determined from the graph (sensitivity curve) shown.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring device (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.
There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

<Binder>
The binder used in the present invention includes a saturated or unsaturated group-containing polybasic acid compound (c ).

-(A) Epoxy compound-
As the epoxy compound (a) having the bisphenol skeleton in a partial structure, a compound represented by any one of the following general formula (1) and general formula (2) is preferable.
However, in said general formula (1), X represents either a hydrogen atom or a glycidyl group, and R represents either a methylene group or an isopropylidene group. n represents an integer of 1 or more.

  The bisphenol cage epoxy resin or bisphenol F epoxy resin represented by the general formula (1) and X is a glycidyl group represented by the following structural formula is, for example, a bisphenol cage type represented by the following general formula (5). It can be obtained by reacting the hydroxyl group of epoxy resin or bisphenol F type epoxy resin with epichlorohydrin. In order to promote the reaction between the hydroxyl group and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. If the reaction temperature is less than 50 ° C., the reaction may be slow, and if the reaction temperature exceeds 120 ° C., many side reactions may occur.

However, in said general formula (5), R represents either a hydrogen atom or a methyl group, and n is an integer greater than or equal to 1.

However, In the general formula (2), ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} and ^{R 3} represents an alkylene group, m and n are positive m + n is 2 to 50 P represents a positive integer.
The m + n is more preferably a positive integer of 2 to 30, and more preferably a positive integer of 2 to 20. Moreover, the integer of 1-25 is more preferable, as for the said p, the integer of 1-15 is still more preferable, and the integer of 1-10 is especially preferable.

The compound (polymer) represented by the general formula (2) is composed of the following repeating unit (1a) and unit (1b). The terminal of the polymer may be either the unit (1a) or the unit (1b). When the unit (1a) is a terminal, the hydroxyl group in bisphenol is substituted with a substituent such as a glycidyl group. Also good. In the units (1a) and (1b), R ¹ represents either a hydrogen atom or a methyl group, and R ² and R ³ represent an alkylene group.

-(B) Unsaturated group-containing monocarboxylic acid-
Examples of the unsaturated group-containing monocarboxylic acid include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid. In addition, a vinyl group-containing monocarboxylic acid such as a half-ester compound, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl which is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride. A half ester compound which is a reaction product of an ester and a saturated or unsaturated dibasic acid anhydride can be used. These half ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound that is an example of the vinyl group-containing monocarboxylic acid include hydroxyethyl acrylate, hydroxyethyl methacrylate, Hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Dipentaerythritol pentaacrylate, pen Dipentaerythritol methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like.

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

  In the reaction between the epoxy resin and the vinyl group-containing monocarboxylic acid, the vinyl group-containing monocarboxylic acid is reacted at a ratio of 0.8 to 1.05 equivalent to 1 equivalent of the epoxy group of the epoxy resin. It is preferably 0.9 to 1.0 equivalent.

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

Furthermore, it is preferable to use a catalyst to promote the reaction. Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, and triphenylphosphine.
As the usage-amount of the said catalyst, 0.1-10 mass parts is preferable with respect to a total of 100 mass parts of the said epoxy resin and the said vinyl group containing monocarboxylic acid.

Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
As the usage-amount of the said polymerization inhibitor, 0.01-1 mass part is preferable with respect to a total of 100 mass parts of the said epoxy resin and the said vinyl group containing monocarboxylic acid. As said reaction temperature, 60-150 degreeC is preferable and 80-120 degreeC is more preferable.

  If necessary, the vinyl group-containing monocarboxylic acid and a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. can be used in combination. .

-(C) Saturated or unsaturated group-containing polybasic acid compound-
Examples of the saturated or unsaturated group-containing polybasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the reaction product with the saturated or unsaturated group-containing polybasic acid anhydride, the saturated or unsaturated group-containing polybasic acid anhydride is added to 0.1 equivalent of the hydroxyl group in the reaction product. The acid value of the binder can be adjusted by reacting with -1.0 equivalent. The acid value of the binder is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. If the acid value is less than 30 mgKOH / g, the solubility of the photocurable resin composition in a dilute alkali solution may be reduced, and if it exceeds 150 mgKOH / g, the electrical characteristics of the cured film may be reduced. The reaction temperature between the reaction product and the saturated or unsaturated group-containing polybasic acid anhydride is preferably 60 to 120 ° C.

