WO2007111003A1 - Photosensitive composition, photosensitive film, method of forming permanent pattern, and printed wiring board - Google Patents

Photosensitive composition, photosensitive film, method of forming permanent pattern, and printed wiring board Download PDF

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Publication number
WO2007111003A1
WO2007111003A1 PCT/JP2006/323909 JP2006323909W WO2007111003A1 WO 2007111003 A1 WO2007111003 A1 WO 2007111003A1 JP 2006323909 W JP2006323909 W JP 2006323909W WO 2007111003 A1 WO2007111003 A1 WO 2007111003A1
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WO
WIPO (PCT)
Prior art keywords
group
photosensitive
exposure
compound
photosensitive composition
Prior art date
Application number
PCT/JP2006/323909
Other languages
French (fr)
Japanese (ja)
Inventor
Toshiaki Hayashi
Original Assignee
Fujifilm Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Priority to KR1020087022064A priority Critical patent/KR101286101B1/en
Priority to JP2008507364A priority patent/JP5107231B2/en
Priority to CN2006800541082A priority patent/CN101416111B/en
Publication of WO2007111003A1 publication Critical patent/WO2007111003A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

Definitions

  • Photosensitive composition photosensitive film, permanent pattern forming method, and printed circuit board
  • the present invention relates to a photosensitive composition having high sensitivity and excellent storage stability and handleability of the photosensitive laminate, a photosensitive film using the photosensitive composition, and high-definition in the semiconductor field.
  • the present invention relates to a permanent pattern forming method capable of forming a permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) with high definition and efficiency, and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.
  • a photosensitive film in which a photosensitive layer is formed by applying a photosensitive composition on a support and drying it has been used.
  • a 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. After the exposure, the photosensitive layer is imaged to form a pattern, followed by a curing process or the like to form the permanent pattern.
  • the ⁇ -aminoalkylphenone compound has an amine structure
  • the reaction of the thermal crosslinking agent is gradually induced even near room temperature, and the sensitivity of the photosensitive film is increased.
  • the raw storage stability such as the stability over time is reduced.
  • liquid registration type a dispersion in which components other than the thermal crosslinking agent are dispersed
  • Rack It is a so-called two-component type that is prepared by mixing and later mixing a solution in which a crosslinking agent is dispersed or dissolved.
  • the layered state on the substrate gradually proceeds with the curing reaction. In some cases, exposure and development cannot be performed over time, and an improvement in storage stability in a laminated state is desired.
  • film type a film having a photosensitive layer made of the photosensitive composition formed on a support is prepared and laminated on a substrate such as a printed board (hereinafter referred to as “film type”).
  • film type a substrate such as a printed board
  • Patent Document 4 has a low sensitivity, and in particular when exposed to a laser, the exposure tact is slow, which is a problem. In addition, there is no mention of both stability and high sensitivity after application of a liquid solder resist!
  • 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. It is.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-232264
  • Patent Document 2 Special Table 2002—519732
  • Patent Document 3 JP 2005-182004 Patent Document 4: Pamphlet of International Publication No.04Z34147
  • 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.
  • An object of the present invention is to provide a permanent pattern forming method capable of efficiently and efficiently forming an insulating film, a solder resist pattern, etc.), and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.
  • a reaction product of an epoxy compound (a) having a bisphenol skeleton in a partial structure and an unsaturated group-containing monocarboxylic acid (b) contains either a saturated group or an unsaturated group.
  • the photosensitive composition characterized by including at least.
  • 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) with the unsaturated group-containing monocarboxylic acid (b).
  • the photosensitive composition according to 1> above which is a photocurable resin obtained by reacting a polybasic acid compound (c) containing either a saturated group or an unsaturated group.
  • X represents either a hydrogen atom or a glycidyl group
  • R represents either a methylene group or an isopropylidene group
  • n represents an integer of 1 or more
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 ⁇ beauty R 3 represents an alkylene group
  • m and n m + n is 2 to 50 Represents a positive integer
  • p represents a positive integer
  • a photosensitive composition of the placing serial to any one of the is 0.
  • Ar represents either an aromatic group or a heterocyclic group
  • Y 1 represents any one of a hydrogen atom and a monovalent substituent
  • Y 2 is an aliphatic group, aromatic group, heterocyclic group
  • COY 3 CO
  • And 5 represents an aliphatic group, an aromatic group, or a heterocyclic group, and m represents an integer of 1 or more.
  • the thermal crosslinking agent is 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.
  • a support and a photosensitive layer made of the photosensitive composition according to any one of ⁇ 1> to ⁇ 13> above on the support, It is a photosensitive film.
  • ⁇ 20> The photosensitive composition according to any one of ⁇ 1> to ⁇ 13> above, on a substrate.
  • a pattern forming apparatus comprising: at least a light modulation unit that performs the above.
  • the light irradiation unit irradiates light toward the light modulation unit.
  • the light modulation means modulates light received from the light irradiation means.
  • 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.
  • the light modulation means further includes a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control generated by the pattern signal generation means for the light emitted from the light irradiation means.
  • the pattern forming apparatus according to ⁇ 22> wherein the pattern is modulated according to a signal.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
  • the light modulation means has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts.
  • the pattern forming apparatus according to any one of the above items 22> and 23> which can be controlled according to pattern information.
  • any less than n pixel parts arranged continuously from the n pixel parts in the light modulation unit are controlled according to pattern information.
  • the light of the light irradiation means power is modulated at high speed.
  • ⁇ 25> The pattern forming apparatus according to any one of ⁇ 22> to ⁇ 24>, wherein the light modulation means 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).
  • DMD digital 'micromirror' device
  • ⁇ 27> The pattern forming apparatus according to any one of the above ⁇ 24>, ⁇ 26>, wherein the pixel part is a micromirror.
  • ⁇ 28> The pattern forming apparatus according to any one of the above ⁇ 22> and ⁇ 27>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
  • 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 to the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated with the plurality of laser forces, respectively, and couples them to the multimode optical fiber.
  • the pattern forming apparatus according to any one of the above items 22> to 28>, which has In the pattern forming apparatus according to ⁇ 29>, the light irradiation unit may collect the laser light emitted from each of the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber. In some cases, 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.
  • a method for forming a permanent pattern comprising exposing the light-sensitive 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.
  • Exposure includes 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. And an exposure head provided with a light modulation means capable of controlling the image element portion according to pattern information, wherein the column direction of the image element portion is set to a predetermined value with respect to the scanning direction of the exposure head. Using an exposure head arranged at an inclination angle of ⁇ ,
  • the exposure head by specifying the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable pixel parts by means of a used pixel part specifying means,
  • the pixel part control unit controls the pixel part so that only the pixel part specified by the used pixel part specifying unit is involved in exposure, and the photosensitive layer
  • the permanent pattern forming method described in 30> Strongly 32> is performed by moving the exposure head relatively in the scanning direction.
  • the exposure head is subjected to N-fold exposure (where N is a natural number equal to or greater than 2) of the usable pixel portions by the used pixel portion specifying means.
  • the pixel part to be used for the image 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 the exposure. .
  • the exposure head 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 resolution and density of the pattern are averaged. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
  • the exposure is performed by a plurality of exposure heads, and the drawing element specifying means is used for the exposure of the joint area between the heads, which is an 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.
  • the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads.
  • the picture element part used for realizing the N-fold exposure in the head-to-head joint area is designated, whereby the exposure head is attached.
  • Variations in the resolution and density unevenness of the pattern formed in the connection area between the heads on the exposed surface of the photosensitive layer due to a shift in position and mounting angle are leveled.
  • the photosensitive layer is exposed with high definition. For example, a high-definition pattern is then formed by developing the photosensitive layer.
  • the exposure is performed by a plurality of exposure heads, and the used pixel part specifying means is a connection between heads that is an overlapped exposure area on an exposed surface formed by the plurality of exposure heads.
  • the permanent pattern according to ⁇ 34> wherein the pixel part used for realizing N-fold exposure in an area other than the head-to-head area among the picture element parts related to exposure other than the area is specified. It is a forming method. In the method for forming a permanent pattern as described in ⁇ 35>, exposure is performed by a plurality of exposure heads, and a used pixel portion designating unit is provided on an exposed surface formed by the plurality of exposure heads.
  • 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
  • a pixel part selecting means for selecting a picture element part to be used for realizing N double exposure
  • the method for forming a permanent pattern according to any one of the above ⁇ 33> Karaku 37> ⁇ 39> The permanent pattern forming method according to any one of the above ⁇ 33> Karaku 38, wherein the used pixel part designating unit designates the used pixel part used to realize N double exposure in units of rows. It is.
  • the light spot position detection means based on at least two light spot positions detected, the light spot column direction on the surface to be exposed and the exposure head running direction when the exposure head is tilted
  • the actual inclination angle ⁇ ′ formed by the image is determined, and the pixel part selection means selects the pixel part to be used so as to absorb the error between the actual inclination angle ⁇ ′ and the set inclination angle ⁇ .
  • ⁇ 39> is the permanent pattern forming method described in any one of the above.
  • the actual inclination angle ⁇ ′ 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 any one of the above.
  • M (where m represents a natural number greater than or equal to 2) in the arranged pixel part, the pixel part from (T + 1) line to m line is identified as an unused pixel part,
  • the permanent pattern forming method according to any one of ⁇ 38> to ⁇ 42>, wherein the pixel part excluding the unused pixel part is selected as a used pixel part.
  • the pixel part selection means In a region including at least a double exposure region on the exposed surface formed by a plurality of pixel part rows, the pixel part selection means,
  • the pixel part selection means has a head-to-head connection area that is a double exposure area on the exposed surface formed by a plurality of exposure heads.
  • the number of pixel units in the overexposed area is equal to the number of pixel units in the underexposed area.
  • N (N ⁇ 1) column-by-column drawings are used for N of N multiple exposures.
  • N of N multiple exposures among the usable pixel parts can be specified.
  • (N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of simple single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
  • the used pixel part specifying means includes a slit and a photodetector as light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit outputs the light emitted from the light irradiation unit.
  • the permanent pattern forming method according to any one of the above items 33> Karaku 50>, which is modulated in accordance with a generated control signal.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is generated by the pattern signal generation unit. Modulated according to the signal.
  • ⁇ 52> The method for forming a permanent pattern according to ⁇ 51>, wherein the light modulation means is a spatial light modulation element.
  • ⁇ 54> The permanent pattern forming method according to any one of the above ⁇ 33>, ⁇ 53>, wherein the picture element portion is a micromirror.
  • the light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system for condensing and coupling the laser beams irradiated to the plurality of laser forces, respectively, to the multimode optical fiber.
  • the permanent pattern forming method according to any one of the above items 33> Karaku 56>.
  • the light irradiating means can condense the laser light irradiated with each of the plurality of laser forces by the collective optical system and couple it to the multimode optical fiber. Therefore, the exposure is performed with exposure light having a deep depth of focus. As a result, the photosensitive film is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very 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. Permanent pattern formation as described in ⁇ 58> In the method, after the exposure, the photosensitive layer is developed to form a highly precise pattern.
  • ⁇ 60> A permanent pattern formed by the pattern forming method according to any one of ⁇ 30> and ⁇ 59>. Since the permanent pattern according to 60> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, etc., and is high-definition, and is a multilayer wiring board for semiconductors and components. This is useful for high-density mounting on PCBs and build-up wiring boards.
  • 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 described in ⁇ 61> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring may be damaged by an external force due to the insulating property, heat resistance, etc. of the film. Protects against impacts and bending.
  • ⁇ 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>.
  • the film type also has good sensitivity and excellent raw storage and handling properties.
  • FIG. 1A is a top view showing an example of a detailed configuration of an 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 a DMD of the pattern forming apparatus.
  • FIG. 3 is an explanatory view showing an example of unevenness in a pattern on an 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 part selected in the example of FIG. 3.
  • the photosensitive composition of the present invention includes (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) other ingredients.
  • the sensitivity of the photosensitive composition is defined as the thickness of the exposed portion of the photosensitive layer after the exposure and development when the photosensitive layer formed using the photosensitive composition is exposed and developed. is more preferred instrument 0. 5 ⁇ 503 ⁇ 4 [Zcm 2 that it is the minimum energy power 0. l ⁇ 200mjZc m 2 of light is preferred instrument 0. 2 ⁇ 100mjZcm 2 used for the exposure is not changed in It is especially preferred.
  • capri may occur in the processing step, and if it exceeds 200 mjZcm 2 , the time required for exposure may become longer and the processing speed may become slower. .
  • 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”)
  • the so-called development sensitivity for example, the relationship between the amount of light energy (exposure amount) used for the exposure when the photosensitive layer is exposed and the thickness of the cured layer generated by the development process following the exposure. Can be obtained from the graph (sensitivity curve).
  • the thickness of the cured layer increases as the exposure amount 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.
  • the difference between the thickness of the cured layer and the thickness of the photosensitive layer before exposure is ⁇ 1 ⁇ m or more.
  • a method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd.
  • Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd.
  • the thickness of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. For example, 1 to 100 ⁇ m is preferable, 2 to 50 ⁇ m is more preferable, and 4 to 30 ⁇ m is preferable. m is particularly preferred.
  • the binder used in the present invention contains a saturated or unsaturated group-containing polybasic acid 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). This is a compound obtained by reacting compound (c).
  • epoxy compound (a) having a bisphenol skeleton in a partial structure a compound represented by any of the following general formulas (1) and (2) is preferable.
  • X represents either a hydrogen atom or a glycidyl group
  • R represents either a methylene group or an isopropylidene group
  • n represents an integer of 1 or more
  • a bisphenol A type epoxy resin or a bisphenol F type epoxy resin represented by the general formula (1), wherein X is a glycidyl group represented by the following structural formula, has, for example, the following general formula: It can be obtained by reacting the hydroxyl group of bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by (5) with epichlorohydrin.
  • polar organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like in the presence of alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. It is preferable to carry out the reaction in the medium.
  • the reaction temperature is less than 50 ° C Reaction may be slow, and side reactions may occur when the reaction temperature exceeds 120 ° C.
  • R represents either a hydrogen atom or a methyl group, and n is an integer of 1 or more.
  • R 1 represents either a hydrogen atom or a methyl group
  • R 2 and R 3 represent an alkylene group
  • m and n have m + n of 250 and P represents a positive integer.
  • n + n is more preferably a positive integer that is an integer of 220, which is more preferably a positive integer of 230.
  • ⁇ is more preferably an integer of 1 25 1 Integer of 15 Is more preferable.
  • An integer of 1 to 10 is particularly preferable.
  • the compound (polymer) represented by the general formula (2) is composed of the following repeating units (la) and units (1b).
  • the unit (la) which may be either the unit (la) or the unit (lb)
  • the hydroxyl group in the bisphenol is replaced by a substituent such as a darisidyl group. May be substituted.
  • R 1 represents either a hydrogen atom or a methyl group
  • R 2 and R 3 represent an alkylene group.
  • Examples of the unsaturated group-containing monocarboxylic acid include acrylic acid, dimer of acrylic acid, methacrylic acid, ⁇ -furfurylacrylic acid, ⁇ -styrylacrylic acid, cinnamic acid, crotonic acid, and acyanamic acid. Also included are bis-group-containing monocarboxylic acids, and half-ester compounds, butyl-group-containing monoglycidyl ethers or butyl-group-containing monodales that are the reaction products of hydroxyl-containing acrylates with saturated or unsaturated dibasic acid anhydrides. Examples thereof include semi-ester compounds which are reaction products of a sidyl ester and a saturated or unsaturated dibasic acid anhydride.
  • These half-ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a beryl group-containing monoglycidyl ether or a bull group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. It is done.
  • These bur group-containing monocarboxylic acids may be used alone or in combination of two or more.
  • Examples of the hydroxyl group-containing acrylate, bure group-containing monoglycidyl ether, and bull group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the bull group-containing monocarboxylic acid include: Hydroxyethyl acrylate, Hydroxy ethinoremethalylate, Hydroxypropinoreatalylate, Hydroxypropinoremethacrylate , Hydroxybutyl acrylate, Hydroxy butyl methacrylate, Polyethylene glycol monomethacrylate, Polyethylene glycol monomethacrylate, Trimethylolpropane ditalylate, Trimethylolpropane dimetatalylate, Pentaerythritol tritalate, Pentaerythritol Noretrimetatalylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate,
  • 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, Ethyltetrahydrophthalic anhydride, hexahydrate Oral phthalic anhydride, Methylhexahydrophthalic anhydride, Ethylhexahydrophthalic anhydride, Itaconic anhydride, etc.
  • the vinyl group-containing monocarboxylic acid is used in an amount of 0.8 to 1.05 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. It is preferable to react at a ratio of 0.9 to 1.0 equivalent is more preferable
  • the epoxy resin and the vinyl group-containing monocarboxylic acid are reacted by dissolving in an organic solvent
  • the organic solvent include ketones such as ethylmethylketone and cyclohexanone, toluene, Aromatic hydrocarbons such as xylene and tetramethylbenzene, methyl cellosolve, butylcetosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol nole chinenore Glycol ethers such as etherol, triethyleneglycolenomethinoleetenole, esters such as ethyl acetate, butyl acetate, butyl acetate sorb acetate, carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether Itotel, oil naphtha
  • a catalyst examples include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium chloride. Romide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like.
  • the amount of the catalyst used is preferably 0.1 to: LO parts by mass with respect to 100 parts by mass in total of the epoxy resin and the bull group-containing monocarboxylic acid.
  • polymerization inhibitor examples include hydroquinone, methylo, idroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
  • the amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy resin and the bull group-containing monostrengthenic acid.
  • the reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
  • the vinyl group-containing monocarboxylic acid and a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Can be used together.
  • saturated or unsaturated group-containing polybasic acid anhydride examples include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydro Examples thereof include phthalic anhydride, methylhexahydrate, phthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.
  • the saturated or unsaturated group-containing polybasic acid with respect to 1 equivalent of a hydroxyl group in the reaction product.
  • the acid value of the binder can be adjusted by reacting 0.1 to 1.0 equivalents of the anhydride.
  • the acid value of the binder is preferably 30 to 150 mg KOHZg, more preferably 50 to 120 mg KOHZg. If the acid value is less than 30 mg KOHZg, the solubility of the photocurable resin composition in a dilute alkaline solution may be reduced, and if it exceeds 150 mg KOHZg, the electrical properties 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.
  • the binder is preferably a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain.
  • the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Of these, a carboxyl group is preferred because of the availability of raw materials.
  • the binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
  • the binder include 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 butyl ether, Various polymerizable double bonds such as aryl ether can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound, for example, a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, or an alicyclic group.
  • an acrylic resin containing a carboxyl group as an acidic group a cyclic ether group-containing polymerizable compound, for example, a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidy
  • an epoxy group-containing polymerizable compound such as an epoxy group (for example, an epoxy group such as cyclohexenoxide in the same molecule) and a compound having a (meth) aryryl group, etc.
  • an isocyanate group-containing polymerizable compound such as isocyanatoethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group.
  • examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as hydroxyalkyl (meth) acrylate to fat.
  • a cyclic ether group-containing polymerizable compound such as glycidyl metatalylate is copolymerized with a butyl monomer such as (meth) atalyloyl alkyl ester, and (meth) acrylic acid is added to the side chain epoxy group.
  • a cyclic ether group-containing polymerizable compound such as glycidyl metatalylate is copolymerized with a butyl monomer such as (meth) atalyloyl alkyl ester, and (meth) acrylic acid is added to the side chain epoxy group.
  • the compound etc. which are obtained by making it also include.
  • Examples of these include compounds described in Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, Japanese Patent Application Laid-Open No. 2000-2232264, and the like.
  • the polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, and has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure.
  • Preferred examples of the compound include at least one selected from monomers having a (meth) acryl group.
  • the monomer having the (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.
  • Monofunctional acrylates and monofunctional methallylates such as rate and phenoxychetyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate Rate, trimethylolpropane ditalylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta erythritol tri (meth) acrylate, dipentaerythritol hexane (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylol propane tri (atalylooxypropyl) ether, tri (atalyloyloxychetyl) isocyanurate
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
  • the solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur. If it exceeds 50% by mass, the adhesiveness of the photosensitive layer becomes too strong. Is not preferable.
  • photopolymerization initiator a compound selected from an acylphosphine oxide compound and an oxime derivative is preferred, and an oxime derivative is particularly preferred. Also, if necessary Accordingly, other photopolymerization initiators may be included.
  • acyl phosphine oxide compound examples include monoacyl phosphine oxide, bisacyl phosphine oxide, and triacyl phosphine oxide compounds.
  • acyl phosphinoxide compound examples include compounds represented by the following general formula (6).
  • R 11 and R 12 are each independently an alkyl group having 1 to 12 carbon atoms, a benzyl group, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms.
  • the group represented by 13 represents a deviation
  • R 11 may be a deviation 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, or a phenyl group substituted 1 to 4 times by a halogen atom.
  • R 14 represents any one of an alkyl group having 1 to 8 carbon atoms, a phenol 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
  • X represents an alkylene group having 1 to 18 carbon atoms and a group represented by the following formula (iii) Represents one of the following.
  • Specific examples of the compound represented by the general formula (6) include bis (2,6 dimethoxybenzoyl) phenol phosphine oxide, bis (2,6 dimethoxybenzoyl) (2, 4, 4 Trimethylpentyl) phosphine oxide, bis (2,6 dimethoxybenzoyl) n-butylphosphine oxide, bis (2,6 dimethoxybenzoyl) mono (2 methylpropane-1-yl) phosphine oxide, bis (2, 6 dimethoxybenzoyl) mono (1-methylpropan-1-yl) phosphine oxide, bis (2, 6 dimethoxybenzoyl) t-butyl phosphine oxide, bis (2, 6 dimethoxybenzoyl) ) Cyclohexylphosphine oxide, bis (2,6 dimethoxybenzoyl) octylphosphine oxide, bis (2-methoxybenzoyl) (2-methylpropane-1-yl)
  • the restriction limit is not particularly limited, but is appropriately selected according to the purpose. Although it can be made of, it is still preferred to be a compound that has at least a fragrant aromatic group.
  • the following general formula ((33)) and the following general formula ((44)) This is a chemical compound that has a structural structure. .
  • the above-described oxyximum-induced conductor may be used in combination of 22 or more types. .
  • Ar represents either an aromatic group or a heterocyclic group
  • Y 1 represents any one of a hydrogen atom and a monovalent substituent
  • Y 2 represents an aliphatic group, an aromatic group, a heterocyclic group, COY 3 , CO
  • And 5 represents an aliphatic group, 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 Y 6
  • Y 6 represents any of an aliphatic group, an aromatic group, and a heterocyclic group.
  • Y 3 and Y 4 are preferably any of an aliphatic group and 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 via a linking group.
  • the aliphatic group represents an alkyl group, a alkenyl group, or an alkyl group, each of which may have a substituent.
  • the aromatic group represents an aryl group or a heterocyclic (heterocyclic) group, each of which may have a substituent, and the monovalent substituent may have a halogen atom or 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 thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indur group, a acenaphthyl group, and a fluorenyl group, and among them, a group having either a phenol group or a naphthyl group. Particularly preferred is a group having a naphthyl group.
  • these aromatic groups may have a substituent.
  • substituents include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • 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, an iso Thiazole ring group, indazole ring group, benzisoxazol 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, quinazo
  • heterocyclic groups may have a substituent.
  • substituents include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.
  • the monovalent substituent may have a halogen atom, a substituent, an amino group, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, A cyan group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, each of which may have a substituent, are preferred.
  • an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent is preferable. .
  • alkyl group which may have a substituent examples include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include , Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl Group, isopropyl group, isobutyl group, sec- butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group , Cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 20
  • the substituent of the alkyl group may include a substituent which is a monovalent non-metallic nuclear energy excluding a hydrogen atom, and a preferable example is a halogen atom (one F, — Br, 1 Cl, 1)), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-anolenoquinoamino group, N, N di group Anolequinolamino group, N-arynoreamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, force ruberamoyloxy group, N-alkyl force ruberamoyloxy group, N-arreyl force ruberamoyloxy group, N, N dialkyl force ruberamoyloxy group, N, N diaryl force ruber
  • Functional base group (referred to as sulfonate group), alkoxysulfol group, aryloxysulfol group
  • Alkylphosphonate group monoarylphosphono group (one PO H (aryl)) and its
  • a functional base group (referred to as an arylphosphonate group), a phosphonoxy group (one OPO H),
  • a functional base group (referred to as a phosphonatoxy group), a dialkylphosphonoxy group (one OPO H (alk
  • alkyl phosphonatoxy group alkyl phosphonatoxy group
  • monoarylphosphonoxy group —OPO H (aryl)
  • aryl phosphonatoxy group aryl phosphonatoxy group
  • alkyl group in these substituents include the aforementioned alkyl groups
  • aryl group in the substituent include a phenyl group, a biphenyl group, Naphtyl group, Tolyl group, Xylyl group, Mesityl group, Taml group, Chlorophenol group, Bromophenol group, Chloromethylphenol group, Hydroxyphenol group, Methoxyphenyl group, Ethoxyphenyl group, Phenooxyphenol -Group, acetylphenol group, benzoylphenol group, methylthiophenyl group, phenylthiol group, methylaminophenol group, dimethylaminophenol group, acetylaminophenol group, Carboxyphenol group, methoxypolyphenyl group, ethoxyphenol group, phenoxycarbonyl group, N-phenylcarbamoyl group, cyanophenol group, sulfophenol group, sulfonato
  • Examples of the alkenyl group in the substituent include a bur group, a 1-probe group, a 1-butur group, a cinnamyl group, a 2-chloro-1-ethenyl group, and the like.
  • Examples of the alkyl group in the group include an ethur group, a 1 propyl group, a 1-butynyl group, a trimethylsilyl ether group, and the like.
  • heterocyclic group in the substituent examples include a pyridyl group and a piperidinyl group.
  • Examples of the silyl group in the substituent include a trimethylsilyl group.
  • Examples of the acyl group in which the substituent may include an acyl group (I ⁇ CO 2) include those in which R G1 is a hydrogen atom, the above alkyl group, or an aryl group.
  • R G1 of Ashiru group hydrogen atom, and the alkyl group include a Ariru group.
  • substituents more preferred are a halogen atom (one F, —Br, —Cl, ⁇ 1), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N , N dialkylamino group, acyloxy group, N alkyl group, rubermoyloxy group, N aryl group, rubermoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxy carb group, aryloxy group, rubamoyl group, N-alkyl-force rubamoyl group, N, N dialkyl carbamoyl group, N allyl force rubamoyl group, N alkyl N allyl carbamoyl group, s
  • examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above.
  • Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, isopropoxymethyl.
  • 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 Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phantolyl group, an indur group, an acenaphthyl group, and a fluorenyl group.
  • a phenyl group and a naphthyl group are more preferable.
  • substituted aryl group those having a monovalent non-metallic atomic group group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used.
  • substituent include the aforementioned alkyl group, substituted alkyl group, and those previously shown as substituents in the substituted alkyl group.
  • substituted aryl group examples include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a tamale group, a chlorophenol group, a bromophenol group, a fluorophenol group, a chloromethyl group.
  • Phenyl group trifluoromethylphenol group, hydroxyphenyl group, methoxyphenyl group, methoxymethoxyphenyl group, aryloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, Tolylthiophenyl group, ethylaminophenyl group, germanaminophenyl group, morpholinophenol group, acetyloxyphenyl group, benzoylphenyl group, N cyclohexylcarbamoylphenyl group, N Phenylcarbamoyl phenyl group, Acetylaminophenol group, N-Methylbenzoylaminophenol group, Carboxyphenol group, Methoxycarbol Benzyl group, aryloxy-hydroxyl-phenyl group, chlorophenol-oxyl-hydroxyl-phenyl group, strong rubamoyl-phenol group, N-methylcarbamoyl-phenol group, N, N
  • R ° 2 , R ° 3 , R ° 4 and R ° 5 are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Examples of these 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.
  • heterocyclic group examples include the pyridyl group exemplified as the substituent of the substituted alkyl group.
  • substituted oxy group those in which 6 is a group consisting of a monovalent nonmetallic atom excluding a hydrogen atom can be used.
  • Preferable substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, rubamoyloxy groups, N alkylcarbamoyloxy groups, N aralkyl rubamoyloxy groups, N, N dialkyl rubamoyloxy groups, N, N diaryl rubamoyloxy groups, N alkyl N allyl force Rubbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group can be mentioned.
  • alkyl group and aryl group in these include the aforementioned alkyl groups, substituted alkyl groups, and those shown as aryl groups and substituted aryl groups.
  • acyl in the acyloxy group examples include those in which R ° 7 is the alkyl group, substituted alkyl group, aryl group and substituted aryl group mentioned above. Of these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
  • preferred substituted oxy groups include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, arryloxy group, phenethyloxy group, and force ruboxy group.