-Other binders-
The binder that may be used in combination with the binder is preferably a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain. Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and a carboxyl group is preferable from the viewpoint of obtaining raw materials.
The binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
In addition, as the binder, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or a (meth) acrylamide group, a vinyl ester of carboxylic acid, a vinyl ether, an allyl ether, etc. Various polymerizable double bonds can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound such as a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, or an alicyclic epoxy group. Examples include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having a (meth) acryloyl group (for example, an epoxy group such as cyclohexene oxide in the same molecule). In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. Also included are compounds obtained by copolymerizing a cyclic ether group-containing polymerizable compound such as glycidyl methacrylate and a vinyl monomer such as (meth) acryloylalkyl ester and adding (meth) acrylic acid to the side chain epoxy group. It is done.
Examples of these include compounds described in Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, and Japanese Patent Application Laid-Open No. 2000-232264.

<(B) Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  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.

  As solid content in the said photosensitive composition solid content of the said polymeric compound, 5-50 mass% is preferable and 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>
As the photopolymerization initiator, compounds selected from acylphosphine oxide compounds and oxime derivatives are preferable, and oxime derivatives are particularly preferable. Moreover, you may contain another photoinitiator as needed.

-Acylphosphine oxide compound-
Examples of the acylphosphine oxide compound include monoacylphosphine oxide, bisacylphosphine oxide, and triacylphosphine oxide compounds.
As said acylphosphine oxide compound, the compound represented by following General formula (6) is mentioned suitably, for example.

However, in the general formula ^{(6), R 11} and ^{R 12,} each independently, an alkyl group having 1 to 12 carbon atoms, a benzyl group, a hydrogen atom, a halogen atom, an alkyl of 1 to 8 carbon atoms A phenyl group substituted 1 to 4 times by a group, a phenyl group substituted 1 to 4 times by an alkoxy group having 1 to 8 carbon atoms, a cyclohexyl group, and a group represented by COR ¹³ in the following formula (i) In addition, R ¹¹ may be any one of —OR ¹⁴ and a group represented by the following formula (i). R ¹³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a phenyl group substituted 1 to 4 times by a halogen atom, and It represents any of the groups represented by the following formula (ii), and R ¹⁴ represents any of an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a benzyl group. Y represents any one of a phenylene group, an alkylene group having 1 to 12 carbon atoms, and a cyclohexylene group, and X represents any one of an alkylene group having 1 to 18 carbon atoms and a group represented by the following formula (iii). Represents.

  Specific examples of the compound represented by the general formula (6) include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl). ) Phosphine oxide, bis (2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxy) Benzoyl)-(1-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) octylphosphine oxide, bis 2-methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (2 -Methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-dibutoxybenzoyl) (2-methylpropane- 1-yl) phosphine oxide, bis (2,4-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4-dipentoxyphenyl) Phosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide Bis (2,6-dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis (2 , 6-Dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) biphenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2-methylphenylphosphineoxy Dobis (2,4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -2,3,5,6-tetramethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4 , 6-Trimethylbenzoyl-n-butylphosphine Xoxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dibutoxyphenylphosphine oxide, 1,10-bis [bis (2,4 , 6-trimethylbenzoyl) phosphine oxide] decane, tri (2-methylbenzoyl) phosphine oxide, and the like. Among these, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide are preferred.

-Oxime derivatives-
There is no restriction | limiting in particular as said oxime derivative, Although it can select suitably according to the objective, It is preferable that it is a compound which has an aromatic group at least, following General formula (3) and following General formula (4) It is more preferable that the compound has a partial structure represented by any of them. Two or more oxime derivatives may be used in combination.

In the general formula (3) and (4), Ar represents an aromatic group, or a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ represent an aliphatic group, It represents either an aromatic group or a heterocyclic group, and m represents an integer of 1 or more.

Y ¹ is preferably a hydrogen atom, an aliphatic group, or an aromatic group.
Y ² is preferably an aliphatic group, COY ⁶ , or CO ₂ Y ⁶ . Y ⁶ represents any ^of an aliphatic group, an aromatic group, and a heterocyclic group.
Y ³ and Y ⁴ are preferably either an aliphatic group or an aromatic group.

  The oxime derivative may be a compound in which a plurality of structures represented by the general formula (3) and the general formula (4) are bonded through a linking group.

  In the general formula (3) and the general formula (4), the aliphatic group represents an alkyl group, an alkenyl group, and an alkynyl group, each of which may have a substituent, and the aromatic group is Each represents an optionally substituted aryl group or heterocyclic (heterocyclic) group, and the monovalent substituent includes a halogen atom, an optionally substituted amino group, an alkoxycarbonyl group, It represents a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent.

Examples of the aromatic group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl Group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group and fluorenyl group can be mentioned. Among them, a group having any of phenyl group and naphthyl group is preferable, and a group having naphthyl group is particularly preferable.
In addition, these aromatic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group etc. can be mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As described above, the phosphonate group (—PO ₃ H ₂ ^— , —PO ₃ H ⁻ ) is a conjugate base anion derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). Means group. Usually, it is preferable to use it with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammonium compounds, sulfonium compounds, phosphonium compounds, iodonium compounds, azinium compounds, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

Of the substituents phosphonato group foregoing substituted phosphono group, but was replaced a hydroxyl group on one organic oxo group is the conjugate base anion group, as specific examples, the aforementioned monoalkyl phosphono group (-PO 3 _H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

Other specific examples of the oxime derivative include, for example, compounds disclosed in JP-A No. 2001-233842, JP-A No. 2004-534797, JP-A No. 2002-519732, and the following structural formula The compound etc. which are represented by these are mentioned.

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

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

  0.1-25 mass% is preferable, as for content of the photoinitiator in the said photosensitive composition, 0.5-20 mass% is more preferable, 0.5-15 mass% is still more preferable, 1-10 Part by mass is particularly preferred.

-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 range of about 300 to 800 nm (more preferably 330 to 500 nm).

Examples of the other photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, ketal compounds, hydroxyalkyl ketone compounds, organic Peroxides, thio compounds, ketone compounds, acridine compounds, metallocenes and the like can be mentioned. Among these, ketone compounds and acridine compounds are preferable from the viewpoints of the sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate.
Specific examples of the other photopolymerization initiators include compounds described in JP-A-2005-258431, [0288] to [0299] and [0305] to [0307].

Examples of the ketal compound include Irgacure 651 as benzylmethyl ketal.
Examples of the hydroxyalkyl ketone compound include Irgacure 184, Darocur 1173, Irgacure 2959, and Irgacure 127 as hydroxyalkyl phenones.

Furthermore, examples of the organic peroxide include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone.
Examples of the thio compound include 2-benzoylmethylene-3-methylnaphthothiazoline.

  The content of all photopolymerization initiators including the acylphosphine oxide compound and the oxime derivative in the photosensitive layer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and 5-15 mass% is especially preferable.

<(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 film, developability, etc. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, Hydrogenated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200") , HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (diglycidyl phthalate) Ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4) Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”) "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin Reaction product of 4-vinylcyclohexene-1-oxide with epoxidation with peracetic acid, an epoxy resin having a linear phosphorus-containing structure, an epoxy resin having a cyclic phosphorus-containing structure, α-methyl Stilbene liquid crystal epoxy resin, dibenzoyloxybenzene liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, azine epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP − 50S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

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

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

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

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

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

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

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

<(E) Elastomer>
There is no restriction | limiting in particular as said elastomer, According to the objective, it can select suitably, For example, the compound etc. which are described in [0061]-[0073] of international publication 04/34147 pamphlet may be used. .

<(F) Phenoxy resin>
There is no restriction | limiting in particular as said phenoxy resin, According to the objective, it can select suitably, For example, the compound etc. as described in international publication 04/34147 pamphlet [0074]-[0078] may be used. .

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

-Fused ring compounds-
Among the above exemplified compounds, hetero-fused compounds are preferred as compounds in which an aromatic ring or a heterocycle is condensed (condensed compounds). The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. As said hetero condensed ring type compound, a hetero condensed ring type ketone compound is mentioned, for example. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are more preferable, and among these, a thioxanthone compound is particularly preferable.
Specific examples of the hetero-fused ketone compound include acridone compounds such as acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; thioxanthone, Thioxanthone compounds such as isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, QuantacureQTX; 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′-carboni Rubis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, 7-diethylamino-4-methylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-2002 Coumarins such as coumarin compounds described in Japanese Patent No. 363209; Can be mentioned.
Also known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squalium (for example, squalium), and the like.