  • Shetyloxy group methoxycarbo-lethyloxy group, ethoxycarbo-tinoyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyl group Xyl group, aryloxyethoxyethoxy group, phenoxy group, triloxy group, xylyloxy group, mesityloxy group, mesityloxy group, tamoxy group, methoxyphenyloxy group, ethoxyphenyloxy group, black mouth phenol
  • Examples thereof include an oxy group, a bromophenyl group, an acetyloxy group, a benzoyloxy group, a naphthyloxy group, a phenylsulfooxy group, a phosphonoxy group, and a phosphonatoxy group.
  • the substituted amino group (R 8 NH—, (R 09 ) (R 010 ) N-) including an amide group includes R 8 , R 9 , and R 01 ° consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • the basic one can be used.
  • R 9 and R 1 () may combine to form a ring.
  • substituted amino group examples 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, an N alkylamino amino group, N arylylamino group, ureido group, N 'alkylureido group, N ,, N, monodialkylureido group, N, arylarylureido group, N ,, diarylureido group, N, Alkyl N, aryl ureido group, N alkyl ureido group, N aryl ureido group, N 'alkyl N alkyl ureido group, N' alkyl N aryl ureido group, N ,, N'-dialkyl-N-alkyl ureido group, N 'Al
  • alkyl groups and aryl groups include those described above as alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups, including acylamino groups, N alkylalkylamino groups, and N arylarylamino groups.
  • R ° 7 of definitive Ashiru group R ° 7 CO
  • R ° 7 CO definitive Ashiru group
  • more preferred are an N alkylamino group, an N, N dialkylamino group, an N arylamino group, and an acylamino group.
  • substituted amino groups include methylamino group, ethylamino group, jetylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.
  • 11 is a non-valent atomic group.
  • the basic one can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group.
  • alkyl group and aryl group in these include the aforementioned alkyl group, substituted alkyl group, and those shown as aryl group and substituted aryl group.
  • Specific examples of such a substituted sulfol group include a butyl sulfol group, a phenol sulfol group, and a black-ended phenol sulfol group.
  • the sulfonate group (one SO-) is a conjugate base anion of the sulfo group (one SO H) as described above.
  • Counter-ions include those generally known, ie, various hums (ammo-ums, sulfomes, phospho- ummes, jordanums, azimuths). Um), and metal ions (Na +, K +, Ca 2+ , Zn 2+, etc.).
  • the substituted carbo group (R 13 — CO 2), a group in which 13 is a non-valent nuclear energy can also be used.
  • the substituted carbo group include formyl group, acyl group, carboxyl group, alkoxy carbo group, aryloxy carbo ol group, force rubamoyl group, N alkyl force rubamoyl group, N, N dialkyl force rubamoyl.
  • Group, N-aryl force rubermoyl group, N, N diaryl force rubermoyl group, N-alkyl N, aryl A strong rubermoyl group can be mentioned.
  • alkyl group and aryl group in these include the aforementioned alkyl group, substituted alkyl group, and those shown as aryl group and substituted aryl group.
  • substituted carbo groups include formyl, acyl, carboxyl, alkoxy carbo, aryloxy carbo, rubamoyl, N-alkyl rubamoyl, N , N-dialkyl-powered rubermoyl groups, N-aryl-powered rubermoyl groups, and even more preferred include formyl, acyl, alkoxycarbol and aryloxycarboro groups. .
  • preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxy carbo ol group, ethoxy carbo ol group, aralkyl carboxy group, dimethylamino phen tert carbo ol group. And methoxy carbo methoxy carbo ol group, N-methyl carbamoyl group, N-furyl carbamoyl group, N, N-jetyl carbamoyl group, morpholino carbo ol group and the like.
  • R 14 As the substituted sulfiel group (R 14 —SO—), those in which R 14 is a group composed of a non-valent nonmetallic atomic group can be used.
  • Preferable examples include alkylsulfiel group, arylsulfyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-di And arylsulfinamoyl group and N-alkyl-N-arylsulfinamoyl group.
  • alkyl group and aryl group in these include the above-described alkyl groups, substituted alkyl groups, and those shown as aryl groups and substituted aryl groups. Of these, more preferred examples include an alkyl sulfiel group and an aryl sulfiel group. Specific examples of such a substituted sulfiel group include a hexyl sulfiel group, a benzyl sulfiel group, a tolyl sulfyl group, and the like.
  • 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.
  • Preferred examples include the above-mentioned dialkylphosphono group, diarylphosphono group. Group, alkylaryl phosphono group, monoalkyl phosphono group and monoaryl phosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a jetyl phosphono group, a dibutyl phosphono group, and a diphenyl phosphono group.
  • the phosphonato group (—PO H—, —PO H_) is, as described above, the phosphono group (—PO H).
  • Such counter cations include those commonly known, ie, various hums (ammo-ums, sulfo-ums, phosphor-ums, jordanums, azimuths). beam, etc.), as well as metal ions (Na +, K +, Ca 2 +, Zn 2+ etc.).
  • the substituted phosphonate group is a conjugated base anion group in which one hydroxyl group is replaced with an organic oxo group among the above-mentioned substituted phosphono groups.
  • oxime derivative examples include compounds disclosed in, for example, JP-A-2001-233842, JP-T-2004-534797, JP-T-2002-519732, and the like. And compounds represented by the following structural formulas.
  • R represents either n-C H or p-CH C H.
  • the content of the photopolymerization initiator in the photosensitive composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and further preferably 0.5 to 15% by mass.
  • the preferred range is 1 to 10 parts by mass.
  • the other photopolymerization initiator has the ability to initiate polymerization of the polymerizable compound.
  • Power that can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has, for example, those that are sensitive to visible light from the ultraviolet region are preferred.
  • Photoexcited sensitizers It may be an activator that produces some kind of action and generates an active radical, and may be an initiator that initiates cationic polymerization according to the type of monomer.
  • 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 initiators include, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexyl monobiimidazoles, ketal compounds, hydroxyalkyl ketones. Examples thereof include compounds, organic peroxides, thio compounds, ketone compounds, ataridin compounds, and meta-octenes. Among these, ketone compounds and atrazine compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate.
  • photopolymerization initiators include the compounds described in [0288] to [0299] and [0305] to [0307] of JP-A-2005-258431. .
  • Examples of the ketal compound include Irgacure 651 as benzylmethyl ketal.
  • hydroxyalkyl ketone compound examples include Irgacure 184, Darocur 1173, Irgacure 2959, and Irgacure 127 as hydroxyalkylphenones.
  • examples of the organic peroxide include 3, 3 ', 4, 4'-tetra (t-butylperoxycarbonyl) benzophenone.
  • Examples of the thioi compound include 2-benzomethylene 3-methylnaphthothiazoline.
  • the content of all the photopolymerization initiators including the acyl acylphosphine compound and oxime derivative in the photosensitive layer is preferably 0.1 to 30% by mass. 20 More preferred is 0.5 to 15% by mass.
  • the thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive film, it is possible to develop it.
  • an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used as long as no adverse effect is exerted.
  • Examples of the epoxy compound having at least two oxysilane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, an isocyanurate skeleton, etc.
  • Heterocyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries", “ALALDITE PT810; manufactured by Ciba Special Chemicals”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin Bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, , Low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novola Type epoxy resin), aryl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenol dimethanol type epoxy resin, phenol biphenol type epoxy resin, dicyclopentaene Type epoxy resin (“HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals” etc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidyl dilin, triglycidyl) Such as
  • an epoxy compound having at least two epoxy groups having an alkyl group at the ⁇ -position in one molecule may be used.
  • Particularly preferred is a compound containing an epoxy group (more specifically, a 13-alkyl-substituted glycidyl group or the like) in which the ⁇ -position is substituted with an alkyl group.
  • the epoxy compound containing at least the epoxy group having an alkyl group at the j8 position is composed of at least one epoxy group in which all of two or more epoxy groups contained in one molecule may be 13 alkyl-substituted glycidyl groups.
  • the group may be a j8-alkyl substituted glycidyl group.
  • the epoxy compound containing an epoxy group having an alkyl group at the 13-position is based on the total amount of the epoxy compound contained in the photosensitive composition.
  • Ratio power of ⁇ -alkyl-substituted glycidyl group in all epoxy groups It is particularly preferable that the upper limit is 40% or more, more preferably 50% or more.
  • the j8-alkyl-substituted glycidyl group is not particularly limited and can be appropriately selected according to the purpose.
  • j8-methyldaricidyl group 13-ethyldaricidyl group, 13 propylglycidyl group, 13- And a butyldaricidyl group.
  • a j8-methyldaricidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive composition and the ease of synthesis.
  • an epoxy compound containing an epoxy group having an alkyl group at the / 3-position for example, an epoxy compound derived from a polyvalent phenol compound and a j8-alkylepihalohydrin is preferable.
  • the / 3-alkylepino and rhohydrin are not particularly limited and may be appropriately selected according to the purpose.
  • j8-methylepichlorohydrin, 13 methylepibromohydrin, 13- J8-methylepihalohydrin such as methylepifluorohydrin; 13-ethylepichlorohydrin, j8-ethylepibu mouth mohydrin, —ethylepifluorohydrin, etc.
  • ⁇ -propyle ⁇ -Propinoreepihalohydrin such as chlorohydrin, ⁇ -propylepib mouth mohydrin, ⁇ -propinoreepifluorohydrin; ⁇ 8-butinoreepichlorohydrin, j8-butylepib mouth mohydrin, j8-butylepihydrohydrin, etc. Pihalohydrin; and the like.
  • ⁇ -methylepino and rhohydrin are preferable from the viewpoints 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.
  • bisphenol compounds such as bisphenol ⁇ ⁇ , bisphenol F and bisphenol S
  • biphenol compounds such as biphenol and tetramethylbiphenol
  • naphthol compounds such as dihydroxynaphthalene and binaphthol
  • phenol-formaldehyde polycondensates C1-C10 monoalkyl substituted phenol-formaldehyde polycondensate such as phenol novolac resin, creso-one formaldehyde polycondensate, etc.
  • C1-C10 dialkyl substituted phenol such as xylenol-formaldehyde polycondensate Ruholmaldehyde polycondensate, bisphenol A formaldehyde Bisphenol of polycondensates such as Compounds include formaldehyde polycondensates, copolycondensates of phenol and monoalkyl-substituted phenols having 1 to 10 carbon atoms with formaldehyde, and polyadducts of phenolic compounds and dibutenebenzene.
  • the above-mentioned bisphenol compound is preferable.
  • Examples of the epoxy compound containing an epoxy group having an alkyl group at the / 3-position include di-13-alkyl glycidyl ether of bisphenol A, di- ⁇ -alkyl glycidyl ether of bisphenol F, and bisphenol S 13 bisphenol compounds such as alkyl glycidyl ethers / 3 alkyl glycidyl ethers; biphenols ge 13 alkyl glycidyl ethers, tetramethylbiphenol diols 13 biphenol compounds such as alkyl glycidyl ethers 13 alkyl glycidyl ethers; dihydroxy Naphthalene Gee / 3 Alkyl Glycidyl Ether, Binaphthol Gee 13 Alkyl Glycidyl Ether, etc.
  • the bisphenol compounds represented by the following structural formula (I), and the resulting polymer force such as epichlorohydrin, induced ⁇ -alkyl glycidyl ether, and the following structural formula ( ⁇ )
  • Poly j8-alkyl glycidyl ether of formaldehyde polycondensate is preferred.
  • R represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 20.
  • R represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R ′′ represents either a hydrogen atom or CH
  • n represents Represents an integer from 0 to 20
  • epoxy compounds containing an epoxy group having an alkyl group at the 13-position may be used alone or in combination of two or more.
  • 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 j8 position can be used in combination.
  • the skeleton of the epoxy compound is at least one selected from bisphenol type epoxy resin, novolac type epoxy resin, alicyclic group-containing type epoxy resin, and poorly soluble epoxy resin.
  • bisphenol type epoxy resin novolac type epoxy resin
  • alicyclic group-containing type epoxy resin alicyclic group-containing type epoxy resin
  • poorly soluble epoxy resin Favored ,.
  • Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxeta-lmethoxy) methyl] ether, 1, 4-bis [(3-methyl-3-oxeta-lmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxeta-lmethoxy) methyl] benzene, (3-methyl-3-oxeta-l) methyl acrylate , (3 Echiru 3 Okiseta -) methyl Atari rate, (3-methyl 3-Okiseta -) methyl meth Tari rate, (3 Echiru 3 Okiseta - Le) methylate Rume Tatari rate or oligomers thereof or copolymers In addition to polyfunctional oxetanes, compounds having an oxetane group, novolac resin, poly (p-hydroxys), poly (
  • 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, triethylbenzylammo- Um chloride, etc.
  • block isocyanate compounds for example, dimethylamine
  • imidazole derivative bicyclic amidine compounds and their salts for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) —4-Methylimidazole, 2-Phenolimidazole, 4-Phenolimidazole, 1-Cyanethyl—2-Fuel-Loimi Dazole,
  • the epoxy resin compound or the oxetane compound is a curing catalyst, or a compound capable of promoting thermal curing other than the above, as long as it can promote the reaction of these with a carboxyl group. May be used.
  • the solid content in the solid content of the photosensitive composition of the epoxy compound, the oxetane compound, and a compound capable of accelerating the thermal curing of these with a carboxylic acid is usually 0.01 to 15% by mass.
  • a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is composed of at least two isocyanates. It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing a monoto group.
  • bifunctional isocyanates eg, mixtures of 1,3 and 1,4-phenolic diisocyanates, 2,4 and 2,6 toluene diisocyanates, 1,3 and 1,4 xylates
  • Range isocyanate bis (4-isocyanate monophenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone di-socyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate
  • a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate or its derivative may be used.
  • isocyanate group blocking agent examples include alcohols (for example, isopropanol, tert-butanol, etc.), ratatas (for example, epsilon-prolactam, etc.), phenols (for example, phenol, crezo-monore, p-tert-butinolephenol) Nore, p-sec butinolevenore, p-sec amylphenol, p-octylphenol, p-norphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline) And the like, and active methylene compounds (for example, dialkyl malonate, methyl ethyl ketoxime, acetyl acetone, alkyl acetoacetonitrile, acetooxime, cyclohexanone oxime, etc.).
  • compounds having at least one polymerizable double bond and at least one block isocyanate group examples include alcohols
  • a melamine derivative may be used as the thermal crosslinking agent.
  • the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, etc.). These may be used alone or in combination of two or more.
  • storage stability Hexamethylated methylol melamine is particularly preferred, with alkylated methylol melamine being preferred, since the surface hardness of the photosensitive layer is good and effective in improving the film strength itself of the cured film.
  • the solid content of the thermal crosslinking agent in the solid content of the photosensitive composition is preferably 1 to 50% by mass, more preferably 3 to 30% by mass.
  • the solid content is less than 1% by mass, improvement in the film strength of the cured film is not observed, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.
  • the thermal crosslinking agent is preferably an epoxy compound from the viewpoint of reactivity.
  • the elastomer can be appropriately selected according to the purpose for which there is no particular limitation.
  • compounds described in [0061] to [0073] of International Publication No. 04Z34147 pamphlet may be used. .
  • the phenoxy resin can be appropriately selected according to the purpose for which there is no particular limitation.
  • the compounds described in International Publication No. 04Z34147 pamphlet [0074] to [0078] are used. Also good.
  • the sensitizer improves the minimum energy (sensitivity) of the light when the photosensitive layer is exposed and developed without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferable to use in combination.
  • the sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light and visible light laser).
  • the light irradiation means for example, visible light, ultraviolet light and visible light laser.
  • 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 causing radicals and It is possible to generate useful groups such as acids.
  • substances for example, radical generator, acid generator, etc.
  • energy transfer, electron transfer, etc. for example, energy transfer, electron transfer, etc.
  • the sensitizer is at least selected from a condensed ring compound, an aminophenol ketone compound, a polynuclear aromatic, an acid nucleus, a basic nucleus, and a fluorescent brightener nucleus. 1 type may be included and another sensitizer may be included as needed. Sensitization As the agent, hetero-fused compounds and amaminobenzophenone compounds are more preferred from the viewpoint of improving sensitivity, and hetero-fused compounds are particularly preferred.
  • a hetero condensed ring compound is preferable as a compound (condensed ring compound) in which an aromatic ring or a heterocyclic ring is condensed.
  • the hetero-fused ring system compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring.
  • Examples of the hetero-fused ring compound include a hetero-fused ketone compound.
  • the hetero-fused ketone compounds attaridone compounds and thixanthone compounds are more preferable, and thixanthone compounds are particularly preferable.
  • hetero-fused ketone ketone compound examples include, for example, attaridone compounds such as attaridone, chloroacridone, N-methyl attaridone, N butyl attaridone, N butyl chloro attaridone, thixanthone, Thioxanthone compounds such as isopropyl thixanthone, 2,4 jetylthioxanthone, 1 chloro-4 propyloxy thixanthone, QuantacureQT X; 3— (2 benzofuroyl) 7 Jetylaminotamarin, 3— (2 benzofuroyl) 7— (1-Pyrrolidyl) coumarin, 3 Benzyl 7- Jetylaminocoumarin, 3 -— (2-Methoxybenzoyl) 7 Jetylaminocoumarin, 3 1 (4-Dimethylaminobenzoyl) 7— Jetylaminocoumarin, 3, 3'-carbonylbis (5,7-di-di
  • polynuclear aromatics for example, pyrene, perylene, triphenylene
  • xanthenes for example, fluorescein, eosin, erythrucine, rhodamine B, rose bengal
  • cyanines for example, indocarbocyanine, Thiacarboxanthine, Oxacarboxin
  • Merocyanines eg, merocyanine, carbomerocyanine
  • thiazines eg, thionine, methylene blue, toluidine blue
  • anthraquinones eg, anthraquinone
  • squaliums eg, squalium
  • the content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, based on all components of the photosensitive composition for photosensitive film. 05-1% by mass is particularly preferred.
  • the sensitivity When the content is less than 0.01% by mass, the sensitivity may be lowered, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.
  • the mass ratio of the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may decrease and the change in sensitivity over time may be adversely affected.
  • the combination of the sensitizer and the photopolymerization initiator is particularly preferably a combination of a thixanthone compound and an oxime derivative from the viewpoint 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 an aminoalkyl group or aminophenyl group in a partial structure.
  • the other components include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other assistants.
  • Agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.
  • the thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
  • thermal polymerization inhibitor examples include 4-methoxyphenol, hydroquinone, and alcohol. Killed or aryl substituted nitroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy1-2hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2, 6 Di-t-butyl-4 cresol, 2,2, -methylenebis (4-methyl-6t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, Nitroso compounds,-Chelates of troso compounds with A1, etc.
  • the content of the thermal polymerization inhibitor is preferably from 0.001 to 5 mass%, more preferably from 0.005 to 2 mass%, based on the polymerizable compound of the photosensitive layer. 01 to 1% by mass is particularly preferred.
  • 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.
  • the plasticizer should be added to control the film physical properties (flexibility) of the photosensitive layer.
  • plasticizer examples include dimethyl phthalate, dibutyl phthalate, diisopropyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diphenyl phthalate.
  • Phthalic acid esters such as ril phthalate and octyl capryl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate
  • Glycol esters such as dimethyl dalycose phthalate, ethino retino eno ethino glycolate, methyl phthal yl ethyl dalicolate, butino retino levino oleglycolate, triethylene glycol dicabrylate; tricresyl phosphate, Phosphate esters such as triphenyl phosphate; 4 Amides such as toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; Diisobutyl adipate, Dioctyl adipate Dibasic acid esters such as dimethyl sebacate, dibutyl sebacate, dioctyl sepacate, dioctyl azelate, dibutyl malate; triethyl taenoate, tributyl taenoate,
  • the content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive layer. preferable.
  • the coloring pigment is not particularly limited and can be appropriately selected according to the purpose.
  • Bikku! J Pure One Blue BO (CI 42595), Auramin (CI 41000), Fat 'Black HB (CI 26150) , Monolight 'Yellow GT (CI Pigment' Yellow 1 2), Permanent 'Yellow GR (CI Pigment' Yellow 17), Permanent 'Yellow HR (CI Pigment' Yellow 83), Permanent 'Carmine FBB (CI Pigment' Red 146) , Hoster Balm Red ESB (CI Pigment 'Violet 19), Permanent' Rubi I FBH (CI Pigment 'Red 11) Huster's' Pink B Supra (CI Pigment 'Red 81) Monastral' First 'Blue (CI Pigment' Blue 15), Monolite 'Fast' Black B (CI Pigment 'Black 1), Carbon, CI Pigment' Red 97 CI Pigment 'Red 122, CI Pigment' Red 149, CI Pigment 'Red 168
  • the solid content of the colored pigment in the solid content of the photosensitive composition can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during the formation of a permanent pattern. Different forces depending on the type of facial material Generally 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.
  • Solid pigment The photosensitive composition is used for the purpose of improving the surface hardness of the permanent pattern or keeping the coefficient of linear expansion low, or keeping the dielectric constant or dielectric loss tangent of the cured film low, if necessary.
  • Inorganic pigments and organic fine particles can be added.
  • the inorganic pigment can be appropriately selected from known ones that are not particularly limited.
  • kaolin barium sulfate, barium titanate, key oxide powder, fine powder oxide oxide, vapor phase method silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and my strength.
  • the average particle diameter of the inorganic pigment is preferably less than 10 m, more preferably 3 m or less. If the average particle size is 10 m or more, the resolution may deteriorate due to light scattering.
  • the organic fine particles can be appropriately selected according to the purpose without particular limitation, and examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle size of 0.01 to 5 / ⁇ ⁇ , an oil absorption of about 100 to 200 m 2 Zg, 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.
  • a known adhesion promoter may be used for each layer.
  • adhesion promoter examples include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3 morpholinomethyl-1 phenyroot triazole-2 thione, 3— morpholinomethyl 5 phenyl oxadiazole 2 thione, 5 amino 3 Examples include ruphorinomethyl thiadiazole-2-thione, and 2 mercapto 5-methylthiothiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.
  • the content of the adhesion promoter is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on all the components of the photosensitive layer. % To 5% by mass is particularly preferred.
  • 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 a thermoplastic resin layer or the like as needed. Preferred to have other layers of.
  • the photosensitive layer is formed by the photosensitive composition of the present invention.
  • the portion provided in the photosensitive film of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose.
  • the sensitivity of the photosensitive layer laminated on the support is as described above. as in, lay preferred that a 0. l ⁇ 200miZcm 2, and particularly preferably it is 0. 2 ⁇ 100mjZcm 2 is more preferred instrument 0. 5 ⁇ 50miZcm 2.
  • the thickness of the photosensitive layer is particularly preferably 1 to: 2 to 50 m, more preferably 4 to 30 ⁇ m, more preferably 2 to 50 m.
  • the support is not particularly limited, and can be appropriately selected according to the purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance. Further, the surface is smooth. It is more preferable that the sex is good. Specific examples of the support and protective film are described in, for example, [0342] to [0348] of JP-A-2005-258431.
  • ⁇ Other layers> Other layers in the photosensitive film are not particularly limited and can be appropriately selected according to the purpose.
  • a cushion layer an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface
  • a protective layer may be provided on the photosensitive layer.
  • the cushion layer is not particularly limited and may be appropriately selected depending on the purpose, and may be swellable or soluble or insoluble in an alkaline liquid.
  • thermoplastic resin examples include, for example, an ethylene / acrylate copolymer copolymer, styrene, and (meth) (Meth) such as saponified acrylate copolymer, kento of butyltoluene and (meth) acrylic ester copolymer, poly (meth) acrylate, butyl (meth) acrylate and vinyl acetate Acrylic ester copolymers, etc., (meth) acrylic acid ester and (meth) acrylic acid copolymer, styrene, (meth) acrylic acid ester and (meth) acrylic acid copolymer Etc.
  • the softness point (Vicat) of the thermoplastic resin in this case is a force that can be appropriately selected according to the purpose without any particular limitation. For example, 80 ° C or less is preferable.
  • the above-mentioned thermoplastic resin has a softness point of 80 ° C or less, as well as “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, Issued on October 25, 1968).
  • the organic polymers whose soft spot is about 80 ° C or less those that are soluble in alkaline liquids are listed.
  • various plasticizers compatible with the organic polymer material are added to the organic polymer material so that a substantial softness can be obtained. It is also possible to lower the point below 80 ° C.
  • the interlayer adhesive force of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. However, for example, it is preferable that the interlayer adhesion between the support and the cushion layer is the smallest among the interlayer adhesion of each layer. Such an interlayer adhesion force
  • the photosensitive layer can be developed using an alkaline developer. Further, after exposing the photosensitive layer while leaving the support, the photosensitive film force is peeled off, and the photosensitive layer is developed using an alkaline developer.
  • the method for adjusting the interlayer adhesive force can be appropriately selected according to the purpose without any particular limitation.
  • a known polymer, supercooling substance, or adhesion improver in the thermoplastic resin can be selected.
  • a method of adding a surfactant, a release agent and the like can be selected.
  • the plasticizer can be appropriately selected according to the purpose without any particular limitation.
  • polypropylene glycol polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutino phthalate, tricres.
  • Alcohols and esters such as zircphosphate, uddernoresiphosphate and biphenyldiphosphate, amides such as toluenesulfonamide, and the like.
  • thermoplastic resin examples include a copolymer whose main component is an essential copolymer component of ethylene.
  • the copolymer having ethylene as an essential copolymer component is a force that can be appropriately selected according to the purpose without any particular limitation.
  • ethylene vinyl acetate copolymer (EV A) ethylene-ethyl acrylate. Copolymer (EEA) and the like.
  • the interlayer adhesive force of the photosensitive film can be appropriately selected according to the purpose without any particular limitation.
  • the adhesive strength between the photosensitive layer and the cushion layer is preferably the smallest.
  • the support and cushion layer are peeled off from the photosensitive film carrier, the photosensitive layer is exposed, and then the photosensitive layer is developed using an alkaline developer. be able to.
  • the support and the cushion layer can be 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 appropriately selected according to the purpose for which there is no particular limitation. For example, a method of adding various polymers, supercooling substances, adhesion improvers, surfactants, mold release agents, etc. to the thermoplastic resin, adjusting the ethylene copolymerization ratio described below The method of doing is mentioned.
  • 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. 60-80% by mass is more preferred. 65-80% by mass is particularly preferred.
  • 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. If the amount exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled off. It may be difficult to produce the photosensitive film.
  • the thickness of the cushion layer is not particularly limited.
  • the force f can be appropriately selected according to the purpose.
  • F column; t is 5-50 111 girls, 10-50 111 girls. Preferably, 15-40111.
  • the thickness is less than 5 m, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition permanent pattern may not be formed. Problems such as increased load may occur.
  • the oxygen barrier layer is preferably a film having a thickness of preferably about 0.5 to 5 ⁇ m, and is preferably formed mainly of polybulal alcohol.
  • 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.
  • the solvent is not particularly limited and may be appropriately selected according to the purpose.
  • examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol.
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone; , Esters of butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; Halogenated hydrocarbons such as tetrasalt carbon, trichloroethylene, blackform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene; tetrahydrofuran, jetyl ether, ethylene alcohol Examples include ethers such as methylenoatenole, ethyleneglycolenoethylenoleatenole, 1-methoxy
  • the photosensitive composition solution is coated 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.
  • the force can be selected appropriately according to the purpose.
  • spray method roll coating method, spin coating method, slit coating method, etatrusion.
  • the coating method include a coating method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
  • the drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
  • the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored.
  • the length of the long photosensitive film is not particularly limited. For example, a range force of 10-20, OOOm can be appropriately selected. In addition, slitting may be performed for the convenience of the user, and a long body in the range of 100 to 1, OOOm may be rolled. In this case, it is preferable that the support is wound up so as to be the outermost side.
  • the roll-shaped photosensitive film may be slit into a sheet shape.
  • a separator especially moisture-proof and desiccant-containing
  • the photosensitive laminate is formed by laminating at least the photosensitive layer on a substrate and other layers appropriately selected according to the purpose.
  • the substrate is a substrate to be processed on which a photosensitive layer is formed, or a transfer target to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is appropriately selected depending on the purpose without particular limitation. For example, it can be arbitrarily selected from those having a high surface smoothness to those having a rough surface.
  • a so-called substrate in which a plate-like substrate is preferred 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.
  • 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, in the photosensitive film of the present invention.
  • a method of laminating by transferring at least one of heating and pressurizing at least one of the photosensitive layer and transferring force is mentioned.
  • the photosensitive composition is applied and dried on the substrate to form a photosensitive layer.
  • the coating and drying method can be appropriately selected according to the purpose without any particular limitation.
  • the photosensitive composition is dissolved, emulsified or dispersed on the surface of the substrate in water or a solvent.
  • a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.
  • the solvent of the photosensitive composition solution can be appropriately selected according to the purpose without any particular limitation, and examples thereof include the same solvents as those used for the photosensitive film. They are
  • One type may be used alone or two or more types may be used in combination. Also, add a known surfactant.
  • the coating method and drying conditions can be appropriately selected according to the purpose without any particular limitation, and the same methods and conditions as those used for the photosensitive film are used.
  • the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing.
  • the protective film it is preferable that the protective film is peeled off and laminated so that the photosensitive layer overlaps the substrate.
  • the heating temperature is not particularly limited, and can be appropriately selected according to the purpose. For example, 15 to 180 ° C is preferable, and 60 to 140 ° C is more preferable.
  • the pressure of the pressurization is not particularly limited, and can be appropriately selected depending on the purpose. For example, 0.1 to 1. OMPa force is preferable, 0.2 to 0.8 MPa force is more preferable! / ⁇ .
  • the apparatus for performing at least one of the heating is not particularly limited, and can be appropriately selected according to the purpose.
  • a laminator for example, Taisei Laminanee VP-II,-Chigo Morton, Inc.
  • Preferable examples include VP130).
  • the photosensitive film of the present invention and the photosensitive laminate use the photosensitive composition of the present invention, the sensitivity is good, the raw storage property is excellent, and a pattern can be formed with high definition. Therefore, for the formation of various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, for the manufacture of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, etc. It can be suitably used for pattern formation of micromachines, proofs, etc., and can be particularly suitably used for permanent pattern formation of printed circuit boards.
  • a permanent pattern such as a protective film, an interlayer insulating film, or a solder resist
  • HAST high acceleration test
  • the pattern forming apparatus of the present invention includes the photosensitive layer and includes at least a light irradiation unit and a light modulation unit.
  • the permanent pattern forming method of the present invention preferably includes at least an exposure step and further includes other steps such as a development step and a curing treatment step.
  • the photosensitive layer in the photosensitive film of the present invention is exposed.
  • 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 the photosensitive layer in the photosensitive film, and can be appropriately selected depending on the purpose. It is preferable that this is performed on a laminated body formed by laminating the optical film while performing at least one of heating and pressing.
  • the exposure can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
  • the analog exposure can be appropriately selected depending on the purpose without any particular limitation. For example, exposure is performed 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. A method is mentioned.
  • the digital exposure can be appropriately selected according to the purpose without any particular restriction.
  • a control signal is generated based on pattern formation information to be formed, and modulated according to the control signal.
  • light For example, n light (where n is a natural number of 2 or more) two-dimensional light receiving means and receiving light from the light irradiating means.
  • the exposure head is arranged so that the column direction of the predetermined inclination angle ⁇ is set, and, for the exposure head, N-exposure (N double exposure) of the usable pixel parts by the used pixel part designating means.
  • N is a natural number of 2 or more
  • N double exposure refers to a straight line parallel to the scanning direction of the exposure head on the exposed surface in almost all of the exposed region on the exposed surface of the photosensitive layer.
  • 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.
  • the arrangement of the picture element portions does not necessarily have to be a rectangular lattice, for example, an arrangement of parallelograms.
  • the “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 picture element parts in the used picture element part decreases, even if it is used to connect multiple exposure heads in such a case, scanning will occur due to errors in the mounting angle and arrangement of the exposure heads.
  • the number of pixel parts in the used pixel part that intersects a straight line parallel to the direction may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is less than the resolution.
  • N double exposure and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” with respect to an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method.
  • N in the N-exposure is a natural number of 2 or more, a force that can be appropriately selected according to the purpose for which there is no particular limitation, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .
  • the development is performed by removing an unexposed portion of the photosensitive layer.
  • the method for removing the uncured region can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a method using a developer.
  • the developer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include an alkaline aqueous solution, an aqueous developer, an organic solvent, and the like. Among these, a weakly alkaline aqueous solution is used. preferable.
  • the base 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, and phosphoric acid. Sodium, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax, etc.
  • the pH of the weakly alkaline aqueous solution is more preferably, for example, about 9 to about 8 to 12: L1.
  • Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.
  • the temperature of the developer is a force that can be appropriately selected according to the developability of the photosensitive layer. For example, about 25 to 40 ° C. is preferable.
  • the developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.)
  • an organic solvent for example, alcohols, ketones, esters, ethers, amides, latatones, 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.
  • the formation of the pattern may include, for example, a curing process, an etching process, a plating process, and the like. These may be used alone or in combination of two or more.
  • the pattern forming method is a permanent pattern forming method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter
  • the photosensitive layer is cured after the developing step. It is preferable to provide the hardening process process which processes.
  • the curing treatment step is not particularly limited and can be appropriately selected depending on the purpose. For example, a full exposure process, a full heat treatment, and the like are preferable.
  • Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. By this overall exposure, curing of the resin in the photosensitive composition forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
  • a force that can be appropriately selected according to the purpose without particular limitation 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, etc. are suitable. Can be mentioned.
  • the exposure dose is usually 10 miZcm 2 to 2,000 mjz cm.
  • Examples of the method of the entire surface heat treatment 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.
  • the heating temperature in the entire surface heating is preferably 120 to 250 ° C, more preferably 120 to 200 ° C. If the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment. If the heating temperature exceeds 250 ° C, the resin in the photosensitive composition may be decomposed, resulting in film quality. May be weak and brittle.
  • the heating time in the whole surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
  • the apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
  • 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 at 405 nm. It can be suitably used to form a pattern that is compatible with productivity.
  • the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, it is possible to protect the wiring from external impact and bending force.
  • the interlayer insulating film for example, for high-density mounting of semiconductors and components on a multilayer wiring board or a build-up wiring board. Useful.
  • a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern is used. It can be suitably used for the manufacture of liquid crystal structural members such as filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., especially for the formation of permanent patterns on printed circuit boards. Can be suitably used.
  • liquid crystal structural members such as filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc.
  • Sensitizer (S—1) represented by the following structural formula (1) 0.5 mass part
  • the barium sulfate dispersion is composed of 28.5 parts by weight of barium sulfate (manufactured by Zhi-Gakusha, B30) and KAYARAD ZFR-1492H (bis F-type epoxy acrylate, concentration 66% Nippon Kayaku Co., Ltd.) 15. After mixing 6 parts by mass, 28.2 parts by weight of normal propyl acetate, and 0.2 parts by weight of phthalocyanine green, the motor mill M-200 (manufactured by Eiger) was used. And then dispersed for 3.5 hours at a peripheral speed of 9 mZs.
  • a surface of a copper-clad laminate (no through-hole, copper thickness 12 m) on which a wiring was formed as a printed board was prepared by chemical polishing treatment.
  • the photosensitive composition is applied by a screen printing method using a 120 mesh Tetron screen so that the thickness after drying is 30 m, and a hot air circulation type at 80 ° C. for 15 minutes.
  • a photosensitive layer was formed by drying with a dryer, and a photosensitive laminate in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared.
  • the photosensitive laminate was evaluated for sensitivity, resolution, storage stability, and edge roughness by the following methods. Table 1 shows the results other than the shortest development time.
  • the shortest development time was 20 seconds.
  • a sensitivity curve was obtained by plotting the relationship between the amount of light irradiation and the thickness of the cured layer. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 m as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.
  • DMD36 controlled to drive only 1024 x 256 6 rows and the optical for imaging the light shown in FIGS. 1A and 1B on the photosensitive film
  • a pattern forming apparatus 10 having an exposure head 30 having a system was used.
  • each exposure head 30 that is, each DMD 36, is slightly larger than the angle ⁇ where double exposure is performed using the available 1024 rows x 256 rows micromirror 58
  • N is the number of double exposures N, the number of micromirrors that can be used 58 s in the row direction, the spacing p of the micromirrors 58 that can be used in the row direction p, and the micromirrors with the exposure head 30 tilted.
  • N is the number of double exposures N, the number of micromirrors that can be used 58 s in the row direction, the spacing p of the micromirrors 58 that can be used in the row direction p, and the micromirrors with the exposure head 30 tilted.
  • FIG. 30 shows the pattern of light spots from the micromirror 58 that can be used for DMD36.
  • the exposure pattern for every other column of the micromirrors 58 that can be used is divided into the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B.
  • the actual exposure on the exposed surface The pattern is a superposition of these two exposure patterns.
  • the light spot position detecting means a set of a slit 28 and a photodetector is used, and an exposure head 30
  • the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head was measured.
  • the natural number T that is closest to the value t that satisfies this relationship is assigned to each of the exposure heads 30 and 30.
  • 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.
  • the regions 82 and shaded areas in FIG. Micromirrors corresponding to the light spots constituting the covered region 84 were identified and added as micromirrors not used during the main exposure.
  • a signal for setting the angle of the always-off state is sent by the pixel unit control means, and these microphone mirrors are substantially It was controlled so that it was not involved in exposure.
  • the exposure areas formed by a plurality of the exposure heads in the exposure areas 32 and 32 are formed by a plurality of the exposure heads in the exposure areas 32 and 32.
  • the photosensitive laminate was stored for 1 day under drying acceleration conditions (relative humidity 50%) at 40 ° C. One day later, in the same manner as described above, sensitivity and resolution were measured, and aging stability was evaluated based on the following criteria.
  • the photosensitive laminate is irradiated with double exposure so that a horizontal line pattern in a direction orthogonal to the scanning direction of the exposure head is formed, and a part of the photosensitive layer is exposed.
  • a pattern was formed in the same manner as in the measurement of the resolution.
  • any five points on a line with a line width of 50 m were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ⁇ ), and the edge position in the field of view was observed.
  • the absolute value of the difference between the most swollen part (mountain peak) and the narrowest part (valley bottom part) was calculated, and the average value of the five observed points was calculated as the edge roughness.
  • the edge roughness is preferably as the value is small, since it exhibits good performance.
  • the photosensitive composition solution obtained in Example 1 was applied to a PET (polyethylene terephthalate) film having a thickness of 16 m, a width of 30 Omm, and a length of 200 m as the support with a bar coater, and 80 ° C.
  • a photosensitive layer having a thickness of 30 m was formed by drying in a hot air circulation dryer.
  • a polypropylene film having a thickness of 20 ⁇ m, a width of 310 mm, and a length of 210 m was formed as a protective film on the photosensitive layer. Were laminated by lamination to produce the photosensitive film.
  • the photosensitive film of the photosensitive film is in contact with the copper-clad laminate, and the protective film on the photosensitive film is peeled off, and a vacuum laminator (A photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) are laminated in this order. Prepared.
  • Crimping conditions are: vacuuming time 40 seconds, crimping temperature 70 ° C, crimping pressure 0.2 MPa, under pressure The interval was 10 seconds.
  • the photosensitive laminate was evaluated for sensitivity, resolution, storage stability, and edge roughness.
  • the resolution, storage stability over time (evaluation of storage stability 1), and edge roughness were evaluated in the same manner as in Example 1.
  • the sensitivity was evaluated as follows.
  • the storage stability was evaluated by the following method. The results are shown in Table 1.
  • 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. I let you. After standing at room temperature for 10 minutes, the support was peeled from the photosensitive laminate, and the amount of light energy required to cure the photosensitive layer was measured in the same manner as in Example 1.
  • the photosensitive film was wound up with a winder to produce a photosensitive film raw roll.
  • the obtained photosensitive film raw roll was slit with a coaxial slitter, and was 300 mm in length and 76 mm in inner diameter.
  • a cylindrical roll core was wound up to 150 m in a width of 250 mm to produce a photosensitive film roll.
  • the photosensitive film roll thus obtained was wrapped in a black polyethylene cylindrical bag (film thickness: 80 m, water vapor transmission rate: 25 gZm 2 '24 hr or less), and a polypropylene bush was pushed into both ends of the winding core.
  • the roll-shaped sample with both ends closed with the bush was stored at 25 ° C and 55% RH for 21 days, and then observed for end face fusion, and the storage stability was evaluated according to the following criteria.
  • ⁇ A part of the end face is glossy, and a slight amount of end face fusion occurs (use limit).
  • X State where the entire end face is glossy and a large amount of end face fusion occurs.
  • Example 3 In Example 1, 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the oxime derivative (1-2, photopolymerization) represented by the following structural formula (2). Polymerization 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • the photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 2.
  • Example 1 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-3, photopolymerization) represented by the following structural formula (3). Initiator) 1 part by weight and N-phenyldaricin (additive) A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 0.5 part by weight. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • the photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
  • Example 1 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-4, photopolymerization) represented by the following structural formula (4). 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. Photosensitivity Using the composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • the photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
  • Example 1 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-5, photopolymerization) represented by the following structural formula (5). 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • Example 1 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-6, photopolymerization) represented by the following structural formula (6). 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • Example 1 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-7, photopolymerization) represented by the following structural formula (7). Initiator) 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • Example 3 instead of the pattern forming apparatus, a glass negative mask having a pattern similar to the above was prepared separately, and this negative mask was brought into contact with the photosensitive laminate, and an exposure amount of 40 miZcm 2 was obtained with an ultrahigh pressure mercury lamp. And exposed.
  • KAYARAD ZFR— 1492H bisphenol F type epoxy acrylate
  • a photosensitive composition solution was prepared in the same manner as in Example 3 except that ZAR-1413H (bisphenol A type epoxy acrylate, concentration 66%, manufactured by Nippon Kayaku Co., Ltd.) was used. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • ZAR-1413H bisphenol A type epoxy acrylate, concentration 66%, manufactured by Nippon Kayaku Co., Ltd.
  • the photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
  • Example 3 KAYARAD ZFR-1492H (bisphenol F-type epoxy acrylate) in the photosensitive composition solution was used as a raw material from the following binder (compound represented by the general formula (2)).
  • a photosensitive composition solution was prepared in the same manner as in Example 3 except that the binder composition was changed to a binder. Using the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
  • the photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
  • Epototo YDPF-1000 (manufactured by Tohto Kasei) 200 parts by weight, 36 parts by weight of acrylic acid, 0.2 part by weight of methyl hydroquinone, 60 parts by weight of propylene glycol monomethyl ether monoacetate are placed in a reaction vessel and stirred at 90 ° C. The reaction was carried out. 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%.
  • Example 1 (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 photosensitive laminate was prepared.
  • the photosensitive laminate was evaluated in the same manner as in Example 1 for sensitivity, resolution, storage stability 1 and edge roughness. The results are shown in Table 1.
  • a photosensitive film was formed in the same manner as in Example 2 except that the photosensitive composition solution of Comparative Example 1 (changed from 6 parts by mass of Irgacure 819 to 3 parts by mass of Irgacure 907) was used.
  • the body was prepared.
  • the photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
  • Example 1 KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate) in the photosensitive composition solution was added to lipoxy PR-300 (taresol novolak type epoxide talate, concentration 65%, Showa A photosensitive composition solution was prepared in the same manner as in Example 1 except that the product was changed to “manufactured by Kobunshi Co., Ltd.” to prepare a photosensitive laminate.
  • KAYARAD ZFR-1492H bisphenol F type epoxy acrylate
  • lipoxy PR-300 taresol novolak type epoxide talate, concentration 65%
  • the photosensitive laminate was evaluated in the same manner as in Example 1 for sensitivity, resolution, storage stability 1 and edge roughness. The results are shown in Table 1.
  • 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. The body was prepared.
  • the photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
  • the photosensitive composition of the present invention is highly sensitive, excellent in preservability and handling properties, can form high-definition patterns, and is suitable for production of printed wiring boards including package substrates. It can be widely used for the formation of permanent patterns (interlayer insulating film, protective film, solder resist pattern, etc.) in patterns or high-definition permanent patterns in the semiconductor field. It can be suitably used for a pattern formation method and formation of a print substrate.
  • the photosensitive film of the present invention can form a high-definition pattern with high sensitivity, excellent raw storage and handling properties, and a non-cage substrate.
  • the permanent pattern forming method of the present invention can be suitably used for forming a printed circuit board.
  • the method for forming a permanent pattern of the present invention is the photosensitive composition or photosensitive film of the present invention.
  • high-definition patterns can be formed with high sensitivity, excellent raw storage and handling, so patterns suitable for manufacturing printed circuit boards including package substrates, or high-definition in the semiconductor field Can be formed with high definition and efficiency, such as various patterns that require high-precision exposure, and can be used to form various permanent patterns (interlayer insulation film, protective film, solder resist pattern, etc.). In particular, it can be suitably used for forming the printed circuit board of the present invention.

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Abstract

A photosensitive composition having satisfactory sensitivity and excellent in raw-stock storability and handleability; a photosensitive film; a method of permanent-pattern formation which enables a high-resolution permanent pattern for use in the semiconductor field (protective film, interlayer dielectric, solder resist pattern, etc.) to be efficiently formed; and a printed wiring board having a permanent pattern formed by the method of permanent-pattern formation. The photosensitive composition comprises: (A) a binder obtained by reacting a reaction product formed from (a) an epoxy compound having a partial structure comprising a bisphenol skeleton and (b) a monocarboxylic acid containing an unsaturated group with (c) a polybasic acid compound containing either of a saturated group and an unsaturated group; (B) a polymerizable compound; and (C) a photopolymerization initiator which is either of an acylphosphine oxide compound and an oxime derivative.

Description

明 細 書  Specification
感光性組成物、及び感光性フィルム、並びに永久パターン形成方法及び プリント基板  Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board
技術分野  Technical field
[0001] 本発明は、高感度で、感光性積層体の保存安定性、取り扱い性に優れる感光性組 成物及びこの感光性組成物を用いた感光性フィルム、並びに、半導体分野における 高精細な永久パターン (保護膜、層間絶縁膜、及びソルダーレジストパターンなど)を 高精細に、かつ、効率よく形成可能な永久パターン形成方法、及び該永久パターン 形成方法により永久パターンが形成されるプリント基板に関する。  [0001] The present invention relates to a photosensitive composition having high sensitivity and excellent storage stability and handleability of the photosensitive laminate, a photosensitive film using the photosensitive composition, and high-definition in the semiconductor field. The present invention relates to a permanent pattern forming method capable of forming a permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) with high definition and efficiency, and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.
背景技術  Background art
[0002] 従来より、ソルダーレジストなどの永久パターンを形成するに際して、支持体上に感 光性組成物を塗布、乾燥することにより感光層を形成させた感光性フィルムが用いら れている。前記永久パターンの製造方法としては、例えば、前記永久パターンが形 成される銅張積層板等の基体上に、前記感光性フィルムを積層させて積層体を形成 し、該積層体における前記感光層に対して露光を行い、該露光後、前記感光層を現 像してパターンを形成させ、その後硬化処理等を行うことにより前記永久パターンが 形成される。  Conventionally, when a permanent pattern such as a solder resist is formed, a photosensitive film in which a photosensitive layer is formed by applying a photosensitive composition on a support and drying it has been used. As a 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. After the exposure, the photosensitive layer is imaged to form a pattern, followed by a curing process or the like to form the permanent pattern.
[0003] 前記永久パターンを高精細かつ効率的に得るためには、感度を向上させることが 求められる。このため、感度の向上を図ることを目的として、光重合開始剤として α— アミノアルキルフエノン化合物（ィルガキュア 907)を用い、かつ増感剤としてチォキサ ントン化合物を (カャキュア DETX— S)含む感光層を有する感光性フィルムを提案 している (特許文献 1参照)。  [0003] In order to obtain the permanent pattern with high definition and efficiency, it is required to improve sensitivity. Therefore, for the purpose of improving sensitivity, a photosensitive layer using an α-aminoalkylphenone compound (Irgacure 907) as a photopolymerization initiator and a thixanthone compound (Cacure DETX-S) as a sensitizer. Has been proposed (see Patent Document 1).
しかし、前記 α—アミノアルキルフエノンィ匕合物はァミン構造を有するため、熱架橋 剤を用いた場合には熱架橋剤の反応を室温付近でも徐々に誘発し、前記感光性フ イルムの感度の経時安定性などの生保存性を低下させてしまうことがあった。  However, since the α-aminoalkylphenone compound has an amine structure, when a thermal crosslinking agent is used, the reaction of the thermal crosslinking agent is gradually induced even near room temperature, and the sensitivity of the photosensitive film is increased. In some cases, the raw storage stability such as the stability over time is reduced.
ここで、感光層を形成する感光性組成物溶液を基体上に直接塗布する場合 (以下 、「液レジタイプ」と称する）には、熱架橋剤以外の成分を分散させた分散液と、熱架 橋剤を分散又は溶解させた液とを作製しておき、後に両者を混合して調製する、い わゆる二液型だが、混合作業後、基体上に積層した状態は徐々に硬化反応が進み 、経時で露光、現像ができなくなる場合があり、積層体状態での保存安定性向上が 望まれている。 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, Rack It is a so-called two-component type that is prepared by mixing and later mixing a solution in which a crosslinking agent is dispersed or dissolved. However, after the mixing operation, the layered state on the substrate gradually proceeds with the curing reaction. In some cases, exposure and development cannot be performed over time, and an improvement in storage stability in a laminated state is desired.
また、支持体上に前記感光性組成物よりなる感光層を形成したフィルムを作製して おき、これをプリント基板等の基体上に積層してなる場合 (以下、「フィルムタイプ」と 称する）には、取り扱い易さが要求されるため上記液レジタイプのような態様は採り難 い。  In addition, when a film having a photosensitive layer made of the photosensitive composition formed on a support is prepared and laminated on a substrate such as a printed board (hereinafter referred to as “film type”). However, since it is required to be easy to handle, it is difficult to adopt an embodiment like the above liquid register type.
[0004] 一方、不飽和二重結合を有するアルカリ可溶性のバインダーと、光重合性化合物 のォキシム化合物と、増感剤のチォキサントン化合物と、重合性化合物と 2個以上の エポキシ基を含むエポキシィ匕合物と、を含む感光性組成物が提案されて ヽる (特許 文献 2及び 3参照)。  On the other hand, an alkali-soluble binder having an unsaturated double bond, an oxime compound as a photopolymerizable compound, a thixanthone compound as a sensitizer, an epoxy compound containing a polymerizable compound and two or more epoxy groups A photosensitive composition containing a product has been proposed (see Patent Documents 2 and 3).
しかし、これらを用いることによつても、感度は高くなる力 やはり感度の経時安定性 などの生保存性が低下する問題があった。  However, even when these are used, there is a problem that the raw storability such as the sensitivity of increasing the sensitivity is deteriorated.
[0005] 他方、感光層に用いられるバインダーとして、ビスフエノール骨格を部分構造に有 するエポキシアタリレートイ匕合物などをバインダーに用いたソルダーレジスト用パター ン形成材料が提案されて ヽる (特許文献 4参照)。 [0005] On the other hand, as a binder used in the photosensitive layer, a solder resist pattern forming material using an epoxy attale toy compound having a bisphenol skeleton in a partial structure as a binder has been proposed (patent). (Ref. 4).
し力しながら、特許文献 4の材料は、感度が低ぐ特にレーザー露光した場合には 露光タクトが遅く問題である。また、液状ソルダーレジスト塗布後の安定性と高感度化 の両立につ!、ては何ら記載がな!、。  However, the material of Patent Document 4 has a low sensitivity, and in particular when exposed to a laser, the exposure tact is slow, which is a problem. In addition, there is no mention of both stability and high sensitivity after application of a liquid solder resist!
したがって、高感度で、かつ積層体での生保存性にすぐれる感光性組成物、感光 性フィルム、前記感光性組成物を用いた感光性フィルム、並びに、保護膜、絶縁膜な どの永久パターンを高精細に、かつ、効率よく形成可能な永久パターン形成方法及 び該永久パターン形成方法によりパターンが形成されるプリント基板は未だ提供され ておらず、更なる改良開発が望まれているのが現状である。  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. It is.
[0006] 特許文献 1：特開 2000— 232264号公報 [0006] Patent Document 1: Japanese Patent Laid-Open No. 2000-232264
特許文献 2 :特表 2002— 519732公報  Patent Document 2: Special Table 2002—519732
特許文献 3 :特開 2005— 182004号公報 特許文献 4:国際公開第 04Z34147号パンフレット Patent Document 3: JP 2005-182004 Patent Document 4: Pamphlet of International Publication No.04Z34147
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明は、従来における前記問題を解決し、以下の目的を達成することを課題とす る。即ち、本発明は、高感度で、積層体の生保存性に優れる感光性組成物及びこの 感光性組成物を用いた感光性フィルム、並びに、半導体分野における高精細な永久 ノターン (保護膜、層間絶縁膜、及びソルダーレジストパターンなど)を高精細に、か つ、効率よく形成可能な永久パターン形成方法、及び該永久パターン形成方法によ り永久パターンが形成されるプリント基板を提供することを目的とする。 [0007] 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. An object of the present invention is to provide a permanent pattern forming method capable of efficiently and efficiently forming an insulating film, a solder resist pattern, etc.), and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method. And
課題を解決するための手段  Means for solving the problem
[0008] 前記課題を解決するための手段としては、以下の通りである。即ち、 [0008] Means for solving the above-described problems are as follows. That is,
< 1 > (A)ビスフエノール骨格を部分構造に有するエポキシィ匕合物（a)と、不飽和 基含有モノカルボン酸 (b)との反応物に、飽和基及び不飽和基のいずれかを含有す る多塩基酸化合物 (c)を反応させて得られるバインダーと、（B)重合性化合物と、 (C )光重合開始剤としてァシルホスフィンォキシド化合物及びォキシム誘導体の!/ヽずれ かと、を少なくとも含むことを特徴とする感光性組成物。  <1> (A) A reaction product of an epoxy compound (a) having a bisphenol skeleton in a partial structure and an unsaturated group-containing monocarboxylic acid (b) contains either a saturated group or an unsaturated group. A binder obtained by reacting the polybasic acid compound (c), (B) a polymerizable compound, and (C) a photo-initiator asylphosphine oxide compound and an oxime derivative! The photosensitive composition characterized by including at least.
< 2> (A)バインダーが、下記一般式（1)及び一般式（2)のいずれかで表される エポキシ化合物 (a)と、不飽和基含有モノカルボン酸 (b)との反応物に、飽和基及び 不飽和基の!/ヽずれかを含有する多塩基酸化合物 (c)を反応させて得られる光硬化 性榭脂である前記く 1 >に記載の感光性組成物である。  <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) with the unsaturated group-containing monocarboxylic acid (b). The photosensitive composition according to 1> above, which is a photocurable resin obtained by reacting a polybasic acid compound (c) containing either a saturated group or an unsaturated group.
[化 5] 一般式（1 )
Figure imgf000005_0001
[Chemical formula 5] General formula (1)
Figure imgf000005_0001
ただし、前記一般式（1)中、 Xは、水素原子及びグリシジル基のいずれかを表し、 R は、メチレン基及びイソプロピリデン基のいずれかを表す。 nは、 1以上の整数を表す  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
[化 6] 一般式（2)
Figure imgf000006_0001
[Chemical 6] General formula (2)
Figure imgf000006_0001
ただし、前記一般式（2)中、 R1は、水素原子及びメチル基のいずれかを表し、 R2及 び R3は、アルキレン基を表し、 m及び nは、 m+nが 2〜50となる正の整数を表し、 p は、正の整数を表す。 However, In the general formula (2), R 1 represents a hydrogen atom or a methyl group, R 2及beauty R 3 represents an alkylene group, m and n, m + n is 2 to 50 Represents a positive integer, and p represents a positive integer.
<3> 感度が、 0. l〜200mjZcm2である前記 <1>から <2>のいずれかに記 載の感光性組成物である。 <3> sensitivity, a photosensitive composition of the placing serial to any one of the is 0. L～200mjZcm 2 <1><2>.
<4> (D)熱架橋剤を、更に含む前記 <1>から <3>のいずれかに記載の感光 性組成物である。  <4> The photosensitive composition according to any one of <1> to <3>, further including (D) a thermal crosslinking agent.
< 5 > ォキシム誘導体が、下記一般式（3)及び一般式 (4)の 、ずれかで表される 部分構造を有する前記く 1 >から <4>のいずれかに記載の感光性組成物である。  <5> The photosensitive composition according to any one of <1> to <4>, wherein the oxime derivative has a partial structure represented by any of the following general formulas (3) and (4): is there.