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

The mass ratio of the sensitizer and the photopolymerization initiator content in the photosensitive composition is [(sensitizer) / (photopolymerization initiator)] = 1 / 0.1 to 1/100. It is preferable that the ratio is 1/1 to 1/50.
When the mass ratio between the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may be lowered and the change in sensitivity over time may be deteriorated.
The combination of the sensitizer and the photopolymerization initiator is particularly preferably a combination of a thioxanthone compound and an oxime derivative in terms of increasing sensitivity. The oxime derivative may be used in combination with another neutral radical generator and a photopolymerization initiator compound containing a small amount of aminoalkyl group or aminophenyl group in the partial structure.

<(H) 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, properties such as the stability, photographic properties, and film physical properties of the intended photosensitive film can be adjusted.

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

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

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

  The content of the plasticizer is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 40 mass%, particularly preferably from 1 to 30 mass%, based on all components of the photosensitive layer.

-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 (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). 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) Monastral Fa Strike 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. Moreover, the dye suitably selected from well-known dye can be used as needed.

  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 itself low. Pigments and organic fine particles can be added.
The inorganic pigment is not particularly limited and can 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 size of 0.01 to 5 μm, 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 pigment added is preferably 1 to 60% by mass. When the addition amount is less than 1% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

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

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

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

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

<Photosensitive layer>
The photosensitive layer is formed by the photosensitive composition of the present invention.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it laminates | stacks on the said support body.
As the sensitivity of the photosensitive layer, as described above, is preferably 0.1~200mJ / cm ^2, more preferably ^{0.2~100mJ / cm 2, 0.5~50mJ / cm} 2 It is particularly preferred that
As described above, the thickness of the photosensitive layer is preferably 1 to 100 μm, more preferably 2 to 50 μm, and particularly preferably 4 to 30 μm.

<Support and protective film>
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. Specific examples of the support and the protective film are described in, for example, [0342] to [0348] of JP-A-2005-258431.

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

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

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

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

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

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

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

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

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

  The method for adjusting the interlayer adhesion is not particularly limited and may 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 the 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 deteriorated, and a high-definition permanent pattern may not be formed. Such a problem may occur.

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

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

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

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

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

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

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

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and may be appropriately selected according to the purpose. 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 known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

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

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

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

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

In the method for producing a photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

  Since the photosensitive film of the present invention and the photosensitive laminate use the photosensitive composition of the present invention, the sensitivity is excellent, the raw storage property is excellent, and the pattern can be formed with high definition, so that the protection is possible. For the formation of various patterns such as films, interlayer insulation films, and permanent patterns such as solder resist patterns, for the production of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. It can be used suitably for pattern formation etc., It can use suitably especially for permanent pattern formation of a printed circuit board.

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

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

The permanent pattern forming method of the present invention preferably includes at least an exposure process and further includes other processes such as a development process and a curing process.
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 can be appropriately selected according to 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) The element part is specified, and for the exposure head, 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 the exposure. 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. .

Examples of the pattern forming apparatus according to the permanent pattern forming method of the present invention include, for example, [0028] to [0139] and [0185] to [0191] of JP-A-2006-284842.
Means described in the above.

<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 alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.