[化 7] [Chemical 7]
Ar-(c(Y1)=N-0-Y2) —般式（3) Ar- (c (Y 1 ) = N-0-Y 2 ) —General formula (3)
\ / m  \ / m
[化 8]  [Chemical 8]
Ar-(cO-C(Y1)=N-0-Y2) —般式（4) Ar- (cO-C (Y 1 ) = N-0-Y 2 ) — General formula (4)
\ I m  \ I m
ただし、前記一般式 (3)及び (4)中、 Arは、芳香族基、及び複素環基のいずれか を表し、 Y1は、水素原子、及び一価の置換基のいずれかを表し、 Y2は、脂肪族基、 芳香族基、複素環基、 COY3, COHowever, in the general formulas (3) and (4), Ar represents either an aromatic group or a heterocyclic group, Y 1 represents any one of a hydrogen atom and a monovalent substituent, Y 2 is an aliphatic group, aromatic group, heterocyclic group, COY 3 , CO
Figure imgf000006_0002
Figure imgf000006_0002
及び Υ5は、脂肪族基、芳香族基、及び複素環基のいずれかを表し、 mは、 1以上の 整数を表す。 And 5 represents an aliphatic group, an aromatic group, or a heterocyclic group, and m represents an integer of 1 or more.
< 6 > (D)熱架橋剤の架橋基と (A)バインダーの酸性基との割合が、熱架橋基 Z 酸性基 =0.3〜3.0である前記 <4>から <5>のいずれかに記載の感光性組成 物である。  <6> The ratio of (D) the crosslinking group of the thermal crosslinking agent to (A) the acidic group of the binder is the thermal crosslinking group Z acidic group = 0.3 to 3.0, or any one of the above <4> to <5> It is a photosensitive composition.
<7> (B)重合性化合物が、（メタ)アクリル基を有するモノマーから選択される少 なくとも 1種を含む前記 <1>から <6>のいずれかに記載の感光性組成物である。 < 8 > (D)熱架橋剤が、エポキシィ匕合物、ォキセタンィ匕合物、ポリイソシァネート 化合物、ポリイソシァネートイ匕合物にブロック剤を反応させて得られる化合物、及びメ ラミン誘導体力 選択される少なくとも 1種である前記く 4 >からく 7 >の 、ずれかに 記載の感光性組成物である。 <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 thermal crosslinking agent is 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. The photosensitive composition according to any one of the above 4> Karaku 7>, which is at least one selected from the group consisting of force.
<9> (E)エラストマ一を、更に含む前記 <1>から <8>のいずれかに記載の感 光性組成物である。  <9> The photosensitive composition according to any one of <1> to <8>, further including (E) an elastomer.
<10> (F)フエノキシ榭脂を、更に含む前記 <1>から <9>のいずれかに記載 の感光性組成物である。  <10> The photosensitive composition as described in any one of <1> to <9>, further including (F) phenoxy resin.
<11> (G)増感剤を、更に含む前記 <1>からく 10>のいずれかに記載の感 光性組成物である。  <11> The photosensitive composition according to any one of <1> to 10, further comprising (G) a sensitizer.
< 12> (G)増感剤が、ヘテロ縮環系化合物を含む前記く 11 >に記載の感光性 組成物である。  <12> The photosensitive composition according to <11>, wherein the (G) sensitizer includes a hetero-fused ring compound.
< 13> ヘテロ縮環系化合物力 チォキサントンィ匕合物である前記く 12>に記載 の感光性組成物である。  <13> Hetero-fused ring compound power The photosensitive composition according to <12>, which is a thixanthone compound.
[0009] <14> 支持体と、該支持体上に前記 <1>から <13>のいずれかに記載の感 光性組成物からなる感光層と、を少なくとも有してなることを特徴とする感光性フィル ムである。 <14> A support, and a photosensitive layer made of the photosensitive composition according to any one of <1> to <13> above on the support, It is a photosensitive film.
<15> 感光層の厚みが、 1〜100 111でぁる前記<14>に記載の感光性フィル ムである。  <15> The photosensitive film according to <14>, wherein the photosensitive layer has a thickness of 1 to 100111.
<16> 支持体が、合成樹脂を含み、かつ透明である前記く 14>力 く 15>の V、ずれかに記載の感光性フィルムである。  <16> The photosensitive film according to any one of 14 and 15>, wherein the support includes a synthetic resin and is transparent.
< 17> 支持体が、長尺状である前記 < 14>力らく 16>のいずれかに記載の感 光性フィルムである。  <17> The light-sensitive film according to any one of the above <14> Force 16 which is a long support.
<18> 長尺状であり、ロール状に巻かれてなる前記く 14>からく 17>のいず れかに記載の感光性フィルムである。  <18> The photosensitive film according to any one of the above items 14> to 17>, which is long and wound in a roll shape.
<19> 感光層上に、保護フィルムを有する前記 < 14 >から < 18 >のいずれか に記載の感光性フィルムである。  <19> The photosensitive film according to any one of <14> to <18>, which has a protective film on the photosensitive layer.
[0010] <20> 基体上に、前記 <1>から <13>のいずれかに記載の感光性組成物か らなる感光層を有することを特徴とする感光性積層体である。 [0010] <20> The photosensitive composition according to any one of <1> to <13> above, on a substrate. A photosensitive laminate having a photosensitive layer.
< 21 > 感光層が、前記 < 14>から < 19 >のいずれかに記載の感光性フィルム により形成された前記く 20 >に記載の感光性積層体である。  <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> 光を照射可能な光照射手段と、該光照射手段からの光を変調し、前記 < 20 >から < 21 >の 、ずれかに記載の感光性積層体における感光層に対して露光 を行う光変調手段と、を少なくとも有することを特徴とするパターン形成装置である。 該< 22 >に記載のパターン形成装置においては、前記光照射手段が、前記光変調 手段に向けて光を照射する。前記光変調手段が、前記光照射手段から受けた光を 変調する。前記光変調手段により変調した光が前記感光層に対して露光させる。例 えば、その後、前記感光層を現像すると、高精細なパターンが形成される。  <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 comprising: at least a light modulation unit that performs the above. In the pattern forming apparatus according to <22>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation means modulates light received from the light irradiation means. 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 > 光変調手段が、形成するパターン情報に基づいて制御信号を生成する パターン信号生成手段を更に有してなり、光照射手段から照射される光を該パター ン信号生成手段が生成した制御信号に応じて変調させる前記 < 22>に記載のバタ ーン形成装置である。該< 23 >に記載のパターン形成装置においては、前記光変 調手段が前記パターン信号生成手段を有することにより、前記光照射手段から照射 される光が該パターン信号生成手段により生成した制御信号に応じて変調される。  <23> The light modulation means further includes a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control generated by the pattern signal generation means for the light emitted from the light irradiation means The pattern forming apparatus according to <22>, wherein the pattern is modulated according to a signal. In the pattern forming apparatus according to <23>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
< 24> 光変調手段が、 n個の描素部を有してなり、該 n個の描素部の中から連続 的に配置された任意の n個未満の前記描素部を、形成するパターン情報に応じて制 御可能である前記く 22 >からく 23 >のいずれかに記載のパターン形成装置である 。該< 24 >に記載のパターン形成装置においては、前記光変調手段における n個 の描素部の中から連続的に配置された任意の n個未満の描素部をパターン情報に 応じて制御することにより、前記光照射手段力 の光が高速で変調される。  <24> The light modulation means has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts. The pattern forming apparatus according to any one of the above items 22> and 23>, which can be controlled according to pattern information. In the pattern forming apparatus according to <24>, any less than n pixel parts arranged continuously from the n pixel parts in the light modulation unit are controlled according to pattern information. As a result, the light of the light irradiation means power is modulated at high speed.
< 25 > 光変調手段が、空間光変調素子である前記く 22>からく 24>のいずれ かに記載のパターン形成装置である。  <25> The pattern forming apparatus according to any one of <22> to <24>, wherein the light modulation means is a spatial light modulation element.
< 26 > 空間光変調素子が、デジタル 'マイクロミラー'デバイス (DMD)である前 記 < 25 >に記載のパターン形成装置である。  <26> The pattern forming apparatus according to <25>, wherein the spatial light modulation element is a digital 'micromirror' device (DMD).
< 27> 描素部が、マイクロミラーである前記く 24>からく 26 >のいずれかに記 載のパターン形成装置である。 < 28 > 光照射手段が、 2以上の光を合成して照射可能である前記く 22>からく 27 >の 、ずれかに記載のパターン形成装置である。該< 28 >に記載のパターン形 成装置においては、前記光照射手段が 2以上の光を合成して照射可能であることに より、露光が焦点深度の深い露光光によって行われる。この結果、前記感光層への 露光が極めて高精細に行われる。例えば、その後、前記感光層を現像すると、極め て高精細なパターンが形成される。 <27> The pattern forming apparatus according to any one of the above <24>, <26>, wherein the pixel part is a micromirror. <28> The pattern forming apparatus according to any one of the above <22> and <27>, wherein the light irradiation unit can synthesize and irradiate 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 to 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 > 光照射手段が、複数のレーザと、マルチモード光ファイバと、該複数のレ 一ザ力 それぞれ照射されたレーザ光を集光して前記マルチモード光ファイバに結 合させる集合光学系とを有する前記く 22>からく 28 >のいずれかに記載のパター ン形成装置である。該< 29 >に記載のパターン形成装置においては、前記光照射 手段が、前記複数のレーザからそれぞれ照射されたレーザ光が前記集合光学系に より集光され、前記マルチモード光ファイバに結合可能であることにより、露光が焦点 深度の深い露光光で行われる。この結果、前記感光層への露光が極めて高精細に 行われる。例えば、その後、前記感光層を現像すると、極めて高精細なパターンが形 成される。  <29> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated with the plurality of laser forces, respectively, and couples them to the multimode optical fiber. The pattern forming apparatus according to any one of the above items 22> to 28>, which has In the pattern forming apparatus according to <29>, the light irradiation unit may collect the laser light emitted from each of the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber. In some cases, 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.
[0012] < 30> 前記く 20>からく 21 >のいずれかに記載の感光性積層体における感 光層に対して、露光を行うことを含むことを特徴とする永久パターン形成方法である。  [0012] <30> A method for forming a permanent pattern, comprising exposing the light-sensitive layer in the photosensitive laminate according to any one of 20> to 21>.
< 31 > 露光が、 350〜415nmの波長のレーザ光を用いて行われる前記く 30> に記載の永久パターン形成方法である。  <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> 露光が、形成するパターン情報に基づいて像様に行われる前記く 30 > 力もく 31 >の 、ずれかに記載の永久パターン形成方法である。  <32> The method for forming a permanent pattern according to any one of the above items, wherein the exposure is performed in an image-like manner based on pattern information to be formed.
[0013] < 33 > 露光が、光照射手段、及び前記光照射手段からの光を受光し出射する n 個（ただし、 nは 2以上の自然数)の 2次元状に配列された描素部を有し、パターン情 報に応じて前記描素部を制御可能な光変調手段を備えた露光ヘッドであって、該露 光ヘッドの走査方向に対し、前記描素部の列方向が所定の設定傾斜角度 Θをなす ように配置された露光ヘッドを用い、 [0013] <33> Exposure includes 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. And an exposure head provided with a light modulation means capable of controlling the image element portion according to pattern information, wherein the column direction of the image element portion is set to a predetermined value with respect to the scanning direction of the exposure head. Using an exposure head arranged at an inclination angle of Θ,
前記露光ヘッドについて、使用描素部指定手段により、使用可能な前記描素部の うち、 N重露光 (ただし、 Nは 2以上の自然数）に使用する前記描素部を指定し、 前記露光ヘッドについて、描素部制御手段により、前記使用描素部指定手段によ り指定された前記描素部のみが露光に関与するように、前記描素部の制御を行い、 前記感光層に対し、前記露光ヘッドを走査方向に相対的に移動させて行われる前 記く 30 >力 く 32>の!、ずれかに記載の永久パターン形成方法である。該< 33 >に記載の永久パターン形成方法においては、前記露光ヘッドについて、使用描素 部指定手段により、使用可能な前記描素部のうち、 N重露光 (ただし、 Nは 2以上の 自然数)に使用する前記描素部が指定され、描素部制御手段により、前記使用描素 部指定手段により指定された前記描素部のみが露光に関与するように、前記描素部 が制御される。前記露光ヘッドを、前記感光層に対し走査方向に相対的に移動させ て露光が行われることにより、前記露光ヘッドの取付位置や取付角度のずれによる前 記感光層の被露光面上に形成される前記パターンの解像度のばらつきや濃度のむ らカ S均される。この結果、前記感光層への露光が高精細に行われ、その後、前記感 光層を現像することにより、高精細なパターンが形成される。 With respect to the exposure head, by specifying the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable pixel parts by means of a used pixel part specifying means, For the exposure head, the pixel part control unit controls the pixel part so that only the pixel part specified by the used pixel part specifying unit is involved in exposure, and the photosensitive layer On the other hand, the permanent pattern forming method described in 30> Strongly 32> is performed by moving the exposure head relatively in the scanning direction. In the method for forming a permanent pattern according to <33>, the exposure head is subjected to N-fold exposure (where N is a natural number equal to or greater than 2) of the usable pixel portions by the used pixel portion specifying means. The pixel part to be used for the image 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 the 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 resolution and density of the pattern are averaged. 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> 露光が複数の露光ヘッドにより行われ、使用描素部指定手段が、複数の 前記露光ヘッドにより形成される被露光面上の重複露光領域であるヘッド間つなぎ 領域の露光に関与する描素部のうち、前記ヘッド間つなぎ領域における N重露光を 実現するために使用する前記描素部を指定する前記 < 33 >に記載の永久パターン 形成方法である。該< 34 >に記載の永久パターン形成方法においては、露光が複 数の露光ヘッドにより行われ、使用描素部指定手段が、複数の前記露光ヘッドにより 形成される被露光面上の重複露光領域であるヘッド間つなぎ領域の露光に関与す る描素部のうち、前記ヘッド間つなぎ領域における N重露光を実現するために使用 する前記描素部が指定されることにより、前記露光ヘッドの取付位置や取付角度の ずれによる前記感光層の被露光面上のヘッド間つなぎ領域に形成される前記パター ンの解像度のばらつきや濃度のむらが均される。この結果、前記感光層への露光が 高精細に行われる。例えば、その後、前記感光層を現像することにより、高精細なパ ターンが形成される。  <34> The exposure is performed by a plurality of exposure heads, and the drawing element specifying means is used for the exposure of the joint area between the heads, which is an 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 permanent pattern forming method according to <34>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads. Among the picture element parts involved in the exposure of the head-to-head joint area, the picture element part used for realizing the N-fold exposure in the head-to-head joint area is designated, whereby the exposure head is attached. Variations in the resolution and density unevenness of the pattern formed in the connection 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 then formed by developing the photosensitive layer.
< 35 > 露光が複数の露光ヘッドにより行われ、使用描素部指定手段が、複数の 前記露光ヘッドにより形成される被露光面上の重複露光領域であるヘッド間つなぎ 領域以外の露光に関与する描素部のうち、前記ヘッド間つなぎ領域以外の領域にお ける N重露光を実現するために使用する前記描素部を指定する前記 < 34 >に記載 の永久パターン形成方法である。該< 35 >に記載の永久パターン形成方法にお!ヽ ては、露光が複数の露光ヘッドにより行われ、使用描素部指定手段が、複数の前記 露光ヘッドにより形成される被露光面上の重複露光領域であるヘッド間つなぎ領域 以外の露光に関与する描素部のうち、前記ヘッド間つなぎ領域以外における N重露 光を実現するために使用する前記描素部が指定されることにより、前記露光ヘッドの 取付位置や取付角度のずれによる前記感光層の被露光面上のヘッド間つなぎ領域 以外に形成される前記パターンの解像度のばらつきや濃度のむらが均される。この 結果、前記感光層への露光が高精細に行われる。例えば、その後、前記感光層を現 像することにより、高精細なパターンが形成される。 <35> The exposure is performed by a plurality of exposure heads, and the used pixel part specifying means is a connection between heads that is an overlapped exposure area on an exposed surface formed by the plurality of exposure heads. The permanent pattern according to <34>, wherein the pixel part used for realizing N-fold exposure in an area other than the head-to-head area among the picture element parts related to exposure other than the area is specified. It is a forming method. In the method for forming a permanent pattern as described in <35>, exposure is performed by a plurality of exposure heads, and a used pixel portion designating unit is provided on an exposed surface formed by the plurality of exposure heads. By specifying the pixel part used to realize N double exposure in areas other than the head-to-head connection area among the picture-element parts involved in exposure other than the head-to-head connection area that is an overlapping exposure 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 the mounting position and mounting angle of the exposure head are equalized. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is then formed by imaging the photosensitive layer.
< 36 > 設定傾斜角度 Θ力 N重露光数の N、描素部の列方向の個数 s、前記描 素部の列方向の間隔 P、及び露光ヘッドを傾斜させた状態にぉ 、て該露光ヘッドの 走査方向と直交する方向に沿った描素部の列方向のピッチ δに対し、次式、 spsin θ ≥Ν δ  <36> Setting tilt angle Θ force N N number of double exposures, number s of pixel parts in the row direction, interval P of the pixel parts in the row direction, and exposure with the exposure head tilted For the pitch δ in the column direction of the pixel part along the direction orthogonal to the scanning direction of the head, the following equation is given: spsin θ ≥Ν δ
ideal を満たす 0  Satisfy ideal 0
idealに対し、 の  against ideal
ideal 関係を満たすように設定される前記 said to be set to satisfy the ideal relationship
< 33 >力ら< 35 >の!、ずれかに記載の永久パターン形成方法である。 <33> Force et al. <35> !, a method for forming a permanent pattern as described in any of them.
< 37> N重露光の N力 3以上の自然数である前記 < 33 >からく 36 >のぃず れかに記載の永久パターン形成方法である。該く 37 >に記載の永久パターン形成 方法においては、 N重露光の N力 3以上の自然数であることにより、多重描画が行 われる。この結果、埋め合わせの効果により、前記露光ヘッドの取付位置や取付角 度のずれによる前記感光層の被露光面上に形成される前記パターンの解像度のば らつきや濃度のむらが、より精密に均される。  <37> The method for forming a permanent pattern according to any one of the above <33> Karaku 36, wherein the N force of N double exposure is a natural number of 3 or more. In the permanent pattern forming method described in 37>, multiple drawing is performed by using a natural number of N force 3 or more in N double exposure. As a result, due to the effect of offsetting, 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 averaged. Is done.
< 38 > 使用描素部指定手段が、  <38> Use pixel part designation means
描素部により生成され、被露光面上の露光領域を構成する描素単位としての光点 位置を、被露光面上において検出する光点位置検出手段と、  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;
前記光点位置検出手段による検出結果に基づき、 N重露光を実現するために使用 する描素部を選択する描素部選択手段と  Based on the detection result by the light spot position detecting means, a pixel part selecting means for selecting a picture element part to be used for realizing N double exposure;
を備える前記 < 33 >からく 37 >の 、ずれかに記載の永久パターン形成方法である < 39 > 使用描素部指定手段が、 N重露光を実現するために使用する使用描素 部を、行単位で指定する前記 < 33 >からく 38 >のいずれかに記載の永久パターン 形成方法である。 The method for forming a permanent pattern according to any one of the above <33> Karaku 37> <39> The permanent pattern forming method according to any one of the above <33> Karaku 38, wherein the used pixel part designating unit designates the used pixel part used to realize N double exposure in units of rows. It is.
[0015] <40> 光点位置検出手段が、検出した少なくとも 2つの光点位置に基づき、露光 ヘッドを傾斜させた状態における被露光面上の光点の列方向と前記露光ヘッドの走 查方向とがなす実傾斜角度 Θ 'を特定し、描素部選択手段が、前記実傾斜角度 Θ ' と設定傾斜角度 Θとの誤差を吸収するように使用描素部を選択する前記く 38 >力 く 39 >の 、ずれかに記載の永久パターン形成方法である。  <40> The light spot position detection means, based on at least two light spot positions detected, the light spot column direction on the surface to be exposed and the exposure head running direction when the exposure head is tilted The actual inclination angle Θ ′ formed by the image is determined, and the pixel part selection means selects the pixel part to be used so as to absorb the error between the actual inclination angle Θ ′ and the set inclination angle Θ. <39> is the permanent pattern forming method described in any one of the above.
<41 > 実傾斜角度 Θ 'が、露光ヘッドを傾斜させた状態における被露光面上の 光点の列方向と前記露光ヘッドの走査方向とがなす複数の実傾斜角度の平均値、 中央値、最大値、及び最小値のいずれかである前記 < 40 >に記載の永久パターン 形成方法である。  <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 method for forming a permanent pattern according to <40>, wherein the permanent pattern is either a maximum value or a minimum value.
<42> 描素部選択手段が、実傾斜角度 θ Ίこ基づき、 ttan 0 ' =Ν (ただし、 Ν は Ν重露光数の Νを表す)の関係を満たす tに近 ヽ自然数 Tを導出し、 m行 (ただし、 mは 2以上の自然数を表す)配列された描素部における 1行目から前記 T行目の前 記描素部を、使用描素部として選択する前記く 38 >からく 41 >のいずれかに記載 の永久パターン形成方法である。  <42> Based on the actual inclination angle θ が, the pixel part selection means derives a natural number T near t that satisfies the relationship ttan 0 '= Ν (where Ν represents Ν of the double exposure number). , M rows (where m represents a natural number greater than or equal to 2) from the first row in the arranged pixel portion to the previous pixel portion in the T-th row is selected as the used pixel portion from the above 38> <41> The permanent pattern forming method according to any one of the above.
<43 > 描素部選択手段が、実傾斜角度 θ Ίこ基づき、 ttan 0 ' =Ν (ただし、 Ν は Ν重露光数の Νを表す)の関係を満たす tに近 ヽ自然数 Tを導出し、 m行 (ただし、 mは 2以上の自然数を表す)配列された描素部における、 (T+ 1)行目から m行目の 前記描素部を、不使用描素部として特定し、該不使用描素部を除いた前記描素部を 、使用描素部として選択する前記 < 38 >から < 42 >の 、ずれかに記載の永久パタ ーン形成方法である。  <43> Based on the actual tilt angle θ が, the pixel part selection means derives a natural number T near t that satisfies the relationship ttan 0 '= Ν (where Ν represents Ν of the double exposure number). , M (where m represents a natural number greater than or equal to 2) in the arranged pixel part, the pixel part from (T + 1) line to m line is identified as an unused pixel part, The permanent pattern forming method according to any one of <38> to <42>, wherein the pixel part excluding the unused pixel part is selected as a used pixel part.
[0016] <44> 描素部選択手段が、複数の描素部列により形成される被露光面上の重 複露光領域を少なくとも含む領域において、  <44> In a region including at least a double exposure region on the exposed surface formed by a plurality of pixel part rows, the pixel part selection means,
(1)理想的な N重露光に対し、露光過多となる領域、及び露光不足となる領域の合 計面積が最小となるように、使用描素部を選択する手段、 (2)理想的な N重露光に対し、露光過多となる領域の描素単位数と、露光不足となる 領域の描素単位数とが等しくなるように、使用描素部を選択する手段、 (1) Means for selecting a pixel part to be used so that the total area of an overexposed area and an underexposed area is minimized with respect to an ideal N double exposure. (2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area is equal to the number of pixel units in an underexposed area for an ideal N double exposure,
(3)理想的な N重露光に対し、露光過多となる領域の面積が最小となり、かつ、露光 不足となる領域が生じないように、使用描素部を選択する手段、及び  (3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur for an ideal N-fold exposure, and
(4)理想的な N重露光に対し、露光不足となる領域の面積が最小となり、かつ、露光 過多となる領域が生じな 、ように、使用描素部を選択する手段  (4) Means for selecting the pixel part to be used so that the area of the underexposed area is minimized and the overexposed area does not occur with respect to the ideal N double exposure.
の！、ずれかである前記 < 38 >カら<43 >に記載の永久パターン形成方法である。 of! The method for forming a permanent pattern according to <38>, et al. <43>.
<45 > 描素部選択手段が、複数の露光ヘッドにより形成される被露光面上の重 複露光領域であるヘッド間つなぎ領域において、  <45> The pixel part selection means has a head-to-head connection area that is a double exposure area on the exposed surface formed by a plurality of exposure heads.
(1)理想的な N重露光に対し、露光過多となる領域、及び露光不足となる領域の合 計面積が最小となるように、前記ヘッド間つなぎ領域の露光に関与する描素部から、 不使用描素部を特定し、該不使用描素部を除いた前記描素部を、使用描素部として 選択する手段、  (1) For the ideal N double exposure, from the pixel part involved in the exposure of the inter-head connecting area, the total area of the overexposed and underexposed areas is minimized. Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2)理想的な N重露光に対し、露光過多となる領域の描素単位数と、露光不足となる 領域の描素単位数とが等しくなるように、前記ヘッド間つなぎ領域の露光に関与する 描素部から、不使用描素部を特定し、該不使用描素部を除いた前記描素部を、使用 描素部として選択する手段、  (2) In relation to the ideal N double exposure, the number of pixel units in the overexposed area is equal to the number of pixel units in the underexposed area. A means for identifying an unused pixel part from the pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3)理想的な N重露光に対し、露光過多となる領域の面積が最小となり、かつ、露光 不足となる領域が生じないように、前記ヘッド間つなぎ領域の露光に関与する描素部 から、不使用描素部を特定し、該不使用描素部を除いた前記描素部を、使用描素部 として選択する手段、及び、  (3) For the ideal N-double exposure, the area of the overexposed area is minimized, and the pixel part involved in the exposure of the connecting area between the heads is used so that the underexposed area does not occur. 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)理想的な N重露光に対し、露光不足となる領域の面積が最小となり、かつ、露光 過多となる領域が生じないように、前記ヘッド間つなぎ領域の露光に関与する描素部 から、不使用描素部を特定し、該不使用描素部を除いた前記描素部を、使用描素部 として選択する手段、  (4) For the ideal N-fold exposure, the area of the underexposed area is minimized, and the pixel part involved in the exposure of the connection area between the heads is used so that the overexposed area does not occur. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
の！、ずれかである前記 < 38 >カら < 44 >の!、ずれかに記載の永久パターン形成 方法である。 of! The method for forming a permanent pattern according to <38> and <44>, which is misalignment.
<46 > 不使用描素部が、行単位で特定される前記く 45 >に記載の永久パター ン形成方法である。 <46> The permanent pattern as described in 45> above, wherein the unused pixel part is specified in units of lines. Forming method.
[0017] <47> 使用描素部指定手段において使用描素部を指定するために、使用可能 な前記描素部のうち、 N重露光の Nに対し、（N— 1)列毎の描素部列を構成する前 記描素部のみを使用して参照露光を行う前記く 38 >からく 46 >のいずれかに記載 の永久パターン形成方法である。該< 47 >に記載の永久パターン形成方法におい ては、使用描素部指定手段において使用描素部を指定するために、使用可能な前 記描素部のうち、 N重露光の Nに対し、（N—1)列毎の描素部列を構成する前記描 素部のみを使用して参照露光が行われ、略 1重描画の単純なパターンが得られる。 この結果、前記ヘッド間つなぎ領域における前記描素部が容易に指定される。  <47> In order to specify the used pixel part in the used pixel part specifying means, out of the usable pixel parts, N (N−1) column-by-column drawings are used for N of N multiple exposures. 48. The permanent pattern forming method according to any one of the above 38> Karaku 46>, wherein the reference exposure is performed using only the drawing element portion constituting the element row. In the method for forming a permanent pattern described in <47>, in order to specify the used pixel part in the used pixel part specifying means, N of N multiple exposures among the usable pixel parts can be specified. , (N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of simple single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<48 > 使用描素部指定手段において使用描素部を指定するために、使用可能 な前記描素部のうち、 N重露光の Nに対し、 1ZN行毎の描素部行を構成する前記 描素部のみを使用して参照露光を行う前記く 38 >からく 47>のいずれかに記載の 永久パターン形成方法である。該く 48 >に記載の永久パターン形成方法において は、使用描素部指定手段において使用描素部を指定するために、使用可能な前記 描素部のうち、 N重露光の Nに対し、 1ZN行毎の描素部列を構成する前記描素部 のみを使用して参照露光が行われ、略 1重描画の単純なパターンが得られる。この 結果、前記ヘッド間つなぎ領域における前記描素部が容易に指定される。  <48> In order to specify the used pixel part in the used pixel part specifying means, among the available pixel parts, for the N-exposure N, the above-mentioned pixel part rows constituting 1ZN rows are configured. 48. The method for forming a permanent pattern according to any one of the above 38> Karaku 47>, wherein reference exposure is performed using only the pixel part. In the permanent pattern forming method described in 48>, in order to designate the use pixel part in the use pixel part specifying means, among the usable picture element parts, 1 N Reference exposure is performed using only the pixel part constituting the pixel part column for each row, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the inter-head connecting region is easily specified.
[0018] <49 > 使用描素部指定手段が、光点位置検出手段としてスリット及び光検出器 、並びに描素部選択手段として前記光検出器と接続された演算装置を有する前記 < 33 >カら< 48 >の!、ずれかに記載の永久パターン形成方法である。  [0018] <49> The <33> card, wherein the used pixel part specifying means includes a slit and a photodetector as light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means. <48> !, a method for forming a permanent pattern as described in any of them.
< 50> N重露光の N力 3以上 7以下の自然数である前記 < 33 >からく 49 >の V、ずれかに記載の永久パターン形成方法である。  <50> The method for forming a permanent pattern according to the above <33> Karaku 49, which is a natural number of N force 3 to 7 in N double exposure.
[0019] < 51 > 光変調手段が、形成するパターン情報に基づいて制御信号を生成する パターン信号生成手段を更に有してなり、光照射手段から照射される光を該パター ン信号生成手段が生成した制御信号に応じて変調させる前記く 33 >からく 50 >の いずれかに記載の永久パターン形成方法である。該< 51 >に記載のパターン形成 装置においては、前記光変調手段が前記パターン信号生成手段を有することにより 、前記光照射手段から照射される光が該パターン信号生成手段により生成した制御 信号に応じて変調される。 [0019] <51> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the pattern signal generation unit outputs the light emitted from the light irradiation unit. The permanent pattern forming method according to any one of the above items 33> Karaku 50>, which is modulated in accordance with a generated control signal. In the pattern forming apparatus according to <51>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is generated by the pattern signal generation unit. Modulated according to the signal.
< 52> 光変調手段が、空間光変調素子である前記 < 51 >に記載の永久パター ン形成方法である。  <52> The method for forming a permanent pattern according to <51>, wherein the light modulation means is a spatial light modulation element.
< 53 > 空間光変調素子が、デジタル 'マイクロミラー'デバイス (DMD)である前 記く 52 >に記載の永久パターン形成方法である。  <53> The method for forming a permanent pattern according to the above 52, wherein the spatial light modulator is a digital 'micromirror' device (DMD).
< 54> 描素部が、マイクロミラーである前記く 33 >からく 53 >のいずれかに記 載の永久パターン形成方法である。  <54> The permanent pattern forming method according to any one of the above <33>, <53>, wherein the picture element portion is a micromirror.
< 55 > パターン情報が表すパターンの所定部分の寸法が、指定された使用描素 部により実現できる対応部分の寸法と一致するように前記パターン情報を変換する 変換手段を有する前記く 33 >からく 54 >のいずれかに記載の永久パターン形成 方法である。  <55> The frame having the 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. The method for forming a permanent pattern according to any one of the above items.
[0020] < 56 > 光照射手段が、 2以上の光を合成して照射可能である前記く 33 >からく 55 >の 、ずれかに記載の永久パターン形成方法である。該< 56 >に記載の永久 ノターン形成方法にぉ 、ては、前記光照射手段が 2以上の光を合成して照射可能 であることにより、露光が焦点深度の深い露光光によって行われる。この結果、前記 感光性フィルムへの露光が極めて高精細に行われる。例えば、その後、前記感光層 を現像すると、極めて高精細なパターンが形成される。  [0020] <56> The permanent pattern forming method according to any one of the above <33> and <55>, wherein the light irradiation means can synthesize and irradiate two or more lights. In the permanent pattern forming method described in <56>, since the light irradiation means can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the photosensitive film is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
< 57> 光照射手段が、複数のレーザと、マルチモード光ファイバと、該複数のレ 一ザ力 それぞれ照射されたレーザ光を集光して前記マルチモード光ファイバに結 合させる集合光学系とを有する前記く 33 >からく 56 >の 、ずれかに記載の永久パ ターン形成方法である。該く 57>に記載の永久パターン形成方法においては、前 記光照射手段が、前記複数のレーザ力 それぞれ照射されたレーザ光が前記集合 光学系により集光され、前記マルチモード光ファイバに結合可能であることにより、露 光が焦点深度の深い露光光で行われる。この結果、前記感光性フィルムへの露光が 極めて高精細に行われる。例えば、その後、前記感光層を現像すると、極めて高精 細なパターンが形成される。  <57> The light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system for condensing and coupling the laser beams irradiated to the plurality of laser forces, respectively, to the multimode optical fiber. The permanent pattern forming method according to any one of the above items 33> Karaku 56>. In the method for forming a permanent pattern described in <57>, the light irradiating means can condense the laser light irradiated with each of the plurality of laser forces by the collective optical system and couple it to the multimode optical fiber. Therefore, the exposure is performed with exposure light having a deep depth of focus. As a result, the photosensitive film is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine pattern is formed.
[0021] < 58 > 露光が行われた後、感光層の現像を行う前記 < 30>から < 57>のいず れかに記載の永久パターン形成方法である。該< 58 >に記載の永久パターン形成 方法においては、前記露光が行われた後、前記感光層を現像することにより、高精 細なパターンが形成される。 [0021] <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. Permanent pattern formation as described in <58> In the method, after the exposure, the photosensitive layer is developed to form a highly precise pattern.
< 59 > 現像が行われた後、永久パターンの形成を行う前記く 58 >に記載の永 久パターン形成方法である。  <59> The method for forming a permanent pattern according to the above item 58, wherein a permanent pattern is formed after the development.
[0022] < 60> 前記 < 30>からく 59 >のいずれかに記載のパターン形成方法により形 成されることを特徴とする永久パターンである。該く 60 >に記載の永久パターンは、 前記パターン形成方法により形成されるので、優れた耐薬品性、表面硬度、耐熱性 などを有し、かつ高精細であり、半導体や部品の多層配線基板やビルドアップ配線 基板などへの高密度実装に有用である。 [0022] <60> A permanent pattern formed by the pattern forming method according to any one of <30> and <59>. Since the permanent pattern according to 60> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, etc., and is high-definition, and is a multilayer wiring board for semiconductors and components. This is useful for high-density mounting on PCBs and build-up wiring boards.
< 61 > 保護膜、層間絶縁膜、及びソルダーレジストパターンの少なくともいずれ かである前記く 60 >に記載の永久パターンである。該< 61 >に記載の永久パター ンは、保護膜、層間絶縁膜、及びソルダーレジストパターンの少なくともいずれかであ るので、該膜の有する絶縁性、耐熱性などにより、配線が外部力ゝらの衝撃や曲げなど 力 保護される。  <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 described in <61> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring may be damaged by an external force due to the insulating property, heat resistance, etc. of the film. Protects against impacts and bending.
[0023] < 62> 前記 < 30>から < 59 >のいずれかに記載の永久パターン形成方法によ り永久パターンが形成されることを特徴とするプリント基板である。  [0023] <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>.
発明の効果  The invention's effect
[0024] 本発明によると、従来における問題を解決することができ、ソルダーレジスト等の永 久パターン形成を目的として、前記フィルムタイプにおいても、感度が良好で、かつ 生保存性及び取り扱い性に優れる感光性組成物、感光性フィルム、並びに、半導体 分野における高精細な永久パターン (保護膜、層間絶縁膜、及びソルダーレジストパ ターンなど)を高精細に、かつ、効率よく形成可能な永久パターン形成方法、及び該 永久パターン形成方法により永久パターンが形成されるプリント基板を提供すること ができる。  [0024] According to the present invention, conventional problems can be solved, and for the purpose of forming a permanent pattern such as a solder resist, the film type also has good sensitivity and excellent raw storage and handling properties. PHOTOSENSITIVE COMPOSITION, PHOTOSENSITIVE FILM, AND METHOD FOR FORMING PERMANENT PATTERN WHICH CAN FORM DEFINED AND EFFICIENTLY AND EFFICIENTLY AND EFFICIENTLY IN DEFINITION And a printed circuit board on which a permanent pattern is formed by the method for forming a permanent pattern.
図面の簡単な説明  Brief Description of Drawings
[0025] [図 1A]図 1Aは、露光ヘッドの詳細な構成の一例を示す上面図である。 FIG. 1A is a top view showing an example of a detailed configuration of an exposure head.
[図 1B]図 1Bは、露光ヘッドの詳細な構成の一例を示す側面図である。  FIG. 1B is a side view showing an example of a detailed configuration of the exposure head.
[図 2]図 2は、パターン形成装置の DMDの一例を示す部分拡大図である。 [図 3]図 3は、隣接する露光ヘッド間に相対位置のずれ及び取付角度誤差がある際 に、被露光面上のパターンに生じるむらの例を示した説明図である。 FIG. 2 is a partially enlarged view showing an example of a DMD of the pattern forming apparatus. FIG. 3 is an explanatory view showing an example of unevenness in a pattern on an exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads.
[図 4]図 4は、図 3の例において選択された使用描素部のみを用いた露光を示す説明 図である。 FIG. 4 is an explanatory diagram showing exposure using only the used pixel part selected in the example of FIG. 3.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
(感光性組成物） (Photosensitive composition)
前記本発明の感光性組成物は、（A)バインダーと、（B)重合性化合物と、（C)光重 合開始剤と、を少なくとも含み、必要に応じて、（D)熱架橋剤、（E)エラストマ一、（F) フヱノキシ榭脂、（G)増感剤、（H)その他成分を含む。  The photosensitive composition of the present invention includes (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) other ingredients.
前記感光性組成物の感度としては、該感光性組成物を用いて形成した感光層を露 光し現像する場合にお!ヽて、該感光層の露光する部分の厚みを該露光及び現像後 において変化させない前記露光に用いる光の最小エネルギー力 0. l〜200mjZc m2であることが好ましぐ 0. 2〜100mjZcm2であることがより好ましぐ 0. 5〜50¾[ Zcm2であることが特に好まし 、。 The sensitivity of the photosensitive composition is defined as the thickness of the exposed portion of the photosensitive layer after the exposure and development when the photosensitive layer formed using the photosensitive composition is exposed and developed. is more preferred instrument 0. 5~50¾ [Zcm 2 that it is the minimum energy power 0. l~200mjZc m 2 of light is preferred instrument 0. 2~100mjZcm 2 used for the exposure is not changed in It is especially preferred.
前記最小エネルギー力 0. lmjZcm2未満であると、処理工程にてカプリが発生 することがあり、 200mjZcm2を超えると、露光に必要な時間が長くなり、処理スピー ド、が遅くなることがある。 If the minimum energy force is less than 0.1 lmjZcm 2 , capri may occur in the processing step, and if it exceeds 200 mjZcm 2 , the time required for exposure may become longer and the processing speed may become slower. .
ここで、「該感光層の露光する部分の厚みを該露光及び現像後において変化させ ない前記露光に用いる光の最小エネルギー」（以下、単に「光の最小エネルギー」と 称することもある）とは、いわゆる現像感度であり、例えば、前記感光層を露光したとき の前記露光に用いた光のエネルギー量 (露光量）と、前記露光に続く前記現像処理 により生成した前記硬化層の厚みとの関係を示すグラフ (感度曲線)から求めることが できる。  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”) The so-called development sensitivity, for example, the relationship between the amount of light energy (exposure amount) used for the exposure when the photosensitive layer is exposed and the thickness of the cured layer generated by the development process following the exposure. Can be obtained from the graph (sensitivity curve).
前記硬化層の厚みは、前記露光量が増えるに従い増加していき、その後、前記露 光前の前記感光層の厚みと略同一かつ略一定となる。前記現像感度は、前記硬化 層の厚みが略一定となったときの最小露光量を読み取ることにより求められる値であ る。  The thickness of the cured layer increases as the exposure amount 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.
ここで、前記硬化層の厚みと前記露光前の前記感光層の厚みとの差が ± 1 μ m以 内であるとき、前記硬化層の厚みが露光及び現像により変化していないとみなす。 前記硬化層及び前記露光前の前記感光層の厚みの測定方法としては、特に制限 はなく、 目的に応じて適宜選択することができるが、膜厚測定装置、表面粗さ測定機Here, the difference between the thickness of the cured layer and the thickness of the photosensitive layer before exposure is ± 1 μm or more. When it is within, 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 the exposure is not particularly limited and may be appropriately selected depending on the intended purpose.
(例えば、サーフコム 1400D (東京精密社製) )などを用いて測定する方法が挙げら れる。 (For example, Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) can be used.
前記感光層の厚みとしては、特に制限はなぐ 目的に応じて適宜選択することがで きるが、例えば、 1-100 μ mが好ましぐ 2〜50 μ mがより好ましぐ 4〜30 μ mが特 に好ましい。  The thickness of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. For example, 1 to 100 μm is preferable, 2 to 50 μm is more preferable, and 4 to 30 μm is preferable. m is particularly preferred.
[0027] <バインダー > [0027] <Binder>
本発明に用いられるバインダーは、ビスフエノール骨格を部分構造に有するェポキ シ化合物（a)と、不飽和基含有モノカルボン酸 (b)との反応物に、飽和もしくは不飽 和基含有多塩基酸化合物 (c)を反応させて得られる化合物である。  The binder used in the present invention contains a saturated or unsaturated group-containing polybasic acid 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). This is a compound obtained by reacting compound (c).
[0028] 一（a)エポキシ化合物一 [0028] One (a) Epoxy Compound One
前記ビスフエノール骨格を部分構造に有するエポキシィ匕合物（a)としては、下記一 般式（1)及び一般式（2)の 、ずれかで表される化合物が好ま 、。  As the epoxy compound (a) having a bisphenol skeleton in a partial structure, a compound represented by any of the following general formulas (1) and (2) is preferable.
[化 9] 一般式（1 )
Figure imgf000018_0001
[Chemical 9] General formula (1)
Figure imgf000018_0001
ただし、前記一般式（1)中、 Xは、水素原子及びグリシジル基のいずれかを表し、 R は、メチレン基及びイソプロピリデン基のいずれかを表す。 nは、 1以上の整数を表す  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
[0029] 前記一般式（1)で表され、 Xが下記構造式で示されるグリシジル基であるビスフ ノ ール A型エポキシ榭脂、又はビスフエノール F型エポキシ榭脂は、例えば、下記一般 式（5)で示されるビスフエノール A型エポキシ榭脂、又はビスフエノール F型エポキシ 榭脂の水酸基と、ェピクロルヒドリンとを反応させることにより得ることができる。水酸基 とェピクロルヒドリンとの反応を促進するためには、反応温度 50〜120°Cでアルカリ 金属水酸化物存在下、ジメチルホルムアミド、ジメチルァセトアミド、ジメチルスルホキ シド等の極性有機溶剤中で反応を行うのが好ましい。前記反応温度が 50°C未満で は反応が遅くなることがあり、反応温度が 120°C超では副反応が多く生じることがあり[0029] A bisphenol A type epoxy resin or a bisphenol F type epoxy resin represented by the general formula (1), wherein X is a glycidyl group represented by the following structural formula, has, for example, the following general formula: It can be obtained by reacting the hydroxyl group of bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by (5) with epichlorohydrin. In order to promote the reaction between the hydroxyl group and epichlorohydrin, polar organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like in the presence of alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. It is preferable to carry out the reaction in the medium. When the reaction temperature is less than 50 ° C Reaction may be slow, and side reactions may occur when the reaction temperature exceeds 120 ° C.
、好ましくない。 Is not preferable.
[0030] [化 12]  [0030] [Chemical 12]
-CH„-CH-CH„  -CH „-CH-CH„
\ /  \ /
[0031] [化 13」 [0031] [Chemical 13]
（5) (Five)
Figure imgf000019_0001
Figure imgf000019_0001
ただし、前記一般式（5)中、 Rは水素原子及びメチル基のいずれかを表し、 nは 1以 上の整数である。  In the general formula (5), R represents either a hydrogen atom or a methyl group, and n is an integer of 1 or more.
[0032] [化 10] [0032] [Chemical 10]
一般式（2)
Figure imgf000019_0002
General formula (2)
Figure imgf000019_0002
ただし、前記一般式（2)中、 R1は、水素原子及びメチル基のいずれかを表し、 R2及 び R3は、アルキレン基を表し、 m及び nは、 m+nが 2 50となる正の整数を表し、 p は、正の整数を表す。 However, in the general formula (2), R 1 represents either a hydrogen atom or a methyl group, R 2 and R 3 represent an alkylene group, and m and n have m + n of 250 and P represents a positive integer.
なお、前記 m+nは、 2 30となる正の整数がより好ましぐ 2 20の整数となる正 の整数が更に好ましい。また、前記 ρは、 1 25の整数がより好ましぐ 1 15の整数 が更に好ましぐ 1〜10の整数が特に好ましい。 Note that m + n is more preferably a positive integer that is an integer of 220, which is more preferably a positive integer of 230. In addition, ρ is more preferably an integer of 1 25 1 Integer of 15 Is more preferable. An integer of 1 to 10 is particularly preferable.
[0033] 前記一般式（2)で表される化合物（ポリマー）は、下記繰り返し単位（la)び単位（1 b)から構成されている。なお、該ポリマーの末端は、単位（la)及び単位（lb)のいず れであってもよぐ単位（la)が末端となる場合、ビスフエノールにおける水酸基がダリ シジル基等の置換基により置換されていてもよい。該単位（la)及び（lb)中、 R1は、 水素原子及びメチル基のいずれかを表し、 R2及び R3は、アルキレン基を表す。 [0033] The compound (polymer) represented by the general formula (2) is composed of the following repeating units (la) and units (1b). In addition, when the unit (la), which may be either the unit (la) or the unit (lb), is the terminal of the polymer, the hydroxyl group in the bisphenol is replaced by a substituent such as a darisidyl group. May be substituted. In the units (la) and (lb), R 1 represents either a hydrogen atom or a methyl group, and R 2 and R 3 represent an alkylene group.
[化 1]  [Chemical 1]
Figure imgf000020_0001
Figure imgf000020_0001
[0034] (b)不飽和基含有モノカルボン酸  [0034] (b) Unsaturated group-containing monocarboxylic acid
前記不飽和基含有モノカルボン酸としては、例えば、アクリル酸、アクリル酸の二量 体、メタクリル酸、 β フルフリルアクリル酸、 βースチリルアクリル酸、桂皮酸、クロト ン酸、 a シァノ桂皮酸等のビュル基含有モノカルボン酸が挙げられ、また、水酸基 含有アタリレートと飽和あるいは不飽和二塩基酸無水物との反応生成物である半ェ ステル化合物、ビュル基含有モノグリシジルエーテル若しくはビュル基含有モノダリ シジルエステルと飽和あるいは不飽和二塩基酸無水物との反応生成物である半エス テルィ匕合物が挙げられる。これら半エステルイ匕合物は、水酸基含有アタリレート、ビ- ル基含有モノグリシジルエーテル若しくはビュル基含有モノグリシジルエステルと飽 和あるいは不飽和二塩基酸無水物とを等モル比で反応させることで得られる。これら ビュル基含有モノカルボン酸は、 1種単独で使用してもよぐ 2種以上を併用してもよ い。  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 acyanamic acid. Also included are bis-group-containing monocarboxylic acids, and half-ester compounds, butyl-group-containing monoglycidyl ethers or butyl-group-containing monodales that are the reaction products of hydroxyl-containing acrylates with saturated or unsaturated dibasic acid anhydrides. Examples thereof include semi-ester compounds which are reaction products of a sidyl ester and a saturated or unsaturated dibasic acid anhydride. These half-ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a beryl group-containing monoglycidyl ether or a bull group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. It is done. These bur group-containing monocarboxylic acids may be used alone or in combination of two or more.
[0035] 前記ビュル基含有モノカルボン酸の一例である上記半エステルイ匕合物の合成に用 いられる水酸基含有アタリレート、ビュル基含有モノグリシジルエーテル、ビュル基含 有モノグリシジルエステルとしては、例えば、ヒドロキシェチルアタリレート、ヒドロキシ ェチノレメタタリレート、ヒドロキシプロピノレアタリレート、ヒドロキシプロピノレメタタリレート 、ヒドロキシブチルアタリレート、ヒドロキシブチルメタタリレート、ポリエチレングリコール モノアタリレート、ポリエチレングリコールモノメタタリレート、トリメチロールプロパンジァ タリレート、トリメチロールプロパンジメタタリレート、ペンタエリスルトールトリアタリレート 、ペンタエリスリトーノレトリメタタリレート、ジペンタエリスリトールペンタアタリレート、ペン タエリスリトールペンタメタクリレート、グリシジルアタリレート、グリシジルメタタリレート、 などが挙げられる。 [0035] Examples of the hydroxyl group-containing acrylate, bure group-containing monoglycidyl ether, and bull group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the bull group-containing monocarboxylic acid include: Hydroxyethyl acrylate, Hydroxy ethinoremethalylate, Hydroxypropinoreatalylate, Hydroxypropinoremethacrylate , Hydroxybutyl acrylate, Hydroxy butyl methacrylate, Polyethylene glycol monomethacrylate, Polyethylene glycol monomethacrylate, Trimethylolpropane ditalylate, Trimethylolpropane dimetatalylate, Pentaerythritol tritalate, Pentaerythritol Noretrimetatalylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, glycidyl methacrylate, and the like.
[0036] 前記半エステル化合物の合成に用いられる飽和あるいは不飽和二塩基酸無水物 としては、例えば、無水コハク酸、無水マレイン酸、テトラヒドロ無水フタル酸、無水フ タル酸、メチルテトラヒドロ無水フタル酸、ェチルテトラヒドロ無水フタル酸、へキサヒド 口無水フタル酸、メチルへキサヒドロ無水フタル酸、ェチルへキサヒドロ無水フタル酸 、無水ィタコン酸、などが挙げられる。  [0036] 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, Ethyltetrahydrophthalic anhydride, hexahydrate Oral phthalic anhydride, Methylhexahydrophthalic anhydride, Ethylhexahydrophthalic anhydride, Itaconic anhydride, etc.
[0037] 前記エポキシ榭脂と前記ビニル基含有モノカルボン酸との反応において、前記ェ ポキシ榭脂のエポキシ基 1当量に対して、前記ビニル基含有モノカルボン酸が 0. 8 〜1. 05当量となる比率で反応させることが好ましぐ 0. 9〜1. 0当量がより好ましい  [0037] In the reaction of the epoxy resin with the vinyl group-containing monocarboxylic acid, the vinyl group-containing monocarboxylic acid is used in an amount of 0.8 to 1.05 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. It is preferable to react at a ratio of 0.9 to 1.0 equivalent is more preferable
[0038] 前記エポキシ榭脂と前記ビニル基含有モノカルボン酸は有機溶剤に溶力して反応 させられ、有機溶剤としては、例えば、ェチルメチルケトン、シクロへキサノン等のケト ン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、メチルセロソ ルブ、ブチルセ口ソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコ ールモノメチルエーテル、ジプロピレングリコールモノェチルエーテル、ジプロピレン グリコーノレジェチノレエーテノレ、トリエチレングリコーノレモノェチノレエーテノレ等のグリコ ールエーテル類、酢酸ェチル、酢酸ブチル、ブチルセ口ソルブアセテート、カルビト ールアセテート等のエステル類、オクタン、デカンなどの脂肪族炭化水素類、石油ェ 一テル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤、などが挙 げられる。 [0038] The epoxy resin and the vinyl group-containing monocarboxylic acid are reacted by dissolving in an organic solvent, and examples of the organic solvent include ketones such as ethylmethylketone and cyclohexanone, toluene, Aromatic hydrocarbons such as xylene and tetramethylbenzene, methyl cellosolve, butylcetosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol nole chinenore Glycol ethers such as etherol, triethyleneglycolenomethinoleetenole, esters such as ethyl acetate, butyl acetate, butyl acetate sorb acetate, carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether Itotel, oil naphtha, hydrogenated Oil naphtha, petroleum solvents such as solvent naphtha, etc. can be mentioned up.
[0039] 更に、前記反応を促進させるために、触媒を用いるのが好ましい。前記触媒として は、例えば、トリェチルァミン、ベンジルメチルァミン、メチルトリェチルアンモ-ゥムク 口ライド、ベンジルトリメチルアンモ -ゥムクロライド、ベンジルトリメチルアンモ-ゥムブ ロマイド、ベンジルトリメチルメチルアンモ -ゥムアイオダイド、トリフエ-ルホスフィン、 などが挙げられる。 [0039] Furthermore, in order to promote the reaction, it is preferable to use a catalyst. Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium chloride. Romide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like.
前記触媒の使用量としては、前記エポキシ榭脂と前記ビュル基含有モノカルボン 酸の合計 100質量部に対して、 0. 1〜： LO質量部が好ましい。  The amount of the catalyst used is preferably 0.1 to: LO parts by mass with respect to 100 parts by mass in total of the epoxy resin and the bull group-containing monocarboxylic acid.
[0040] また、反応中の重合を防止する目的で、重合禁止剤を使用するのが好ま 、。重 合禁止剤としては、例えば、ハイドロキノン、メチルノ、イドロキノン、ハイドロキノンモノメ チルエーテル、カテコール、ピロガロール等が挙げられる。 [0040] For the purpose of preventing polymerization during the reaction, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methylo, idroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
前記重合禁止剤の使用量としては、前記エポキシ榭脂と前記ビュル基含有モノ力 ルボン酸の合計 100質量部に対して、 0. 01〜1質量部が好ましい。前記反応温度と しては、 60〜150°Cが好ましぐ 80〜120°Cがより好ましい。  The amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy resin and the bull group-containing monostrengthenic acid. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
[0041] 必要に応じて前記ビニル基含有モノカルボン酸と、無水トリメリット酸、無水ピロメリッ ト酸、ベンゾフヱノンテトラカルボン酸無水物、ビフヱ-ルテトラカルボン酸無水物等 の多塩基酸無水物とを併用することができる。  [0041] If necessary, the vinyl group-containing monocarboxylic acid and a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Can be used together.
[0042] (c)飽和若しくは不飽和基含有多塩基酸化合物  [0042] (c) Saturated or unsaturated group-containing polybasic acid compound
前記飽和若しくは不飽和基含有多塩基酸無水物としては、例えば、無水コハク酸、 無水マレイン酸、テトラヒドロ無水フタル酸、無水フタル酸、メチルテトラヒドロ無水フタ ル酸、ェチルテトラヒドロ無水フタル酸、へキサヒドロ無水フタル酸、メチルへキサヒド 口無水フタル酸、ェチルへキサヒドロ無水フタル酸、無水ィタコン酸等が挙げられる。  Examples of the saturated or unsaturated group-containing polybasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydro Examples thereof include phthalic anhydride, methylhexahydrate, phthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.
[0043] 前記反応生成物と前記飽和若しくは不飽和基含有多塩基酸無水物との反応にお いて、反応生成物中の水酸基 1当量に対して、前記飽和若しくは不飽和基含有多塩 基酸無水物を 0. 1〜1. 0当量反応させることで、前記バインダーの酸価を調整でき る。前記バインダーの酸価としては、 30〜150mgKOHZgであることが好ましぐ 50 〜120mgKOHZgであることが更に好ましい。該酸価が、 30mgKOHZg未満では 光硬化性榭脂組成物の希アルカリ溶液への溶解性が低下することがあり、 150mgK OHZgを超えると硬化膜の電気特性が低下することがある。前記反応生成物と前記 飽和若しくは不飽和基含有多塩基酸無水物との反応温度としては、 60〜120°Cが 好ましい。  [0043] 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 with respect to 1 equivalent of a hydroxyl group in the reaction product. The acid value of the binder can be adjusted by reacting 0.1 to 1.0 equivalents of the anhydride. The acid value of the binder is preferably 30 to 150 mg KOHZg, more preferably 50 to 120 mg KOHZg. If the acid value is less than 30 mg KOHZg, the solubility of the photocurable resin composition in a dilute alkaline solution may be reduced, and if it exceeds 150 mg KOHZg, the electrical properties 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.
[0044] その他のバインダ 前記のバインダーと併用してもよ 、バインダーとしては、酸性基とエチレン性不飽和 結合を側鎖に含む高分子化合物が好ましい。前記酸性基としては、カルボキシル基 、リン酸基、スルホン酸基等があげられるが、原料入手の点カゝらカルボキシル基が好 ましい。 [0044] Other binders Even if it is used in combination with the above-mentioned binder, 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. Of these, a carboxyl group is preferred because of the availability of raw materials.