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

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

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

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

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

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

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

(Example 1)
-Preparation of photosensitive composition-
-Preparation of photosensitive composition-
Each component was mix | blended in the following quantity and the photosensitive composition solution was prepared.
[Each component amount of photosensitive composition solution]
---------------------------------
· KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate, 66% concentration by Nippon Kayaku Co., Ltd.) · · · 46.8 parts · dipentaerythritol hexaacrylate (polymerizable compound) · · · 9 parts · Irgacure 819 (I-1, photopolymerization initiator): 6 parts by mass. Sensitizer represented by the following structural formula (1) (S-1): 0.5 parts by mass. Epototo ZX-1059 ( Thermal crosslinking agent (manufactured by Tohto Kasei Co., Ltd.) ... 6 parts by mass / Epototo YP-50 (phenoxy resin, manufactured by Tohto Kasei Co., Ltd.) ... 4 parts by mass / thermosetting agent (dicyandiamide) ... 0.77 parts by mass・ Fluorosurfactant (Megafac F-176, manufactured by Dainippon Ink & Chemicals, Inc., 30% 2-butanone solution) ... 0.2 parts by mass Barium sulfate dispersion (manufactured by Sakai Chemical Industry Co., Ltd.) , B-3 0) ... 80 parts by mass, methyl ethyl ketone ... 30 parts by mass --------------------------------
The barium sulfate dispersion was composed of 28.5 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30), KAYARAD ZFR-1492H (bis F type epoxy acrylate, 66% concentration by Nippon Kayaku Co., Ltd.). 6 parts by mass, 28.2 parts by mass of normal propyl acetate, and 0.2 parts by mass of phthalocyanine green were mixed in advance, and then a motor mill M-200 (manufactured by Eiger) was used with zirconia beads having a diameter of 1.0 mm. It was prepared by dispersing for 3.5 hours at a peripheral speed of 9 m / s. The ratio of the crosslinking group of the thermal crosslinking agent and the acidic group of the binder in Example 1 is thermal crosslinking group / acidic group = 0.5 / 1.0 = 0.5.

-Preparation of photosensitive laminate-
Next, as the substrate, a surface of a copper-clad laminate (no through hole, copper thickness 12 μm) on which wiring was formed as a printed board was prepared by performing chemical polishing treatment. On the copper-clad laminate, the photosensitive composition was applied by a screen printing method using a 120 mesh Tetron screen so that the thickness after drying was 30 μm, and a hot air circulating dryer at 80 ° C. for 15 minutes. Was dried to form a photosensitive layer, 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 evaluated for sensitivity, resolution, storage stability, and edge roughness by the following methods. The results other than the shortest development time are shown in Table 1.

<Evaluation of the shortest development time>
A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa, and the photosensitive layer on the copper clad laminate is dissolved from the start of spraying of the sodium carbonate aqueous solution. The time required for removal was measured and this was taken as the shortest development time.
The shortest development time was 20 seconds.

<Evaluation of sensitivity>
The photosensitive layer in the photosensitive laminate prepared above by using a pattern forming apparatus described below, the light energy different light from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval Were exposed twice to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time. The uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve was obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 μm as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.

<< Pattern Forming Apparatus >>
A combined laser light source described in JP-A-2005-258431 as the light irradiating means, and a micromirror array in which 1024 micromirrors 58 are arranged in the main scanning direction schematically shown in FIG. 2 as the light modulating means. , DMD 36 controlled to drive only 1024 × 256 rows among 768 sets arranged in the sub-scanning direction, and an optical system for imaging the light shown in FIGS. 1A and 1B on the photosensitive film, The pattern forming apparatus 10 including the exposure head 30 having the above is 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 1024 columns × 256 rows of usable micromirrors 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. 3, the light spot group from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive film 12 with the stage 14 being stationary. Showed the pattern. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 3, for convenience of explanation, every other column exposure pattern of the micromirror 58 that can be used is divided into an exposure pattern by the pixel column group A and an exposure pattern by the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 3, 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. 4 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 4 were similarly covered with the regions 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

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

<Evaluation of storage stability 1>
The photosensitive laminate was stored for 1 day under drying acceleration conditions (relative humidity 50%) at 40 ° C. One day later, the sensitivity and resolution were measured in the same manner as described above, and the stability over time was evaluated based on the following criteria.
〔Evaluation criteria〕
○: There is almost no change in sensitivity and resolution, and the stability over time is excellent.
Δ: Sensitivity and resolution decrease, development becomes difficult, and stability over time is poor.
X: Sensitivity and resolution are remarkably lowered, stability over time is extremely inferior, or storage is impossible.

<Evaluation of edge roughness>
Using the pattern forming apparatus, the photosensitive laminate is irradiated with double exposure so that a horizontal line pattern in a direction perpendicular to the scanning direction of the exposure head is formed, and a partial region of the photosensitive layer A pattern was formed in the same manner as the resolution measurement. Among the obtained patterns, arbitrary five points of a line having a line width of 50 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and among the edge positions in the field of view Then, the difference between the most swollen portion (mountain peak portion) and the most constricted portion (valley bottom portion) was obtained as an absolute value, and an average value of five observed positions was calculated, and this was defined as edge roughness. The edge roughness is preferably as the value is small because it exhibits good performance.