前記バインダーは、水に不溶で、かつ、アルカリ性水溶液により膨潤あるいは溶解 する化合物が好ましい。  The binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
また、前記バインダーとしては、分子内に少なくとも 1つの重合可能な二重結合、例 えば、（メタ）アタリレート基又は (メタ)アクリルアミド基等のアクリル基、カルボン酸のビ -ルエステル、ビュルエーテル、ァリルエーテル等の各種重合性二重結合を用いる ことができる。より具体的には、酸性基としてカルボキシル基を含有するアクリル榭脂 に、環状エーテル基含有重合性化合物、たとえばグリシジルアタリレート、グリシジル メタタリレート、桂皮酸等の不飽和脂肪酸のグリシジルエステルや、脂環式エポキシ 基 (たとえば同一分子中にシクロへキセンォキシド等のエポキシ基）と (メタ)アタリロイ ル基を有する化合物等のエポキシ基含有の重合性ィ匕合物を付加させて得られるィ匕 合物などが挙げられる。また、酸性基及び水酸基を含有するアクリル榭脂に、イソシ アナートェチル (メタ)アタリレート等のイソシァネート基含有の重合性ィ匕合物を付加さ せて得られる化合物、無水物基を含有するアクリル榭脂に、ヒドロキシアルキル (メタ） アタリレート等の水酸基を含有する重合性ィ匕合物を付加させて得られる化合物なども 挙げられる。また、グリシジルメタタリレートなどの環状エーテル基含有重合性ィ匕合物 と（メタ）アタリロイルアルキルエステルなどのビュルモノマーを共重合し、側鎖のェポ キシ基に (メタ)アクリル酸を付加させて得られる化合物なども挙げられる。  Examples of the binder include 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 butyl ether, Various polymerizable double bonds such as aryl ether can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound, for example, a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, or an alicyclic group. Compound obtained by adding an epoxy group-containing polymerizable compound such as an epoxy group (for example, an epoxy group such as cyclohexenoxide in the same molecule) and a compound having a (meth) aryryl group, etc. Can be mentioned. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanatoethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group. Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as hydroxyalkyl (meth) acrylate to fat. In addition, a cyclic ether group-containing polymerizable compound such as glycidyl metatalylate is copolymerized with a butyl monomer such as (meth) atalyloyl alkyl ester, and (meth) acrylic acid is added to the side chain epoxy group. The compound etc. which are obtained by making it also include.
これらの例としては、特許 2763775号公報、特開平 3— 172301号公報、特開 20 00— 232264号公報に記載の化合物などが挙げられる。  Examples of these include compounds described in Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, Japanese Patent Application Laid-Open No. 2000-2232264, and the like.
< (B)重合性化合物 > <(B) Polymerizable compound>
前記重合性化合物としては、特に制限はなぐ 目的に応じて適宜選択することがで き、分子中に少なくとも 1個の付加重合可能な基を有し、沸点が常圧で 100°C以上で ある化合物が好ましぐ例えば、（メタ)アクリル基を有するモノマーから選択される少 なくとも 1種が好適に挙げられる。 [0046] 前記 (メタ）アクリル基を有するモノマーとしては、特に制限はなぐ 目的に応じて適 宜選択することができ、例えば、ポリエチレングリコールモノ (メタ)アタリレート、ポリプ ロピレングリコールモノ（メタ）アタリレート、フエノキシェチル (メタ）アタリレート等の単 官能アタリレートや単官能メタタリレート；ポリエチレングリコールジ (メタ)アタリレート、 ポリプロピレングリコールジ (メタ）アタリレート、トリメチロールェタントリアタリレート、トリ メチロールプロパントリアタリレート、トリメチロールプロパンジアタリレート、ネオペンチ ルグリコールジ (メタ）アタリレート、ペンタエリトリトールテトラ (メタ）アタリレート、ペンタ エリトリトールトリ（メタ）アタリレート、ジペンタエリトリトールへキサ（メタ）アタリレート、ジ ペンタエリトリトールペンタ（メタ）アタリレート、へキサンジオールジ (メタ）アタリレート、 トリメチロールプロパントリ（アタリロイルォキシプロピル）エーテル、トリ（アタリロイルォ キシェチル)イソシァヌレート、トリ（アタリロイルォキシェチル）シァヌレート、グリセリン トリ（メタ）アタリレート、トリメチロールプロパンやグリセリン、ビスフエノール等の多官能 アルコールに、エチレンオキサイドやプロピレンオキサイドを付加反応した後で (メタ） アタリレートイ匕したもの、特公昭 48— 41708号、特公昭 50— 6034号、特開昭 51— 37193号等の各公報に記載されているウレタンアタリレート類;特開昭 48— 64183 号、特公昭 49 43191号、特公昭 52— 30490号等の各公報に記載されているポリ エステルアタリレート類；エポキシ榭脂と (メタ)アクリル酸の反応生成物であるェポキ シアタリレート類等の多官能アタリレートやメタタリレートなどが挙げられる。これらの中 でも、トリメチロールプロパントリ (メタ)アタリレート、ペンタエリトリトールテトラ (メタ)ァク リレート、ジペンタエリトリトールへキサ（メタ）アタリレート、ジペンタエリトリトールペンタ (メタ)アタリレートが特に好ましい。 The polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose, and has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. Preferred examples of the compound include at least one selected from monomers having a (meth) acryl group. [0046] The monomer having the (meth) acryl group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monofunctional acrylates and monofunctional methallylates such as rate and phenoxychetyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate Rate, trimethylolpropane ditalylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta erythritol tri (meth) acrylate, dipentaerythritol hexane (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylol propane tri (atalylooxypropyl) ether, tri (atalyloyloxychetyl) isocyanurate, tri (atalyloyl) Oxetyl) cyanurate, glycerin tri (meth) atarylate, polyfunctional alcohols such as trimethylolpropane, glycerin, bisphenol, etc., after addition reaction of ethylene oxide or propylene oxide with (meth) aterol toy Urethane acrylates described in JP-B 48-41708, JP-B 50-6034, JP-A 51-37193, etc .; JP-A 48-64183, JP-B 49 43191, Polyesters described in JP-B 52-30490 and other publications Atalylates; polyfunctional acrylates and metatalates such as epoxide acrylates which are reaction products of epoxy resin and (meth) acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.
[0047] 前記重合性ィ匕合物の前記感光性組成物固形分中の固形分含有量としては、 5〜5 0質量％が好ましぐ 10〜40質量％がより好ましい。該固形分含有量が 5質量％未 満であると、現像性の悪化、露光感度の低下などの問題を生ずることがあり、 50質量 %を超えると、感光層の粘着性が強くなりすぎることがあり、好ましくない。  [0047] The solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur. If it exceeds 50% by mass, the adhesiveness of the photosensitive layer becomes too strong. Is not preferable.
[0048] < (C)光重合開始剤 >  [0048] <(C) Photopolymerization initiator>
光重合開始剤としては、ァシルホスフィンォキシドィ匕合物及びォキシム誘導体から 選択される化合物が好ましぐ特にォキシム誘導体が特に好ましい。また、必要に応 じて、その他の光重合開始剤を含んでもよい。 As the photopolymerization initiator, a compound selected from an acylphosphine oxide compound and an oxime derivative is preferred, and an oxime derivative is particularly preferred. Also, if necessary Accordingly, other photopolymerization initiators may be included.
[0049] ァシルホスフィンォキシド化合物  [0049] Acylphosphine oxide compound
ァシルホスフィンォキシド化合物としては、モノァシルホスフィンォキシド、ビスァシ ルホスフィンォキシド、トリァシルホスフィンォキシド化合物が挙げられる。  Examples of the acyl phosphine oxide compound include monoacyl phosphine oxide, bisacyl phosphine oxide, and triacyl phosphine oxide compounds.
前記ァシルホスフィンォキシドィ匕合物としては、例えば、下記一般式 (6)で表される 化合物が好適に挙げられる。  Preferred examples of the acyl phosphinoxide compound include compounds represented by the following general formula (6).
[0050] [化 14] [0050] [Chemical 14]
0 0  0 0
II II 〜  II II ~
R11— P— C一 R13 —般式（6) R11— P— C 1 R 13 — General formula (6)
R12 R 12
ただし、前記一般式 (6)中、 R11 及び R12は、それぞれ独立して、炭素原子数 1〜1 2のアルキル基、ベンジル基、水素原子、ハロゲン原子、炭素原子数 1〜8のアルキ ル基により 1〜4回置換されたフエニル基、炭素原子数 1〜8のアルコキシ基により 1 〜4回置換されたフヱ-ル基、シクロへキシル基、及び下記式 (i)中の COR13で表さ れる基の 、ずれかを表し、さらに R11は OR14及び下記式 (i)で表される基の 、ずれ かであってもよい。 R13は水素原子、炭素原子数 1〜8のアルキル基、炭素原子数 1 〜8のアルコキシ基、炭素原子数 1〜8のアルキルチオ基、ハロゲン原子により 1〜4 回置換されたフエ-ル基、及び下記式 (ii)で表される基のいずれかを表し、 R14は炭 素原子数 1〜8のアルキル基、フエ-ル基、及びべンジル基のいずれかを表す。 Yは フエ-レン基、炭素原子数 1〜12のアルキレン基、及びシクロへキシレン基のいずれ かを表し、 Xは炭素原子数 1〜18のアルキレン基及び下記式 (iii)で表される基のい ずれかを表す。 However, in the general formula (6), R 11 and R 12 are each independently an alkyl group having 1 to 12 carbon atoms, a benzyl group, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms. A phenyl group substituted 1 to 4 times by a ruthel group, a phenyl group substituted 1 to 4 times by an alkoxy group having 1 to 8 carbon atoms, a cyclohexyl group, and a COR in the following formula (i) The group represented by 13 represents a deviation, and R 11 may be a deviation 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, or a phenyl group substituted 1 to 4 times by a halogen atom. And R 14 represents any one of an alkyl group having 1 to 8 carbon atoms, a phenol 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 an alkylene group having 1 to 18 carbon atoms and a group represented by the following formula (iii) Represents one of the following.
[0051] [化 15] 式（ i ) [0051] [Chemical 15] Formula (i)
Figure imgf000026_0001
式（ ii )
Figure imgf000026_0001
Formula (ii)
式（iii )Formula (iii)
Figure imgf000026_0002
Figure imgf000026_0002
前記一般式 (6)で表される具体的な化合物としては、例えば、ビス（2, 6 ジメトキ シベンゾィル）フエ-ルホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル）（2, 4, 4 トリメチルペンチル）ホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル） n— ブチルホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル）一（2 メチルプロパン —1—ィル）ホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル）一（1—メチルプロ パン— 1—ィル）ホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル） t—ブチル ホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル）シクロへキシルホスフィンォキ シド、ビス（2, 6 ジメトキシベンゾィル）ォクチルホスフィンォキシド、ビス（2—メトキシ ベンゾィル）（2—メチルプロパン— 1—ィル）ホスフィンォキシド、ビス（2—メトキシべ ンゾィル）（1—メチルプロパン一 1—ィル）ホスフィンォキシド、ビス（2, 6 ジエトキシ ベンゾィル）（2 メチルプロパン 1 ィル）ホスフィンォキシド、ビス（2, 6 ジェトキ シベンゾィル）（1—メチルプロパン— 1—ィル）ホスフィンォキシド、ビス（2, 6 ジブト キシベンゾィル）（2 メチルプロパン 1 ィル）ホスフィンォキシド、ビス（2, 4 ジメ トキシベンゾィル）（2 メチルプロパン 1 ィル）ホスフィンォキシド、ビス（2, 4, 6 —トリメチルベンゾィル）（2, 4 ジペントキシフエ-ル）ホスフィンォキシド、ビス（2, 6 -ジメトキシベンゾィル）ベンジルホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィ ル）—2 フエ-ルプロピルホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル） 2—フエ-ルェチルホスフィンォキシド、ビス（2, 6 ジメトキシベンゾィル）ベンジルホ スフインォキシド、ビス（2, 6 ジメトキシベンゾィル） 2 フエ-ルプロピルホスフィ ンンォォキキシシドド、、ビビスス（（22,, 66 ジジメメトトキキシシベベンンゾゾィィルル））一一 22——フフエエ--ルルェェチチルルホホススフフィィンンォォキキシシ ドド、、 22,, 66 ジジメメトトキキシシベベンンゾゾィィルルベベンンジジルルブブチチルルホホススフフィィンンォォキキシシドド、、 22,, 66 ジジメメトトキキシシ ベベンンゾゾィィルルベベンンジジルルォォククチチルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル ))——22,, 55 ジジイイソソププロロピピルルフフエエ--ルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンン ゾゾィィルル）） 22 メメチチルルフフエエ--ルルホホススフフィィンンォォキキシシドドビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル）） ——44——メメチチルルフフエエ--ルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル））一一22,, 55 ジジェェチチルルフフエエ--ルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル）） 22,,Specific examples of the compound represented by the general formula (6) include bis (2,6 dimethoxybenzoyl) phenol phosphine oxide, bis (2,6 dimethoxybenzoyl) (2, 4, 4 Trimethylpentyl) phosphine oxide, bis (2,6 dimethoxybenzoyl) n-butylphosphine oxide, bis (2,6 dimethoxybenzoyl) mono (2 methylpropane-1-yl) phosphine oxide, bis (2, 6 dimethoxybenzoyl) mono (1-methylpropan-1-yl) phosphine oxide, bis (2, 6 dimethoxybenzoyl) t-butyl phosphine oxide, bis (2, 6 dimethoxybenzoyl) ) Cyclohexylphosphine oxide, bis (2,6 dimethoxybenzoyl) octylphosphine oxide, bis (2-methoxybenzoyl) (2-methylpropane-1-yl) Sphinoxide, bis (2-methoxybenzoyl) (1-methylpropane-1-yl) phosphine oxide, bis (2,6 diethoxybenzoyl) (2 methylpropane 1yl) phosphinoxide, bis (2, 6 Jetoxybenzoyl) (1-methylpropane-1-yl) phosphine oxide, bis (2,6 dibutoxybenzoyl) (2 methylpropane 1yl) phosphine oxide, bis (2,4 dimethoxybenzoyl) (2 methylpropane) 1yl) phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) (2,4 dipentoxyphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis (2,6 dimethoxybenzoyl) -2 phenolpropylphosphine oxide, bis (2,6 dimethoxybenzoyl) 2-phenol Tylphosphine oxide, bis (2,6 dimethoxybenzoyl) benzyl phosphate, bis (2,6 dimethoxybenzoyl) 2 phenolpropylphosphite Nonoxyxid, Bibissu ((22, 66 Didimethoxixibenbenzozoyl)) 1 22——Fuee--Lulecetyl Lufosphosphine oxydoxide ,,, 22, 66 Dizimetoxixibebenzozyl rubenben dizylrubbutyryl phosphosphine oxycidide,,, 22, 66 Didimethotoxixi bebenzozoyl rubenbenji Diruoctoctyl ruphosphosphine oxyxid, bibissu ((22 ,, 44, 66 tririmethicyl rubenbenzozoyl)) —— 22, 55 didiisosopprolo Pipilrufue--Ruluhophos-Fusinoxycide, Bibiss ((22, 44, 66) Trimethyle-Lubenben Zozilulu) 22 Ninoki Xidosidobibiss ((22 ,, 44, 66 Totrilimethicyl rubenbenzozoyl)) ——44——Memethytil rufue--rulufophos succinic acid, Bibiss ((22, 44, 66), 22, 55 Dijetitil rufue--Lulhophos sulphin oxycide, Bibiss ((22, 44, 66 Toririmichichirurubenbenzozoirru)) 22 ,,
33,, 55,, 66——テテトトララメメチチルルフフエエ--ルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィ ルル）） 22,, 44 ジジ一一 nn——ブブトトキキシシフフエエ--ルルホホススフフィィンンォォキキシシドド、、 22,, 44,, 66 トトリリメメチチルルベベンンゾゾ ィィルルジジフフエエ--ルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 66 ジジメメトトキキシシベベンンゾゾィィルル））一一22,, 44,, 44 トトリリ メメチチルルペペンンチチルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル））イイソソブブチチルル ホホススフフィィンンォォキキシシドド、、 22,, 66 ジジメメチチトトキキシシベベンンゾゾィィルルーー 22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルルーー nn——ブブチチルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル））フフエエ--ルルホホススフフィィ ンンォォキキシシドド、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル））一一22,, 44 ジジブブトトキキシシフフエエ--ルルホホススフフ イインンォォキキシシドド、、 11,, 1100 ビビスス [[ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル））ホホススフフィィンンォォキキシシドド]] デデカカンン、、トトリリ（（22——メメチチルルベベンンゾゾィィルル））ホホススフフィィンンォォキキシシドド、、ななどどがが挙挙げげらられれるる。。ここれれららのの中中 ででもも特特にに、、ビビスス（（22,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルル））フフエエ--ルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,,33 ,, 55, 66——Tetetratramethicyl rufue--Lulufos phosphine oxycidide, Bibiss ((22, 44, 66 66) Lulu)) 22 ,, 44 jidi nn——Bubutoxoxyfwei--Lulhophossphineoxyxid, 22, 44, 66 66 Trilmemethicyl rubenbenzozoil Dijihue-Lulufosphosphineoxycide, Bibisus ((22 ,, 66 Dijimetoxixibebenzozoyl)) 1 22, 22, 44, 44 Pepenicillylphosphosphine oxycide, Bibiss ((22, 44, 66) Trisylmethytilylbenbenzozyl)) Isoisobutytilyl Phophosphine Cisidod, 22, 66 Didimethititotoxicoxiben Zoyl luo 22 ,, 44 ,, 66 trimethylmethyrubyben zoyl luo nn—-butytilylphosphosphine oxyxid, bibis ((22, 44, 66 Tillebebenzozoil)) Hue--Rulufossus vinoxyside, bivis ((22, 44, 66 trimethylmethylebebenzozoil)) 1-22 ,, 44 Djibubutoxixifue--Rulhophos Sulfin Inoxoxyside, 11 ,, 1100 Bibiss [[Bibisu ((22 ,, 44, 66 Tritrimethylmethylurubenbenzozoir)) Susfinfinoxyside]] Dedecacan, Totrili ((22--methictillubenbenzozoil)) Jophos Sufinfinoxyside, etc. I will be disappointed. . Of these, especially among them, Bibiss ((22, 44, 66) is also known as Huvier-Lulhophossphine oxydoxyside. De, bivis ((22 ,,
44,, 66 トトリリメメチチルルベベンンゾゾィィルル））——22,, 44 ジジ—— nn——ブブトトキキシシフフエエ--ルルホホススフフィィンンォォキキシシドド、、 22 ,, 44,, 66 トトリリメメチチルルベベンンゾゾィィルルジジフフエエ--ルルホホススフフィィンンォォキキシシドド、、ビビスス（（22,, 66 ジジメメトトキキシシべべ ンンゾゾィィルル）） 22,, 44,, 44 トトリリメメチチルルペペンンチチルルホホススフフィィンンォォキキシシドドがが好好ままししいい。。 44 ,, 66 Trimethylmethyryl rubenbenzozyl)) —— 22, 44 Digi—— nn——Buttoxoxy fue--Lulhophosphosphine oxycide, 22, , 44 ,, 66 Trimethylmethyle rubenbenzozyl rudizifue--lulujophosphineoxyside, bibis ((22, 66 didimethoxixibenzozoir)) 22, , 44 ,, 44 Tritrimethicyl rupepenty nylphoshophosphine oxyxid may be preferred. .
[[00005533]] ーーォォキキシシムム誘誘導導体体  [[00005533]] --Oxiki shim induced conductor
前前記記ォォキキシシムム誘誘導導体体ととししててはは、、特特にに制制限限ははななぐぐ目目的的にに応応じじてて適適宜宜選選択択すするるここととがが ででききるるがが、、少少ななくくとともも芳芳香香族族基基をを有有すするる化化合合物物ででああるるここととがが好好ままししぐぐ下下記記一一般般式式 ((33)) 及及びび下下記記一一般般式式 ((44))のの ヽヽずずれれかかでで表表さされれるる部部分分構構造造をを有有すするる化化合合物物ででああるるここととががよよ りり好好ままししいい。。前前記記ォォキキシシムム誘誘導導体体はは、、 22種種以以上上をを併併用用ししててももよよいい。。  As the above-mentioned oxystimum induction conductor, the restriction limit is not particularly limited, but is appropriately selected according to the purpose. Although it can be made of, it is still preferred to be a compound that has at least a fragrant aromatic group. The following general formula ((33)) and the following general formula ((44)) This is a chemical compound that has a structural structure. . The above-described oxyximum-induced conductor may be used in combination of 22 or more types. .
[[00005544]] [[化化 1166]]
Figure imgf000027_0001
[[00005544]] [[Chemicalization 1166]]
Figure imgf000027_0001
[0055] [化 17] Ar -( cO-C(Y1 ) = N-0-Y2 —般式（4) [0055] [Chemical 17] Ar-(cO-C (Y 1 ) = N-0-Y 2 —General formula (4)
\ / m  \ / m
[0056] ただし、前記一般式 (3)及び (4)中、 Arは、芳香族基、及び複素環基のいずれか を表し、 Y1は、水素原子、及び一価の置換基のいずれかを表し、 Y2は、脂肪族基、 芳香族基、複素環基、 COY3, CO[0056] However, in the general formulas (3) and (4), Ar represents either an aromatic group or a heterocyclic group, and Y 1 represents any one of a hydrogen atom and a monovalent substituent. Y 2 represents an aliphatic group, an aromatic group, a heterocyclic group, COY 3 , CO
Figure imgf000028_0001
Figure imgf000028_0001
及び Υ5は、脂肪族基、芳香族基、及び複素環基のいずれかを表し、 mは 1以上の整 数を表す。 And 5 represents an aliphatic group, an aromatic group, or a heterocyclic group, and m represents an integer of 1 or more.
[0057] 前記 Y1としては、水素原子、脂肪族基、及び芳香族基のいずれかであることが好ま しい。 [0057] Y 1 is preferably a hydrogen atom, an aliphatic group, or an aromatic group.
前記 Y2としては、脂肪族基、 COY6,及び CO Y6のいずれかであることが好ましい Y 2 is preferably an aliphatic group, COY 6 , or CO Y 6
2  2
。 Y6は、脂肪族基、芳香族基、及び複素環基のいずれかを表す。 . Y 6 represents any of an aliphatic group, an aromatic group, and a heterocyclic group.
前記 Y3及び Y4としては、脂肪族基及び芳香族基の 、ずれかであることが好ま ヽ Y 3 and Y 4 are preferably any of an aliphatic group and an aromatic group.
[0058] 前記ォキシム誘導体としては、前記一般式 (3)及び前記一般式 (4)で表される構 造が、連結基を介して複数結合してなる化合物であってもよい。 [0058] 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 via a linking group.
[0059] なお、前記一般式 (3)及び前記一般式 (4)中、前記脂肪族基は、それぞれ置換基 を有していてもよいアルキル基、ァルケ-ル基、アルキ-ル基を表し、前記芳香族基 は、それぞれ置換基を有していてもよいァリール基、複素環 (ヘテロ環)基を表し、前 記 1価の置換基としては、ハロゲン原子、置換基を有してもよいアミノ基、アルコキシ カルボニル基、水酸基、エーテル基、チオール基、チォエーテル基、シリル基、ニトロ 基、シァノ基、それぞれ置換基を有していてもよいアルキル基、ァルケ-ル基、アル キニル基、ァリール基、ヘテロ環基を表す。  [0059] In the general formula (3) and the general formula (4), the aliphatic group represents an alkyl group, a alkenyl group, or an alkyl group, each of which may have a substituent. The aromatic group represents an aryl group or a heterocyclic (heterocyclic) group, each of which may have a substituent, and the monovalent substituent may have a halogen atom or a substituent. Good amino group, alkoxycarbonyl group, hydroxyl group, ether group, thiol group, thioether group, silyl group, nitro group, cyano group, alkyl group, alkenyl group, alkynyl group, which may have a substituent, Represents an aryl group or a heterocyclic group.
[0060] 前記芳香族基としては、 1個から 3個のベンゼン環が縮合環を形成したもの、ベンゼ ン環と 5員不飽和環が縮合環を形成したものを挙げることができ、具体例としては、フ ェ-ル基、ナフチル基、アントリル基、フエナントリル基、インデュル基、ァセナフテ- ル基、フルォレニル基を挙げることができ、中でも、フエ-ル基及びナフチル基のい ずれかを有する基が好ましぐナフチル基を有する基が特に好ましい。 [0060] 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 Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indur group, a acenaphthyl group, and a fluorenyl group, and among them, a group having either a phenol group or a naphthyl group. Particularly preferred is a group having a naphthyl group.
また、これらの芳香族基は置換基を有していてもよぐそのような置換基としては、水 素原子を除く一価の非金属原子団からなる基が挙げられる。例えば、後述のアルキ ル基、置換アルキル基、又は置換アルキル基における置換基として示したものなどを 挙げることができる。 Moreover, these aromatic groups may have a substituent. Examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, Group, a substituted alkyl group, or the substituents in the substituted alkyl group.
[0061] また、前記複素環 (ヘテロ環)基としては、ピロール環基、フラン環基、チォフェン環 基、ベンゾピロール環基、ベンゾフラン環基、ベンゾチォフェン環基、ピラゾール環基 、イソキサゾール環基、イソチアゾール環基、インダゾール環基、ベンゾイソキサゾ一 ル環基、ベンゾイソチアゾール環基、イミダゾール環基、ォキサゾール環基、チアゾ ール環基、ベンズイミダゾール環基、ベンズォキサゾール環基、ベンゾチアゾール環 基、ピリジン環基、キノリン環基、イソキノリン環基、ピリダジン環基、ピリミジン環基、ピ ラジン環基、フタラジン環基、キナゾリン環基、キノキサリン環基、ァシリジン環基、フエ ナントリジン環基、力ルバゾール環基、プリン環基、ピラン環基、ピぺリジン環基、ピぺ ラジン環基、モルホリン環基、インドール環基、インドリジン環基、クロメン環基、シンノ リン環基、アタリジン環基、フヱノチアジン環基、テトラゾール環基、トリアジン環基等 が挙げられ、中でも、フラン環基、チォフェン環基、イミダゾール環基、チアゾール環 基、ベンゾチアゾール環基、ピリジン環基、インドール環基、アタリジン環基が特に好 ましい。  [0061] 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, an iso Thiazole ring group, indazole ring group, benzisoxazol 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, assiridine ring group, phenanthridine ring group, force rubazole ring Group, purine ring group, pyran ring group, piperidine ring group, piperazine ring group, morpholine ring group Indole ring group, indolizine ring group, chromene ring group, cinnoline ring group, atalidine ring group, phenothiazine ring group, tetrazole ring group, triazine ring group, etc., among which furan ring group, thiophene ring group, imidazole ring Particularly preferred are the group, thiazole ring group, benzothiazole ring group, pyridine ring group, indole ring group and atalidine ring group.
また、これらの複素環基は置換基を有していてもよぐそのような置換基としては、水 素原子を除く 1価の非金属原子団からなる基が挙げられる。例えば、後述のアルキル 基、置換アルキル基、又は置換アルキル基における置換基として示したものを挙げる ことができる。  These heterocyclic groups may have a substituent. 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.
[0062] 前記 1価の置換基としては、ハロゲン原子、置換基を有してもょ 、ァミノ基、アルコキ シカルボニル基、水酸基、エーテル基、チオール基、チォエーテル基、シリル基、二 トロ基、シァノ基、それぞれ置換基を有していてもよいアルキル基、ァルケ-ル基、ァ ルキニル基、ァリール基、ヘテロ環基が好ましい。  [0062] The monovalent substituent may have a halogen atom, a substituent, an amino group, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, A cyan group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, each of which may have a substituent, are preferred.
[0063] また、前記非金属原子力もなる 1価の置換基としては、それぞれ置換基を有してい てもよいアルキル基、ァルケ-ル基、アルキニル基、ァリール基、ヘテロ環基が好まし い。  [0063] Further, as the monovalent substituent that also constitutes the nonmetallic nuclear power, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent, is preferable. .
[0064] 前記置換基を有していてもよいアルキル基としては、炭素原子数が 1から 20までの 直鎖状、分岐状、および環状のアルキル基を挙げることができ、その具体例としては 、メチル基、ェチル基、プロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル 基、ォクチル基、ノニル基、デシル基、ゥンデシル基、ドデシル基、トリデシル基、へキ サデシル基、ォクタデシル基、エイコシル基、イソプロピル基、イソブチル基、 sーブチ ル基、 t ブチル基、イソペンチル基、ネオペンチル基、 1 メチルブチル基、イソへ キシル基、 2—ェチルへキシル基、 2—メチルへキシル基、シクロへキシル基、シクロ ペンチル基、 2—ノルボル-ル基を挙げることができる。これらの中では、炭素原子数 1から 12までの直鎖状、炭素原子数 3から 12までの分岐状、並びに炭素原子数 5か ら 10までの環状のアルキル基がより好ましい。 [0064] Examples of the alkyl group which may have a substituent include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include , Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl Group, isopropyl group, isobutyl group, sec- butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group , Cyclopentyl group and 2-norbornyl group. 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.
前記置換基を有して 、てもよ 、アルキル基の置換基としては、水素原子を除く一価 の非金属原子力もなる置換基が挙げられ、好ましい例としては、ハロゲン原子（一 F、 — Br、 一 Cl、 一1)、ヒドロキシル基、アルコキシ基、ァリーロキシ基、メルカプト基、ァ ルキルチオ基、ァリールチオ基、アルキルジチォ基、ァリールジチォ基、アミノ基、 N ーァノレキノレアミノ基、 N, N ジァノレキノレアミノ基、 N ァリーノレアミノ基、 N, N ジァ リールアミノ基、 N—アルキル—N ァリールアミノ基、ァシルォキシ基、力ルバモイル ォキシ基、 N アルキル力ルバモイルォキシ基、 N ァリール力ルバモイルォキシ基 、 N, N ジアルキル力ルバモイルォキシ基、 N, N ジァリール力ルバモイルォキシ 基、 N アルキル N ァリール力ルバモイルォキシ基、アルキルスルホキシ基、ァリ 一ルスルホキシ基、ァシルチオ基、ァシルァミノ基、 N—アルキルァシルァミノ基、 N —ァリールァシルァミノ基、ウレイド基、 N，—アルキルウレイド基、 N，， N，—ジアルキ ルゥレイド基、 N，ーァリールウレイド基、 Ν，， N，ージァリールウレイド基、 N，一アルキ ルー N，ーァリールウレイド基、 N—アルキルウレイド基、 N ァリールウレイド基、 N' アルキル N アルキルウレイド基、 N' アルキル N ァリールウレイド基、 N' , N，ージアルキル—N—アルキルウレイド基、 N，， N，ージアルキル N ァリール ウレイド基、 N，ーァリール—N—アルキルウレイド基、 N，ーァリール—N ァリールゥ レイド基、 Ν' , Ν，—ジァリール— Ν アルキルウレイド基、 Ν，， Ν，—ジァリール— Ν ーァリールウレイド基、 Ν，一アルキル一 Ν，ーァリール—Ν—アルキルウレイド基、 Ν， アルキル—N'—ァリール—Ν ァリールウレイド基、アルコキシカルボ-ルァミノ 基、ァリーロキシカルボ-ルァミノ基、 Ν—アルキル—Ν—アルコキシカルボ-ルアミ ノ基、 N—アルキル— N—ァリーロキシカルボ-ルァミノ基、 N—ァリール— N—アル コキシカルボ-ルァミノ基、 N—ァリール—N—ァリーロキシカルボ-ルァミノ基、ホル ミル基、ァシル基、カルボキシル基、アルコキシカルボ-ル基、ァリーロキシカルボ- ル基、力ルバモイル基、 N—アルキル力ルバモイル基、 N, N—ジアルキルカルバモ ィル基、 N—ァリール力ルバモイル基、 N, N—ジァリール力ルバモイル基、 N—アル キル—N—ァリール力ルバモイル基、アルキルスルフィエル基、ァリールスルフィエル 基、アルキルスルホ-ル基、ァリールスルホ-ル基、スルホ基（一 SO H)及びその共 However, the substituent of the alkyl group may include a substituent which is a monovalent non-metallic nuclear energy excluding a hydrogen atom, and a preferable example is a halogen atom (one F, — Br, 1 Cl, 1)), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-anolenoquinoamino group, N, N di group Anolequinolamino group, N-arynoreamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, force ruberamoyloxy group, N-alkyl force ruberamoyloxy group, N-arreyl force ruberamoyloxy group, N, N dialkyl force ruberamoyloxy group, N, N diaryl force ruberamoyloxy group, N alkyl N arylyl force ruberamoyloxy group, al Killsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N —arylarylsamino group, ureido group, N, -alkylureido group, N, N, — Dialkylureido group, N, aryl ureido group, Ν, N, dialyl ureido group, N, one alkyl N, aryl ureido 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 aryleleureido group, N, alkylaleido-N-alkylureido group, N, er reel—N aryl reel group, Ν ', Ν, —di reel— ジ alkyl ureido group, Ν ,, Ν, —di reel—Ν reel reel group, Ν, Monoalkyl, ァ -aryl-Ν-alkylureido, Ν, alkyl-N'-aryl- urelide-ureido, alkoxycarbolamino, aryloxycarbolamino, ア ル キ ル -alkyl- ア ル キ ル -alkoxycarbo -Lumi Group, N-alkyl-N-aryloxycarbo-lamino group, N-aryl-N-alkoxycarbo-lamino group, N-aryl-N-aryloxycarbo-lamino group, formyl group, acyl group, Carboxyl group, alkoxy carb group, aryloxy carbo yl group, force rubamoyl group, N-alkyl force rubamoyl group, N, N-dialkyl carbamoyl group, N-aryl rubamoyl group, N, N— Diaryl-force rubermoyl group, N-alkyl-N-aryl-rurubamoyl group, alkyl sulfier group, allyl sulfier group, alkyl sulfol group, aryl sulfol group, sulfo group (one SO H)
3  Three
役塩基基 (スルホナト基と称す）、アルコキシスルホ -ル基、ァリーロキシスルホ -ル基Functional base group (referred to as sulfonate group), alkoxysulfol group, aryloxysulfol group
、スルフイナモイル基、 N—アルキルスルフイナモイル基、 N, N—ジアルキルスルフィ イナモイル基、 N—ァリールスルフイナモイル基、 N, N—ジァリールスルフイナモイル 基、 N—アルキル—N—ァリールスルフイナモイル基、スルファモイル基、 N—アルキ ルスルファモイル基、 N, N—ジアルキルスルファモイル基、 N—ァリールスルファモイ ル基、 N, N—ジァリールスルファモイル基、 N—アルキル— N—ァリールスルファモ ィル基、ホスホノ基（一 PO H )およびその共役塩基基 (ホスホナト基と称す）、ジアル Sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinaimoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-a Lillesulfinamoyl, sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl, N-arylsulfamoyl, N, N-diarylsulfamoyl, N-alkyl-N —Arylsulfamoyl group, phosphono group (one PO H) and its conjugate base group (referred to as phosphonato group), dial
3 2  3 2
キルホスホノ基（一PO (alkyl) )「alkyl =アルキル基、以下同」、ジァリールホスホノ Kill phosphono group (one PO (alkyl)) "alkyl = alkyl group, the same shall apply hereafter", diarylphosphono
3 2  3 2
基（一 PO (arvl) )「aryl=ァリール基、以下同」、アルキルァリールホスホノ基（一 P Group (one PO (arvl)) “aryl = aryl group, hereinafter the same”, alkylaryl phosphono group (one P
3 2  3 2
O (alkyl) (aryl) )、モノアルキルホスホノ基（一 PO (alkyl) )及びその共役塩基基（ O (alkyl) (aryl)), a monoalkylphosphono group (one PO (alkyl)) and its conjugate base group (
3 3 3 3
アルキルホスホナト基と称す）、モノアリールホスホノ基（一 PO H (aryl) )及びその共 Alkylphosphonate group), monoarylphosphono group (one PO H (aryl)) and its
3  Three
役塩基基 (ァリールホスホナト基と称す）、ホスホノォキシ基（一 OPO H )及びその共 A functional base group (referred to as an arylphosphonate group), a phosphonoxy group (one OPO H),
3 2  3 2
役塩基基 (ホスホナトォキシ基と称す）、ジアルキルホスホノォキシ基（一 OPO H (alk A functional base group (referred to as a phosphonatoxy group), a dialkylphosphonoxy group (one OPO H (alk
3 yl) )、ジァリールホスホノォキシ基（一 OPO (aryl) )、アルキルァリールホスホノォ 3yl)), diarylphosphonooxy group (one OPO (aryl)), alkylarylphosphono
2 3 2 2 3 2
キシ基（一 OPO (alkyl) (aryl) )、モノアルキルホスホノォキシ基（一OPO H (alkyl) Xyl group (one OPO (alkyl) (aryl)), monoalkyl phosphonoxy group (one OPO H (alkyl)
3 3  3 3
)及びその共役塩基基 (アルキルホスホナトォキシ基と称す）、モノアリールホスホノォ キシ基（— OPO H (aryl) )及びその共役塩基基 (ァリールホスホナトォキシ基と称す  ) And its conjugated base group (referred to as alkyl phosphonatoxy group), monoarylphosphonoxy group (—OPO H (aryl)) and its conjugated base group (referred to as aryl phosphonatoxy group)
3  Three
；)、シァノ基、ニトロ基、ァリール基、アルケニル基、アルキ-ル基、ヘテロ環基、シリル 基等が挙げられる。  ;), Cyano group, nitro group, aryl group, alkenyl group, alkyl group, heterocyclic group, silyl group and the like.
これらの置換基におけるアルキル基の具体例としては、前述のアルキル基が挙げら れ、前記置換基におけるァリール基の具体例としては、フエ-ル基、ビフヱ-ル基、 ナフチル基、トリル基、キシリル基、メシチル基、タメ-ル基、クロロフヱ-ル基、ブロモ フエ-ル基、クロロメチルフヱ-ル基、ヒドロキシフヱ-ル基、メトキシフエ-ル基、エト キシフエ-ル基、フエノキシフエ-ル基、ァセトキシフエ-ル基、ベンゾイロキシフエ- ル基、メチルチオフエ-ル基、フエ-ルチオフエ-ル基、メチルァミノフエ-ル基、ジメ チルァミノフエ-ル基、ァセチルァミノフエ-ル基、カルボキシフヱ-ル基、メトキシカ ルポ-ルフエ-ル基、エトキシフエ-ルカルポ-ル基、フエノキシカルボ-ルフエ-ル 基、 N フエ-ルカルバモイルフヱ-ル基、シァノフエ-ル基、スルホフヱ-ル基、ス ルホナトフヱ-ル基、ホスホノフエ-ル基、ホスホナトフヱ-ル基等が挙げられる。 Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, Naphtyl group, Tolyl group, Xylyl group, Mesityl group, Taml group, Chlorophenol group, Bromophenol group, Chloromethylphenol group, Hydroxyphenol group, Methoxyphenyl group, Ethoxyphenyl group, Phenooxyphenol -Group, acetylphenol group, benzoylphenol group, methylthiophenyl group, phenylthiol group, methylaminophenol group, dimethylaminophenol group, acetylaminophenol group, Carboxyphenol group, methoxypolyphenyl group, ethoxyphenol group, phenoxycarbonyl group, N-phenylcarbamoyl group, cyanophenol group, sulfophenol group, sulfonatophenol Group, phosphonophenol group, phosphonaphthol group and the like.
[0067] また、前記置換基におけるァルケ-ル基の例としては、ビュル基、 1—プロべ-ル 基、 1ーブテュル基、シンナミル基、 2—クロロー 1ーェテニル基等が挙げられ、前記 置換基におけるアルキ-ル基の例としては、ェチュル基、 1 プロピ-ル基、 1ーブ チニル基、トリメチルシリルェチュル基等が挙げられる。 [0067] Examples of the alkenyl group in the substituent include a bur group, a 1-probe group, a 1-butur group, a cinnamyl group, a 2-chloro-1-ethenyl group, and the like. Examples of the alkyl group in the group include an ethur group, a 1 propyl group, a 1-butynyl group, a trimethylsilyl ether group, and the like.
前記置換基におけるヘテロ環基としては、例えば、ピリジル基、ピペリジニル基、な どが挙げられる。  Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
前記置換基におけるシリル基としてはトリメチルシリル基等が挙げられる。 前記置換基にはァシル基 (I^CO ）を含んでいてもよぐ該ァシル基としては、該 RG1が、例えば、水素原子、上記のアルキル基、ァリール基のものなどが挙げられる。 Examples of the silyl group in the substituent include a trimethylsilyl group. Examples of the acyl group in which the substituent may include an acyl group (I ^ CO 2) include those in which R G1 is a hydrogen atom, the above alkyl group, or an aryl group.
[0068] ァシル基 (RG1CO )の RG1としては、水素原子、並びに前記アルキル基、ァリール 基を挙げることができる。これらの置換基の内、さらにより好ましいものとしてはハロゲ ン原子（一 F、—Br、—Cl、—1)、アルコキシ基、ァリーロキシ基、アルキルチオ基、ァ リールチオ基、 N—アルキルアミノ基、 N, N ジアルキルアミノ基、ァシルォキシ基、 N アルキル力ルバモイルォキシ基、 N ァリール力ルバモイルォキシ基、ァシルァ ミノ基、ホルミル基、ァシル基、カルボキシル基、アルコキシカルボ-ル基、ァリーロキ シカルボ-ル基、力ルバモイル基、 N—アルキル力ルバモイル基、 N, N ジアルキ ルカルバモイル基、 N ァリール力ルバモイル基、 N アルキル N ァリールカル バモイル基、スルホ基、スルホナト基、スルファモイル基、 N アルキルスルファモイ ル基、 N, N ジアルキルスルファモイル基、 N ァリールスルファモイル基、 N ァ ルキル— N ァリールスルファモイル基、ホスホノ基、ホスホナト基、ジアルキルホスホ ノ基、ジァリールホスホノ基、モノアルキルホスホノ基、アルキルホスホナト基、モノァリ ールホスホノ基、ァリールホスホナト基、ホスホノォキシ基、ホスホナトォキシ基、ァリー ル基、ァルケ-ル基が挙げられる。 [0068] As and R G1 of Ashiru group (R G1 CO), hydrogen atom, and the alkyl group include a Ariru group. Of these substituents, more preferred are a halogen atom (one F, —Br, —Cl, −1), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N , N dialkylamino group, acyloxy group, N alkyl group, rubermoyloxy group, N aryl group, rubermoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxy carb group, aryloxy group, rubamoyl group, N-alkyl-force rubamoyl group, N, N dialkyl carbamoyl group, N allyl force rubamoyl group, N alkyl N allyl carbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N alkyl sulfamoyl group, N, N dialkyl sulfa group Moyl group, N arylsulfamoyl group, N alkyl—N aryl Sulfamoyl group, phosphono group, phosphonato group, dialkylphospho Group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylophosphonate group, phosphonoxy group, phosphonatoxy group, aryl group and alkaryl group.
一方、置換アルキル基におけるアルキレン基としては前述の炭素数 1から 20までの アルキル基上の水素原子のいずれか 1つを除し、 2価の有機残基としたものを挙げる ことができ、好ましくは炭素原子数 1から 12までの直鎖状、炭素原子数 3から 12まで の分岐状ならびに炭素原子数 5から 10までの環状のアルキレン基を挙げることがで きる。このような置換基とアルキレン基を組み合わせることで得られる置換アルキル基 の、好ましい具体例としては、クロロメチル基、ブロモメチル基、 2—クロ口ェチル基、ト リフルォロメチル基、メトキシメチル基、イソプロポキシメチル基、ブトキシメチル基、 s ブトキシブチル基、メトキシェトキシェチル基、ァリルォキシメチル基、フエノキシメ チル基、メチルチオメチル基、トリルチオメチル基、ピリジルメチル基、テトラメチルピ ベリジ-ルメチル基、 N ァセチルテトラメチルピベリジ-ルメチル基、トリメチルシリ ルメチル基、メトキシェチル基、ェチルアミノエチル基、ジェチルァミノプロピル基、モ ルホリノプロピル基、ァセチルォキシメチル基、ベンゾィルォキシメチル基、 N—シクロ へキシルカルバモイルォキシェチル基、 N フエ-ルカルバモイルォキシェチル基、 ァセチルアミノエチル基、 N メチルベンゾィルァミノプロピル基、 2—ォキソェチル基 、 2—ォキソプロピル基、カルボキシプロピル基、メトキシカルボ-ルェチル基、ァリル ォキシカルボ-ルブチル基、クロ口フエノキシカルボ-ルメチル基、力ルバモイルメチ ル基、 N—メチルカルバモイルェチル基、 N, N ジプロピル力ルバモイルメチル基、 N— (メトキシフヱ-ル）力ルバモイルェチル基、 N—メチルー N— (スルホフヱ-ル）力 ルバモイルメチル基、スルホブチル基、スルホナトブチル基、スルファモイルブチル基 、 N ェチルスルファモイルメチル基、 N, N ジプロピルスルファモイルプロピル基、 N トリルスルファモイルプロピル基、 N—メチルー N （ホスホノフエ-ル）スルファモ ィルォクチル基、ホスホノブチル基、ホスホナトへキシル基、ジェチルホスホノブチル 基、ジフエ-ルホスホノプロピル基、メチルホスホノブチル基、メチルホスホナトブチル 基、トリルホスホノへキシル基、トリルホスホナトへキシル基、ホスホノォキシプロピル基 、ホスホナトォキシブチル基、ベンジル基、フエネチル基、 a メチルベンジル基、 1 ーメチルー 1 フエ-ルェチル基、 p—メチルベンジル基、シンナミル基、ァリル基、 1 プロべ-ルメチル基、 2—ブテュル基、 2—メチルァリル基、 2—メチルプロべ-ルメ チル基、 2 プロピニル基、 2 プチ二ル基、 3 ブチュル基等が挙げられる。 On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above. Can be a straight-chain chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkylene group 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 chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, isopropoxymethyl. Group, butoxymethyl group, s-butoxybutyl group, methoxyethoxystiltyl group, aryloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidylmethyl group, N-acetyl Tetramethylpiberidylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, jetylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N— Cyclohexylcarbamoyloxychetyl group , N-phenylcarbamoyloxychetyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarboleethyl group, aryloxycarboxylbutyl Group, chlorophenoxycarboromethyl group, strong rubamoyl methyl group, N-methylcarbamoylethyl group, N, N dipropyl strong rubamoylmethyl group, N- (methoxyphenyl) strong rubamoylethyl group, N-methyl-N- (sulfophenyl) ) Force Rubamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N ethylsulfamoylmethyl group, N, N dipropylsulfamoylpropyl group, N tolylsulfamoylpropyl group, N-methyl-N (phosphonophe- E) Sulfamoyloctyl group Phosphonobutyl group, Phosphonatohexyl group, Jetylphosphonobutyl group, Diphenylphosphonopropyl group, Methylphosphonobutyl group, Methylphosphonatobutyl group, Tolylphosphonohexyl group, Tolylphosphonatohexyl group, Phosphonoxypropyl group , Phosphonatoxybutyl group, benzyl group, phenethyl group, a methylbenzyl group, 1 -Methyl-1 phenethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propylmethyl group, 2-buturyl group, 2-methylaryl group, 2-methylpropylmethyl group, 2-propynyl group, 2 Examples include a butyryl group and a 3 butur group.
[0070] 前記ァリール基としては、 1個から 3個のベンゼン環が縮合環を形成したもの、ベン ゼン環と 5員不飽和環が縮合環を形成したものを挙げることができ、具体例としては、 フエニル基、ナフチル基、アントリル基、フ ナントリル基、インデュル基、ァセナフテ -ル基、フルォレニル基を挙げることができ、これらのなかでは、フエ-ル基、ナフチ ル基がより好ましい。 [0070] 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 Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phantolyl group, an indur group, an acenaphthyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
前記置換ァリール基としては、前述のァリール基の環形成炭素原子上に置換基と して、水素原子を除く一価の非金属原子団カ なる基を有するものが用いられる。好 ましい置換基の例としては前述のアルキル基、置換アルキル基、ならびに、先に置換 アルキル基における置換基として示したものを挙げることができる。  As the substituted aryl group, those having a monovalent non-metallic atomic group group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those previously shown as substituents in the substituted alkyl group.
[0071] 前記置換ァリール基の好ましい具体例としては、ビフヱニル基、トリル基、キシリル基 、メシチル基、タメ-ル基、クロ口フエ-ル基、ブロモフエ-ル基、フルオロフェ-ル基 、クロロメチルフエ-ル基、トリフルォロメチルフエ-ル基、ヒドロキシフエ-ル基、メトキ シフエ-ル基、メトキシェトキシフエ-ル基、ァリルォキシフエ-ル基、フエノキシフエ- ル基、メチルチオフエ-ル基、トリルチオフエ-ル基、ェチルアミノフヱ-ル基、ジェチ ルァミノフエ-ル基、モルホリノフエ-ル基、ァセチルォキシフエ-ル基、ベンゾィルォ キシフエ-ル基、 N シクロへキシルカルバモイルォキシフエ-ル基、 N フエ-ルカ ルバモイルォキシフエ-ル基、ァセチルァミノフエ-ル基、 N メチルベンゾィルァミノ フエ-ル基、カルボキシフヱ-ル基、メトキシカルボ-ルフヱ-ル基、ァリルォキシカル ボ -ルフヱ-ル基、クロロフヱノキシカルボ-ルフヱ-ル基、力ルバモイルフヱ-ル基 、 N—メチルカルバモイルフエ-ル基、 N, N ジプロピル力ルバモイルフエ-ル基、 N— (メトキシフヱ-ル）力ルバモイルフヱ-ル基、 N—メチルー N— (スルホフヱ-ル） 力ルバモイルフヱ-ル基、スルホフヱ-ル基、スルホナトフヱ-ル基、スルファモイル フエ-ル基、 N ェチルスルファモイルフエ-ル基、 N, N ジプロピルスルファモイ ルフエ-ル基、 N トリルスルファモイルフエ-ル基、 N—メチル N— (ホスホノフエ -ル）スルファモイルフヱ-ル基、ホスホノフヱ-ル基、ホスホナトフヱ-ル基、ジェチ ルホスホノフヱ-ル基、ジフヱ-ルホスホノフヱ-ル基、メチルホスホノフヱ-ル基、メ チルホスホナトフヱ-ル基、トリルホスホノフエ-ル基、トリルホスホナトフヱ-ル基、ァ リルフエ-ル基、 1 プロぺ-ルメチルフエ-ル基、 2—ブテユルフェ-ル基、 2—メチ ルァリルフエ-ル基、 2—メチルプロべ-ルフヱ-ル基、 2—プロピ-ルフヱ-ル基、 2 ーブチュルフエ-ル基、 3—ブチュルフエ-ル基等を挙げることができる。 [0071] Preferable specific examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a tamale group, a chlorophenol group, a bromophenol group, a fluorophenol group, a chloromethyl group. Phenyl group, trifluoromethylphenol group, hydroxyphenyl group, methoxyphenyl group, methoxymethoxyphenyl group, aryloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, Tolylthiophenyl group, ethylaminophenyl group, germanaminophenyl group, morpholinophenol group, acetyloxyphenyl group, benzoylphenyl group, N cyclohexylcarbamoylphenyl group, N Phenylcarbamoyl phenyl group, Acetylaminophenol group, N-Methylbenzoylaminophenol group, Carboxyphenol group, Methoxycarbol Benzyl group, aryloxy-hydroxyl-phenyl group, chlorophenol-oxyl-hydroxyl-phenyl group, strong rubamoyl-phenol group, N-methylcarbamoyl-phenol group, N, N dipropyl-strong rubamoyl-phenol group, N — (Methoxy file) Forced rubermoyl file group, N-Methyl-N— (Sulfophenyl) Forced rubamoyl filed group, Sulfofol group, Sulfontofyl group, Sulfamoyl filed group, N Ethylsulfamoylphenol N-, N, N Dipropylsulfamoylphenol, N-Tolylsulfamoylphenol, N-Methyl N- (Phosphophenol) sulfamoylphenol, Phosphophenol, Phosphonatophenol -Lu group, Jec L-phosphonophenol group, di-phenyl phosphono-phenol group, methyl-phosphono-phenol group, methyl-phospho-naphthol group, tolyl-phosphonophenol group, tolyl-phosphonaphthol group, aryl-phenyl group 1-methylpropyl group, 2-butylphenol group, 2-methylphenyl group, 2-methylpropyl group, 2-propyl group, 2-butyl group, A 3-butyrphenol group and the like can be mentioned.
[0072] 前記アルケニル基、前記置換アルケニル基、前記アルキニル基、及び前記置換ァ ルキ -ル基（-C (R°2) =C (R°3) (R°4)、及び— C≡C (R°5) )としては、 R°2、 R°3、 R°4 、 5がー価の非金属原子力もなる基のものが使用できる。 [0072] The alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkenyl group (-C (R ° 2 ) = C (R ° 3 ) (R ° 4 ), and —C≡C As (R ° 5 )), R ° 2 , R ° 3 , R ° 4 , 5 can be used as a non-metallic nuclear power.
R°2、 R°3、 R°4、 R°5としては、水素原子、ハロゲン原子、アルキル基、置換アルキル 基、ァリール基、及び置換ァリール基が好ましぐこれらの具体例としては、前述の例 として示したものを挙げることができる。これらの中でも、水素原子、ハロゲン原子、炭 素原子数 1から 10までの直鎖状、分岐状、環状のアルキル基がより好ましい。 Specific examples of R ° 2 , R ° 3 , R ° 4 and R ° 5 are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Examples of these 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.
具体的には、ビュル基、 1 プロべ-ル基、 1ーブテュル基、 1 ペンテ-ル基、 1 一へキセ -ル基、 1—オタテュル基、 1ーメチルー 1 プロぺ-ル基、 2—メチルー 1 プロぺ-ル基、 2—メチルー 1ーブテュル基、 2—フエ-ルー 1 エテュル基、 2— クロロー 1 エテュル基、ェチュル基、 1 プロピ-ル基、 1—プチ-ル基、フエ-ル ェチニル基等が挙げられる。  Specifically, butyl group, 1 probe group, 1-butur group, 1 pentyl group, 1 monohexyl group, 1-octatur group, 1-methyl-1 1-propyl group, 2-methyl- 1 Propyl group, 2-Methyl-1-butur group, 2-Fuel, 1 Etul group, 2-Chloro-1 Etul group, Etul group, 1 Propyl group, 1-Petyl group, Phenyl ethynyl Groups and the like.
ヘテロ環基としては、置換アルキル基の置換基として例示したピリジル基等が挙げ られる。  Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.
[0073] 上記置換ォキシ基 (R 60 ）としては、 6が水素原子を除く一価の非金属原子か らなる基であるものを用いることができる。好ましい置換ォキシ基としては、アルコキシ 基、ァリーロキシ基、ァシルォキシ基、力ルバモイルォキシ基、 N アルキルカルバモ ィルォキシ基、 N ァリール力ルバモイルォキシ基、 N, N ジアルキル力ルバモイル ォキシ基、 N, N ジァリール力ルバモイルォキシ基、 N アルキル N ァリール力 ルバモイルォキシ基、アルキルスルホキシ基、ァリールスルホキシ基、ホスホノォキシ 基、ホスホナトォキシ基を挙げることができる。これらにおけるアルキル基、ならびにァ リール基としては前述のアルキル基、置換アルキル基ならびに、ァリール基、置換ァリ ール基として示したものを挙げることができる。また、ァシルォキシ基におけるァシル 基 (R°7CO )としては、 R°7が、先の例として挙げたアルキル基、置換アルキル基、 ァリール基ならびに置換ァリール基のものを挙げることができる。これらの置換基の中 では、アルコキシ基、ァリーロキシ基、ァシルォキシ基、ァリールスルホキシ基がより好 ましい。好ましい置換ォキシ基の具体例としては、メトキシ基、エトキシ基、プロピルォ キシ基、イソプロピルォキシ基、ブチルォキシ基、ペンチルォキシ基、へキシルォキシ 基、ドデシルォキシ基、ベンジルォキシ基、ァリルォキシ基、フエネチルォキシ基、力 ルボキシェチルォキシ基、メトキシカルボ-ルェチルォキシ基、エトキシカルボ-ルェ チノレ才キシ基、メトキシェトキシ基、フエノキシエトキシ基、メトキシェトキシェトキシ基、 エトキシエトキシエトキシ基、モルホリノエトキシ基、モルホリノプロピルォキシ基、ァリ ロキシエトキシエトキシ基、フエノキシ基、トリルォキシ基、キシリルォキシ基、メシチル ォキシ基、メシチルォキシ基、タメ-ルォキシ基、メトキシフエニルォキシ基、エトキシ フエ-ルォキシ基、クロ口フエ-ルォキシ基、ブロモフエ-ルォキシ基、ァセチルォキ シ基、ベンゾィルォキシ基、ナフチルォキシ基、フエ-ルスルホ-ルォキシ基、ホスホ ノォキシ基、ホスホナトォキシ基等が挙げられる。 As the above substituted oxy group (R 6 0), those in which 6 is a group consisting of a monovalent nonmetallic atom excluding a hydrogen atom can be used. Preferable substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, rubamoyloxy groups, N alkylcarbamoyloxy groups, N aralkyl rubamoyloxy groups, N, N dialkyl rubamoyloxy groups, N, N diaryl rubamoyloxy groups, N alkyl N allyl force Rubbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group can be mentioned. Examples of the alkyl group and aryl group in these include the aforementioned alkyl groups, substituted alkyl groups, and those shown as aryl groups and substituted aryl groups. In addition, acyl in the acyloxy group Examples of the group (R ° 7 CO 2) include those in which R ° 7 is the alkyl group, substituted alkyl group, aryl group and substituted aryl group mentioned above. Of 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 group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, arryloxy group, phenethyloxy group, and force ruboxy group. Shetyloxy group, methoxycarbo-lethyloxy group, ethoxycarbo-tinoyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyl group Xyl group, aryloxyethoxyethoxy group, phenoxy group, triloxy group, xylyloxy group, mesityloxy group, mesityloxy group, tamoxy group, methoxyphenyloxy group, ethoxyphenyloxy group, black mouth phenol Examples thereof include an oxy group, a bromophenyl group, an acetyloxy group, a benzoyloxy group, a naphthyloxy group, a phenylsulfooxy group, a phosphonoxy group, and a phosphonatoxy group.