(Example 2)
-Production of photosensitive film-
The photosensitive composition solution obtained in Example 1 was applied to a PET (polyethylene terephthalate) film having a thickness of 16 μm, a width of 300 mm, and a length of 200 m as the support with a bar coater, and dried at 80 ° C. with hot air circulation. It was dried in the machine to form a photosensitive layer having a thickness of 30 μm. Next, a polypropylene film having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated on the photosensitive layer as a protective film by lamination to produce the photosensitive film.

-Preparation of photosensitive laminate-
Next, on the same copper clad laminate as that of Example 1 as the substrate, the photosensitive film of the photosensitive film was in contact with the copper clad laminate, and the protective film on the photosensitive film was peeled off, and a vacuum laminator ( Nitgo Morton Co., Ltd., VP130) was used to prepare a photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated 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 time of 10 seconds.

  The photosensitive laminate was evaluated for sensitivity, resolution, storage stability, and edge roughness. The resolution, storage stability over time (evaluation 1 of storage stability) and edge roughness were evaluated in the same manner as in Example 1. The sensitivity was evaluated as follows. In addition to the stability over time, the storage stability was evaluated by the following method. The results are shown in Table 1.

<Evaluation of sensitivity>
For the photosensitive layer of the photosensitive film in the prepared photosensitive laminate, a part of the photosensitive layer is cured from the support side in the same manner as in Example 1 by the pattern forming apparatus described in Example 1. It was. After leaving still at room temperature for 10 minutes, the said support body was peeled off from the said photosensitive laminated body, and it carried out similarly to Example 1, and measured the amount of light energy required in order to harden a photosensitive layer.

<Evaluation of storage stability 2>
The said photosensitive film was wound up with the winder, and the photosensitive film original fabric roll was manufactured.
The obtained photosensitive film original roll was slit with a coaxial slitter, and wound on an ABS resin cylindrical core having a length of 300 mm and an inner diameter of 76 mm, and wound up to 150 m in a width of 250 mm to prepare a photosensitive film roll.
The photosensitive film roll thus obtained was wrapped in a black polyethylene cylindrical bag (film thickness: 80 μm, water vapor transmission rate: 25 g / m ² · 24 hr or less), and a polypropylene bush was pushed into both ends of the core. .
The roll-shaped sample whose both ends were closed with the bush was stored at 25 ° C. and 55% RH for 21 days, and then the presence or absence of end face fusion was observed, and the storage stability was evaluated according to the following criteria.
〔Evaluation criteria〕
○: End face fusion is not confirmed, and the laminate can be used satisfactorily.
(Triangle | delta): The state in which a part of end surface is glossy and a slight amount of end surface fusion has occurred (use limit).
X: A state in which the entire end surface is glossy and a large amount of end surface fusion occurs.

(Example 3)
In Example 1, 6 parts by mass of Irgacure 819 (I-1, photopolymerization initiator) in the photosensitive composition solution was replaced with an oxime derivative (I-2, photopolymerization initiator) represented by the following structural formula (2). ) A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 2 parts by mass. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.

  About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 2.

(Example 4)
In Example 1, 6 parts by mass of Irgacure 819 (I-1, photopolymerization initiator) in the photosensitive composition solution was replaced with a compound represented by the following structural formula (3) (I-3, photopolymerization initiator). A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 1 part by mass and 0.5 part by mass of N-phenylglycine (additive). Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.

  About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

(Example 5)
In Example 1, 6 parts by mass of Irgacure 819 (I-1, photopolymerization initiator) in the photosensitive composition solution was replaced with a compound (I-4, photopolymerization initiator) represented by the following structural formula (4). A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 2 parts by mass. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.

  About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

(Example 6)
In Example 1, 6 parts by mass of Irgacure 819 (I-1, photopolymerization initiator) in the photosensitive composition solution was replaced with a compound represented by the following structural formula (5) (I-5, photopolymerization initiator). A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 2 parts by mass. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.

  About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

(Example 7)
In Example 1, 6 parts by mass of Irgacure 819 (I-1, photopolymerization initiator) in the photosensitive composition solution was replaced with a compound (I-6, photopolymerization initiator) represented by the following structural formula (6). A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 2 parts by mass. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.

  About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

(Example 8)
In Example 1, 6 parts by mass of Irgacure 819 (I-1, photopolymerization initiator) in the photosensitive composition solution was replaced with a compound (I-7, photopolymerization initiator) represented by the following structural formula (7). A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 3 parts by mass. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.

  About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

Example 9
In Example 3, 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 at 40 mJ / cm ² with an ultrahigh pressure mercury lamp. Exposed in quantity.
The resolution, storage stability 1 and 2, and edge roughness were evaluated in the same manner as in Example 2 except that the exposure method was used. The results are shown in Table 1.

(Example 10)
In the second embodiment, the set inclination angle θ is calculated with N = 1 based on the equation 3, the natural number T closest to the value t satisfying the relationship of t tan θ ′ = 1 is derived based on the equation 4, and N double exposure ( The sensitivity, resolution, storage stability 1 and 2 and edge roughness were evaluated in the same manner as in Example 2 except that N = 1). The results are shown in Table 1.

Example 11
In Example 3, KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate) and KAYARAD ZFR-1492H in the photosensitive composition solution were changed to KAYARAD ZAR-1413H (bisphenol A type epoxy acrylate, concentration 66%, manufactured by Nippon Kayaku Co., Ltd.). A photosensitive composition solution was prepared in the same manner as in Example 3 except for changing to. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1. In Example 11, the ratio of the crosslinking group of the thermal crosslinking agent to the acidic group of the binder is thermal crosslinking group / acidic group = 0.5 / 1.0 = 0.5.

Example 12
In Example 3, except that KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate) in the photosensitive composition solution was changed to the following binder (binder made from the compound represented by the general formula (2)). In the same manner as in Example 3, a photosensitive composition solution was prepared. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

-Preparation of binder-
Epototo YDPF-1000 (manufactured by Tohto Kasei Co., Ltd.) 200 parts by mass, acrylic acid 36 parts by mass, methyl hydroquinone 0.2 parts by mass, propylene glycol monomethyl ether monoacetate 60 parts by mass in a reaction vessel and reacted at 90 ° C I did it. Subsequently, the internal temperature was cooled to 60 ° C., 1 part by mass of triphenylphosphine was added, and the mixture was stirred at 100 ° C. for 3 hours. Next, 50 parts by mass of tetrahydrophthalic anhydride and 94 parts by mass of propylene glycol monomethyl ether monoacetate were added and stirred at 85 ° C. for 6 hours to obtain a binder having a concentration of 65%.

(Comparative Example 1)
In Example 1, a photosensitive composition solution was prepared in the same manner as in Example 1 except that 6 parts by mass of Irgacure 819 in the photosensitive composition solution was changed to 3 parts by mass of Irgacure 907. A laminate was prepared.
About the said photosensitive laminated body, it carried out similarly to Example 1, and evaluated the sensitivity, the resolution, the storage stability 1, and the edge roughness. The results are shown in Table 1.

(Comparative Example 2)
A photosensitive film was formed in the same manner as in Example 2, except that the photosensitive composition solution of Comparative Example 1 (6 parts by mass of Irgacure 819 was changed to 3 parts by mass of Irgacure 907) was formed. The body was prepared.
About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

(Comparative Example 3)
In Example 1, KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate) in the photosensitive composition solution was changed to lipoxy PR-300 (cresol novolac type epoxy acrylate, concentration 65%, manufactured by Showa Polymer Co., Ltd.). Except for the above, a photosensitive composition solution was prepared in the same manner as in Example 1 to prepare a photosensitive laminate.
About the said photosensitive laminated body, it carried out similarly to Example 1, and evaluated the sensitivity, the resolution, the storage stability 1, and the edge roughness. The results are shown in Table 1.

(Comparative Example 4)
A photosensitive film was formed in the same manner as in Example 2 except that the photosensitive composition solution of Comparative Example 3 (KAYARAD ZFR-1492H was changed to Lipoxy PR-300) was used. Prepared.
About the said photosensitive laminated body, it carried out similarly to Example 2, and evaluated sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.

From the results in Table 1, it was found that in Examples 1 to 12 using the photosensitive composition of the present invention and the photosensitive film of the present invention, a pattern with high sensitivity, excellent storage stability, and high resolution could be formed.

The photosensitive composition of the present invention is highly sensitive, excellent in preservability and handleability, can form a high-definition pattern, a pattern suitable for manufacturing a printed wiring board including a package substrate, or It can be widely used for the formation of permanent patterns (interlayer insulating film, protective film, solder resist pattern, etc.) in high-definition permanent patterns in the semiconductor field, formation of the photosensitive film of the present invention, permanent pattern forming method, printed circuit board It can use suitably for formation of.
By using the photosensitive composition of the present invention, the photosensitive film of the present invention is highly sensitive, excellent in preservability and handling, can form a high-definition pattern, and is a printed wiring including a package substrate. It can be widely used for forming a pattern suitable for manufacturing a substrate or the like, or a permanent pattern (interlayer insulating film, protective film, solder resist pattern, etc.) in a high-definition permanent pattern in the semiconductor field. It can use suitably for formation of a formation method and a printed circuit board.
The permanent pattern forming method of the present invention can form a high-definition pattern with high sensitivity, excellent raw storability and handleability by using the photosensitive composition or photosensitive film of the present invention. Because it is possible to form high-definition and efficient patterns that are suitable for manufacturing printed wiring boards and the like, or high-definition permanent patterns (interlayer insulation film, protective film, solder resist pattern, etc.) in the semiconductor field, It can be suitably used for forming various patterns that require high-definition exposure, and can be particularly suitably used for forming the printed circuit board of the present invention.

Claims (13)

  (A) A polybasic acid compound containing either a saturated group or an unsaturated group in a reaction product of an epoxy compound (a) having a bisphenol skeleton in a partial structure and an unsaturated group-containing monocarboxylic acid (b) ( a photosensitive composition comprising at least a binder obtained by reacting c), (B) a polymerizable compound, and (C) any of an acylphosphine oxide compound and an oxime derivative as a photopolymerization initiator. . (A) The binder is a saturated group in a reaction product of the epoxy compound (a) represented by any one of the following general formula (1) and general formula (2) and the unsaturated group-containing monocarboxylic acid (b). The photosensitive composition according to claim 1, which is a photocurable resin obtained by reacting a polybasic acid compound (c) containing any one of an unsaturated group and an unsaturated group.
However, in said general formula (1), X represents either a hydrogen atom or a glycidyl group, and R represents either a methylene group or an isopropylidene group. n represents an integer of 1 or more.
However, In the general formula (2), ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} and ^{R 3} represents an alkylene group, m and n are positive m + n is 2 to 50 P represents a positive integer. The photosensitive composition according to claim 1, wherein the sensitivity is 0.1 to 200 mJ / cm ² .   (D) The photosensitive composition in any one of Claim 1 to 3 which further contains a thermal crosslinking agent. The photosensitive composition in any one of Claim 1 to 4 in which an oxime derivative has the partial structure represented by either the following general formula (3) and general formula (4).
In the general formula (3) and (4), Ar represents an aromatic group, or a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ are an aliphatic group, It represents either an aromatic group or a heterocyclic group, and m represents an integer of 1 or more.   6. The photosensitive composition according to claim 4, wherein the ratio of (D) the crosslinking group of the thermal crosslinking agent and (A) the acidic group of the binder is thermal crosslinking group / acidic group = 0.3 to 3.0. Sex composition.   It has at least a support, a photosensitive layer made of the photosensitive composition according to any one of claims 1 to 6 on the support, and a protective film on the photosensitive layer. Photosensitive film.   The photosensitive film according to claim 7, which is long and wound in a roll shape.   A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition according to claim 1 on a substrate.   The photosensitive laminated body of Claim 9 in which the photosensitive layer was formed with the photosensitive film in any one of Claims 7-8.   The permanent pattern formation method characterized by including exposing at least the photosensitive layer in the photosensitive laminated body in any one of Claims 9-10.   The permanent pattern formation method according to claim 11, wherein the exposure is performed using laser light having a wavelength of 350 to 415 nm.   A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 11.