アミド基も含む置換アミノ基 (R 8NH―、 (R09) (R010) N-)としては、 R 8、 R 9、 R01° が水素原子を除く一価の非金属原子団からなる基のものを使用できる。なお R 9と R 1()とは結合して環を形成してもよい。置換アミノ基の好ましい例としては、 N アルキ ルァミノ基、 N, N—ジアルキルアミノ基、 N—ァリールアミノ基、 N, N—ジァリールァ ミノ基、 N アルキル— N ァリールアミノ基、ァシルァミノ基、 N アルキルァシルァ ミノ基、 N ァリールァシルァミノ基、ウレイド基、 N' アルキルウレイド基、 N，， N，一 ジアルキルウレイド基、 N，ーァリールウレイド基、 N，， N，ージァリールウレイド基、 N， アルキル N，ーァリールウレイド基、 N アルキルウレイド基、 N ァリールゥレイ ド基、 N' アルキル N アルキルウレイド基、 N' アルキル N ァリールゥレイ ド基、 N，， N'—ジアルキル—N—アルキルウレイド基、 N' アルキル—N'—ァリー ルゥレイド基、 N，， N，ージアルキル—N—アルキルウレイド基、 N，， N，ージアルキ ルー N，ーァリールウレイド基、 N，ーァリール—N—アルキルウレイド基、 N，ーァリー ルー N ァリールウレイド基、 N，， N，ージァリール—N—アルキルウレイド基、 N，， N，—ジァリール— N ァリールウレイド基、 N，—アルキル N，—ァリール— N ァ ルキルウレイド基、 N， 一アルキル N，ーァリール N ァリールウレイド基、アルコ キシカルボ-ルァミノ基、ァリーロキシカルボ-ルァミノ基、 N—アルキル—N—アル コキシカルボ-ルァミノ基、 N—アルキル—N ァリーロキシカルボ-ルァミノ基、 N— ァリーノレ N ァノレコキシカノレボニノレアミノ基、 N ァリーノレ N ァリー口キシカノレ ボニルァミノ基が挙げられる。これらにおけるアルキル基、ァリール基としては前述の アルキル基、置換アルキル基、ならびにァリール基、置換ァリール基として示したもの を挙げることができ、ァシルァミノ基、 N アルキルァシルァミノ基、 N ァリールァシ ルァミノ基おけるァシル基 (R°7CO )の R°7は前述のとおりである。これらの中でも、 より好ましいものとしては、 N アルキルアミノ基、 N, N ジアルキルアミノ基、 N ァ リールアミノ基、ァシルァミノ基が挙げられる。好ましい置換アミノ基の具体例としては 、メチルァミノ基、ェチルァミノ基、ジェチルァミノ基、モルホリノ基、ピペリジノ基、ピロ リジノ基、フエニルァミノ基、ベンゾィルァミノ基、ァセチルァミノ基等が挙げられる。 The substituted amino group (R 8 NH—, (R 09 ) (R 010 ) N-) including an amide group includes R 8 , R 9 , and R 01 ° consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom. The basic one can be used. R 9 and R 1 () 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, an N alkylamino amino group, N arylylamino group, ureido group, N 'alkylureido group, N ,, N, monodialkylureido group, N, arylarylureido group, N ,, N, diarylureido group, N, Alkyl N, aryl ureido group, N alkyl ureido group, N aryl ureido group, N 'alkyl N alkyl ureido group, N' alkyl N aryl ureido group, N ,, N'-dialkyl-N-alkyl ureido group, N 'Alkyl—N'—ary ureido group, N ,, N, dialkyl—N—alkyl ureido group, N, N, dialkyl N, arreel Raid group, N, aryl-N-alkylureido group, N, aryl roe N allyleureido group, N, N, diaryl-N—alkylureido group, N ,, N, —diaryl-N arylureido group, N, —Alkyl N, —Ariel—N Rukyureido group, N, monoalkyl N, aryl ureido N aryl ureido group, alkoxy carbolumino group, aryloxy carbolumino group, N-alkyl-N-alkoxy carbolumino group, N-alkyl-N allyloxy Examples thereof include a carbo-amino group, an N-aryl group, an N-alkoxy carbonyl group, a non-carbonyl group, and a N-type group. Examples of these alkyl groups and aryl groups include those described above as alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups, including acylamino groups, N alkylalkylamino groups, and N arylarylamino groups. R ° 7 of definitive Ashiru group (R ° 7 CO) are as described above. Among these, more preferred are an N alkylamino group, an N, N dialkylamino group, an N arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, jetylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.
[0075] 置換スルホ -ル基 ( 11 SO―)としては、 11がー価の非金属原子団からなる [0075] As the substituted sulfo group ( 11 SO-), 11 is a non-valent atomic group.
2  2
基のものを使用できる。より好ましい例としては、アルキルスルホ-ル基、ァリールスル ホニル基を挙げることができる。これらにおけるアルキル基、ァリール基としては前述 のアルキル基、置換アルキル基、ならびにァリール基、置換ァリール基として示したも のを挙げることができる。このような、置換スルホ-ル基の具体例としては、ブチルス ルホ-ル基、フエ-ルスルホ-ル基、クロ口フエ-ルスルホ -ル基等が挙げられる。  The basic one 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 the aforementioned alkyl group, substituted alkyl group, and those shown as aryl group and substituted aryl group. Specific examples of such a substituted sulfol group include a butyl sulfol group, a phenol sulfol group, and a black-ended phenol sulfol group.
[0076] スルホナト基（一 SO―)は前述のとおり、スルホ基（一 SO H)の共役塩基陰イオン  [0076] The sulfonate group (one SO-) is a conjugate base anion of the sulfo group (one SO H) as described above.
3 3  3 3
基を意味し、通常は対陽イオンとともに使用されるのが好ましい。このような対陽ィォ ンとしては、一般に知られるもの、すなわち、種々のォ-ゥム類（アンモ -ゥム類、スル ホ -ゥム類、ホスホ-ゥム類、ョードニゥム類、アジ-ゥム類等）、ならびに金属イオン 類 (Na+、 K+、 Ca2+、 Zn2+等）が挙げられる。 Means a group, usually preferably used with a counter cation. Such counter-ions include those generally known, ie, various hums (ammo-ums, sulfomes, phospho- ummes, jordanums, azimuths). Um), and metal ions (Na +, K +, Ca 2+ , Zn 2+, etc.).
[0077] 置換カルボ-ル基 (R 13— CO ）としては、 13がー価の非金属原子力もなる基の ものを使用できる。置換カルボ-ル基の好ましい例としては、ホルミル基、ァシル基、 カルボキシル基、アルコキシカルボ-ル基、ァリーロキシカルボ-ル基、力ルバモイル 基、 N アルキル力ルバモイル基、 N, N ジアルキル力ルバモイル基、 N ァリール 力ルバモイル基、 N, N ジァリール力ルバモイル基、 N—アルキル N，ーァリール 力ルバモイル基が挙げられる。これらにおけるアルキル基、ァリール基としては前述 のアルキル基、置換アルキル基、ならびにァリール基、置換ァリール基として示したも のを挙げることができる。これらの内、より好ましい置換カルボ-ル基としては、ホルミ ル基、ァシル基、カルボキシル基、アルコキシカルボ-ル基、ァリーロキシカルボ-ル 基、力ルバモイル基、 N—アルキル力ルバモイル基、 N, N—ジアルキル力ルバモイ ル基、 N—ァリール力ルバモイル基が挙げられ、さらにより好ましいものとしては、ホル ミル基、ァシル基、アルコキシカルボ-ル基ならびにァリーロキシカルボ-ル基が挙 げられる。好ましい置換カルボニル基の具体例としては、ホルミル基、ァセチル基、ベ ンゾィル基、カルボキシル基、メトキシカルボ-ル基、エトキシカルボ-ル基、ァリルォ キシカルボ-ル基、ジメチルァミノフエ-ルェテュルカルボ-ル基、メトキシカルボ- ルメトキシカルボ-ル基、 N—メチルカルバモイル基、 N—フヱ-ルカルバモイル基、 N, N—ジェチルカルバモイル基、モルホリノカルボ-ル基等が挙げられる。 [0077] As the substituted carbo group (R 13 — CO 2), a group in which 13 is a non-valent nuclear energy can also be used. Preferable examples of the substituted carbo group include formyl group, acyl group, carboxyl group, alkoxy carbo group, aryloxy carbo ol group, force rubamoyl group, N alkyl force rubamoyl group, N, N dialkyl force rubamoyl. Group, N-aryl force rubermoyl group, N, N diaryl force rubermoyl group, N-alkyl N, aryl A strong rubermoyl group can be mentioned. Examples of the alkyl group and aryl group in these include the aforementioned alkyl group, substituted alkyl group, and those shown as aryl group and substituted aryl group. Among these, more preferred substituted carbo groups include formyl, acyl, carboxyl, alkoxy carbo, aryloxy carbo, rubamoyl, N-alkyl rubamoyl, N , N-dialkyl-powered rubermoyl groups, N-aryl-powered rubermoyl groups, and even more preferred include formyl, acyl, alkoxycarbol and aryloxycarboro groups. . Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxy carbo ol group, ethoxy carbo ol group, aralkyl carboxy group, dimethylamino phen tert carbo ol group. And methoxy carbo methoxy carbo ol group, N-methyl carbamoyl group, N-furyl carbamoyl group, N, N-jetyl carbamoyl group, morpholino carbo ol group and the like.
[0078] 置換スルフィエル基 (R 14— SO—）としては R 14がー価の非金属原子団からなる基 のものを使用できる。好ましい例としては、アルキルスルフィエル基、ァリールスルフィ -ル基、スルフイナモイル基、 N—アルキルスルフイナモイル基、 N, N—ジアルキル スルフイナモイル基、 N—ァリールスルフイナモイル基、 N, N—ジァリールスルフイナ モイル基、 N—アルキル—N—ァリールスルフイナモイル基が挙げられる。これらにお けるアルキル基、ァリール基としては前述のアルキル基、置換アルキル基、ならびに ァリール基、置換ァリール基として示したものを挙げることができる。これらの内、より 好まし 、例としてはアルキルスルフィエル基、ァリールスルフィエル基が挙げられる。 このような置換スルフィエル基の具体例としては、へキシルスルフィエル基、ベンジル スルフィエル基、トリルスルフィ -ル基等が挙げられる。 As the substituted sulfiel group (R 14 —SO—), those in which R 14 is a group composed of a non-valent nonmetallic atomic group can be used. Preferable examples include alkylsulfiel group, arylsulfyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-di And arylsulfinamoyl group and N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include the above-described alkyl groups, substituted alkyl groups, and those shown as aryl groups and substituted aryl groups. Of these, more preferred examples include an alkyl sulfiel group and an aryl sulfiel group. Specific examples of such a substituted sulfiel group include a hexyl sulfiel group, a benzyl sulfiel group, a tolyl sulfyl group, and the like.
[0079] 置換ホスホノ基とはホスホノ基上の水酸基の一つもしくは二つが他の有機ォキソ基 によって置換されたものを意味し、好ましい例としては、前述のジアルキルホスホノ基 、ジァリールホスホノ基、アルキルァリールホスホノ基、モノアルキルホスホノ基、モノ ァリールホスホノ基が挙げられる。これらの中ではジアルキルホスホノ基、ならびにジ ァリールホスホノ基がより好ましい。このような具体例としては、ジェチルホスホノ基、 ジブチルホスホノ基、ジフエ-ルホスホノ基等が挙げられる。 [0080] ホスホナト基（— PO H―、 -PO H_)とは前述のとおり、ホスホノ基（— PO H )の [0079] 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. Preferred examples include the above-mentioned dialkylphosphono group, diarylphosphono group. Group, alkylaryl phosphono group, monoalkyl phosphono group and monoaryl phosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a jetyl phosphono group, a dibutyl phosphono group, and a diphenyl phosphono group. [0080] The phosphonato group (—PO H—, —PO H_) is, as described above, the phosphono group (—PO H).
3 2 3 3 2 3 2 3 3 2
、酸第一解離もしくは、酸第二解離に由来する共役塩基陰イオン基を意味する。通 常は対陽イオンと共に使用されるのが好ましい。このような対陽イオンとしては、一般 に知られるもの、すなわち、種々のォ-ゥム類（アンモ -ゥム類、スルホ -ゥム類、ホス ホ -ゥム類、ョードニゥム類、アジ-ゥム類等）、ならびに金属イオン類 (Na+、 K+、 Ca 2+、Zn2+等）が挙げられる。 Mean a conjugated base anion group derived from acid first dissociation or acid second dissociation. Usually, it is preferably used together with a counter cation. Such counter cations include those commonly known, ie, various hums (ammo-ums, sulfo-ums, phosphor-ums, jordanums, azimuths). beam, etc.), as well as metal ions (Na +, K +, Ca 2 +, Zn 2+ etc.).
[0081] 置換ホスホナト基とは前述の置換ホスホノ基の内、水酸基を一つ有機ォキソ基に置 換したものの共役塩基陰イオン基であり、具体例としては、前述のモノアルキルホス ホノ基（一PO H (alkyl) )、モノアリールホスホノ基（一PO H (aryl) )の共役塩基が [0081] The substituted phosphonate group is a conjugated base anion group in which one hydroxyl group is replaced with an organic oxo group among the above-mentioned substituted phosphono groups. PO H (alkyl)), monoarylphosphono group (one PO H (aryl)) conjugate base
3 3  3 3
挙げられる。  Can be mentioned.
[0082] 前記ォキシム誘導体のその他の具体的な例としては、例えば、特開 2001— 2338 42号公報、特表 2004— 534797号公報、及び特表 2002— 519732号公報等に開 示された化合物、並びに下記構造式で表される化合物などが挙げられる。  [0082] Other specific examples of the oxime derivative include compounds disclosed in, for example, JP-A-2001-233842, JP-T-2004-534797, JP-T-2002-519732, and the like. And compounds represented by the following structural formulas.
[0083] [化 18]
Figure imgf000039_0001
Figure imgf000039_0002
[0083] [Chemical 18]
Figure imgf000039_0001
Figure imgf000039_0002
[0084] [化 19] [0084] [Chemical 19]
Figure imgf000040_0001
Figure imgf000040_0001
上記構造式中、 Rは、 n-C H、及び p— CH C Hのいずれかを表す。  In the above structural formula, R represents either n-C H or p-CH C H.
22] twenty two]
Figure imgf000041_0001
Figure imgf000041_0002
Figure imgf000041_0003
Figure imgf000041_0001
Figure imgf000041_0002
Figure imgf000041_0003
[0088] [化 23]
Figure imgf000042_0001
[0088] [Chemical 23]
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000043_0001
Figure imgf000043_0002
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000043_0003
[0090] 前記感光性組成物における光重合開始剤の含有量は、 0. 1〜25質量％が好まし ぐ 0. 5〜20質量％がより好ましぐ 0. 5〜15質量％が更に好ましぐ 1〜10質量部 が特に好ましい。  [0090] The content of the photopolymerization initiator in the photosensitive composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and further preferably 0.5 to 15% by mass. The preferred range is 1 to 10 parts by mass.
[0091] その他の光重合開始剤  [0091] Other photopolymerization initiators
前記その他の光重合開始剤としては、前記重合性化合物の重合を開始する能力を 有する限り、特に制限はなぐ公知の光重合開始剤の中から適宜選択することができ る力 例えば、紫外線領域から可視の光線に対して感光性を有するものが好ましぐ 光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であつ てもよぐモノマーの種類に応じてカチオン重合を開始させるような開始剤であっても よい。 The other photopolymerization initiator has the ability to initiate polymerization of the polymerizable compound. Power that can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has, for example, those that are sensitive to visible light from the ultraviolet region are preferred. Photoexcited sensitizers It may be an activator that produces some kind of action and generates an active radical, and may be an initiator that initiates cationic polymerization according to the type of monomer.
また、前記光重合開始剤は、約 300〜800nm (より好ましくは 330〜500nm)の範 囲内に少なくとも約 50の分子吸光係数を有する成分を少なくとも 1種含有して ヽるこ とが好ましい。  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).
[0092] 前記その他の光重合開始剤としては、例えば、ハロゲンィ匕炭化水素誘導体 (例え ば、トリァジン骨格を有するもの、ォキサジァゾール骨格を有するもの等）、へキサァリ 一ルビイミダゾール、ケタール化合物、ヒドロキシアルキルケトン化合物、有機過酸ィ匕 物、チォ化合物、ケトンィ匕合物、アタリジンィ匕合物、メタ口セン類などが挙げられる。こ れらの中でも、感光層の感度、保存性、及び感光層と基板との密着性等の観点から 、ケトンィ匕合物及びアタリジンィ匕合物が好ましい。  [0092] Examples of the other photopolymerization initiators include, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexyl monobiimidazoles, ketal compounds, hydroxyalkyl ketones. Examples thereof include compounds, organic peroxides, thio compounds, ketone compounds, ataridin compounds, and meta-octenes. Among these, ketone compounds and atrazine compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate.
前記その他の光重合開始剤としては、具体的には、特開 2005— 258431号公報 の〔0288〕〜〔0299〕及び〔0305〕〜〔0307〕に記載されて 、る化合物などが挙げら れる。  Specific examples of the other photopolymerization initiators include the compounds described in [0288] to [0299] and [0305] to [0307] of JP-A-2005-258431. .
[0093] また、前記ケタール化合物としては、例えば、ベンジルメチルケタールとして、ィル ガキュア 651などが挙げられる。  [0093] Examples of the ketal compound include Irgacure 651 as benzylmethyl ketal.
前記ヒドロキシアルキルケトン化合物としては、例えば、ヒドロキシアルキルフエノンと して、ィルガキュア 184、ダロキュア 1173、ィルガキュア 2959、ィルガキュア 127など が挙げられる。  Examples of the hydroxyalkyl ketone compound include Irgacure 184, Darocur 1173, Irgacure 2959, and Irgacure 127 as hydroxyalkylphenones.
[0094] 更に、前記有機過酸化物としては、例えば、 3, 3 ' , 4, 4'ーテトラ (t ブチルパー ォキシカルボ-ル）ベンゾフエノン、などが挙げられる。  [0094] Further, examples of the organic peroxide include 3, 3 ', 4, 4'-tetra (t-butylperoxycarbonyl) benzophenone.
前記チオイ匕合物としては、例えば、 2 べンゾィルメチレン 3—メチルナフトチアゾ リン、などが挙げられる。  Examples of the thioi compound include 2-benzomethylene 3-methylnaphthothiazoline.
[0095] 前記ァシルホスフィンォキシドィ匕合物およびォキシム誘導体を含む全ての光重合 開始剤の前記感光層中の含有量としては、 0. 1〜30質量％が好ましぐ 0. 5〜20 質量％がより好ましぐ 0. 5〜15質量％が特に好ましい。 [0095] The content of all the photopolymerization initiators including the acyl acylphosphine compound and oxime derivative in the photosensitive layer is preferably 0.1 to 30% by mass. 20 More preferred is 0.5 to 15% by mass.
< (D)熱架橋剤 > <(D) Thermal crosslinking agent>
前記熱架橋剤としては、特に制限はなぐ 目的に応じて適宜選択することができ、 前記感光性フィルムを用いて形成される感光層の硬化後の膜強度を改良するために 、現像性等に悪影響を与えない範囲で、例えば、 1分子内に少なくとも 2つのォキシ ラン基を有するエポキシィ匕合物、 1分子内に少なくとも 2つのォキセタニル基を有する ォキセタンィ匕合物を用いることができる。  The thermal crosslinking agent is not particularly limited and can be appropriately selected according to the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive film, it is possible to develop it. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used as long as no adverse effect is exerted.
前記 1分子中に少なくとも 2つのォキシラン基を有するエポキシィ匕合物としては、例 えば、ビキシレノール型もしくはビフエノール型エポキシ榭脂（「YX4000ジャパンェ ポキシレジン社製」等)又はこれらの混合物、イソシァヌレート骨格等を有する複素環 式エポキシ榭脂（「TEPIC ;日産化学工業社製」、「ァラルダイト PT810 ;チバ'スぺシ ャルティ'ケミカルズ社製」等）、ビスフエノール A型エポキシ榭脂、ノボラック型ェポキ シ榭脂、ビスフエノール F型エポキシ榭脂、水添ビスフエノール A型エポキシ榭脂、ビ スフエノール S型エポキシ榭脂、フエノールノボラック型エポキシ榭脂、クレゾ ルノボ ラック型エポキシ榭脂、ハロゲンィ匕エポキシ榭脂 (例えば、低臭素化エポキシ榭脂、 高ハロゲン化エポキシ榭脂、臭素化フエノールノボラック型エポキシ榭脂など）、ァリ ル基含有ビスフエノール A型エポキシ榭脂、トリスフエノールメタン型エポキシ榭脂、 ジフエ-ルジメタノール型エポキシ榭脂、フエノールビフエ-レン型エポキシ榭脂、ジ シクロペンタジェン型エポキシ榭脂（「HP— 7200, HP— 7200H ;大日本インキ化 学工業社製」等）、グリシジルァミン型エポキシ榭脂（ジアミノジフエ-ルメタン型ェポ キシ榭脂、ジグリシジルァ二リン、トリグリシジルァミノフエノール等）、グリジジルエステ ル型エポキシ榭脂（フタル酸ジグリシジルエステル、アジピン酸ジグリシジルエステル 、へキサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステル等）ヒ ダントイン型エポキシ榭脂、脂環式エポキシ榭脂（3, 4—エポキシシクロへキシルメチ ノレ 3 '、 4' エポキシシクロへキサン力ノレボキシレート、ビス（3, 4—エポキシシクロ へキシルメチル）アジペート、ジシクロペンタジェンジエポキシド、 「GT— 300、 GT— 400、 ZEHPE3150 ;ダイセルィ匕学工業製」等、）、イミド型脂環式エポキシ榭脂、トリ ヒドロキシフエ-ルメタン型エポキシ榭脂、ビスフエノール Aノボラック型エポキシ榭脂 、テトラフエ-ロールエタン型エポキシ榭脂、グリシジルフタレート榭脂、テトラグリシジ ルキシレノィルエタン榭脂、ナフタレン基含有エポキシ榭脂（ナフトールァラルキル型 エポキシ榭脂、ナフトールノボラック型エポキシ榭脂、 4官能ナフタレン型エポキシ榭 月旨、巿販品としては「ESN—190, ESN— 360 ;新曰鉄ィ匕学社製」、「HP—4032, E XA-4750, EXA— 4700 ;大日本インキ化学工業社製」等）、フエノール化合物と ジビュルベンゼンゃジシクロペンタジェン等のジォレフイン化合物との付カ卩反応によ つて得られるポリフエノール化合物と、ェピクロルヒドリンとの反応物、 4 ビュルシクロ へキセン 1 オキサイドの開環重合物を過酢酸等でエポキシィ匕したもの、線状含リ ン構造を有するエポキシ榭脂、環状含リン構造を有するエポキシ榭脂、 α—メチルス チルベン型液晶エポキシ榭脂、ジベンゾィルォキシベンゼン型液晶エポキシ榭脂、 ァゾフエ-ル型液晶エポキシ榭脂、ァゾメチンフエ-ル型液晶エポキシ榭脂、ビナフ チル型液晶エポキシ榭脂、アジン型エポキシ榭脂、グリシジルメタアタリレート共重合 系エポキシ榭脂（「CP— 50S, CP— 50M ;日本油脂社製」等）、シクロへキシルマレ イミドとグリシジルメタアタリレートとの共重合エポキシ榭脂、ビス (グリシジルォキシフ ェニル）フルオレン型エポキシ榭脂、ビス（グリシジルォキシフエ-ル）ァダマンタン型 エポキシ榭脂などが挙げられる力 これらに限られるものではない。これらのエポキシ 榭脂は、 1種単独で使用してもよいし、 2種以上を併用してもよい。 Examples of the epoxy compound having at least two oxysilane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, an isocyanurate skeleton, etc. Heterocyclic epoxy resin ("TEPIC; manufactured by Nissan Chemical Industries", "ALALDITE PT810; manufactured by Ciba Special Chemicals", etc.), bisphenol A type epoxy resin, novolak type epoxy resin Bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, , Low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novola Type epoxy resin), aryl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenol dimethanol type epoxy resin, phenol biphenol type epoxy resin, dicyclopentaene Type epoxy resin (“HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals” etc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidyl dilin, triglycidyl) Such as aminophenol), glycidyl ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Alicyclic epoxy resin (3,4-epoxycyclohexylmethyl 3 ', 4' epoxies Xycyclohexane strength norevoxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentagen diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc.), imide type fat Cyclic epoxy resin, trihydroxyphenol methane type epoxy resin, bisphenol A novolac type epoxy resin , Tetraphenol-roll ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenol ethane resin, naphthalene group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional Naphthalene type epoxy resin “Made in Japan”, “ESN-190, ESN-360; manufactured by Shinsetsu Steel Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemicals, Inc. Etc.), a reaction product of a polyphenol compound obtained by the addition reaction of a phenol compound with a diolefin compound such as dibutenebenzene or dicyclopentagen and epichlorohydrin, An epoxy ring-opened polymer of xene 1 oxide with peracetic acid or the like, an epoxy resin having a linear phosphorus-containing structure, or an epoxy resin having a cyclic phosphorus-containing structure , Α-methyl stilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenol type liquid crystal epoxy resin, azomethine type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type Epoxy resin, glycidyl meta acrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), Copolymerization of cyclohexyl maleimide and glycidyl meta acrylate, epoxy resin (Glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, and the like. These epoxy resins may be used alone or in combination of two or more.
[0097] また、 1分子中に少なくとも 2つのォキシラン基を有する前記エポキシィ匕合物以外に 、 β位にアルキル基を有するエポキシ基を少なくとも 1分子中に 2つ含むエポキシィ匕 合物を用いることが出来、 β位がアルキル基で置換されたエポキシ基 (より具体的に は、 13—アルキル置換グリシジル基など）を含む化合物が特に好ましい。 [0097] In addition to the epoxy compound having at least two oxysilane groups in one molecule, an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule may be used. Particularly preferred is a compound containing an epoxy group (more specifically, a 13-alkyl-substituted glycidyl group or the like) in which the β-position is substituted with an alkyl group.
前記 j8位にアルキル基を有するエポキシ基を少なくとも含むエポキシィ匕合物は、 1 分子中に含まれる 2個以上のエポキシ基のすべてが 13 アルキル置換グリシジル基 であってもよぐ少なくとも 1個のエポキシ基が j8—アルキル置換グリシジル基であつ てもよい。  The epoxy compound containing at least the epoxy group having an alkyl group at the j8 position is composed of at least one epoxy group in which all of two or more epoxy groups contained in one molecule may be 13 alkyl-substituted glycidyl groups. The group may be a j8-alkyl substituted glycidyl group.
[0098] 前記 13位にアルキル基を有するエポキシ基を含むエポキシィ匕合物は、室温におけ る保存安定性の観点から、前記感光性組成物中に含まれる前記エポキシィ匕合物全 量中における、全エポキシ基中の β—アルキル置換グリシジル基の割合力 30%以 上であるのが好ましぐ 40%以上であるのがより好ましぐ 50%以上であるのが特に 好ましい。 [0098] From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the 13-position is based on the total amount of the epoxy compound contained in the photosensitive composition. , Ratio power of β-alkyl-substituted glycidyl group in all epoxy groups It is particularly preferable that the upper limit is 40% or more, more preferably 50% or more.
前記 j8—アルキル置換グリシジル基としては、特に制限は無ぐ 目的に応じて適宜 選択することができ、例えば、 j8—メチルダリシジル基、 13ーェチルダリシジル基、 13 プロピルグリシジル基、 13ーブチルダリシジル基、などが挙げられ、これらの中でも 、前記感光性組成物の保存安定性を向上させる観点、及び合成の容易性の観点か ら、 j8—メチルダリシジル基が好ましい。  The j8-alkyl-substituted glycidyl group is not particularly limited and can be appropriately selected according to the purpose. For example, j8-methyldaricidyl group, 13-ethyldaricidyl group, 13 propylglycidyl group, 13- And a butyldaricidyl group. Among these, a j8-methyldaricidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive composition and the ease of synthesis.
[0099] 前記 /3位にアルキル基を有するエポキシ基を含むエポキシィ匕合物としては、例え ば、多価フエノール化合物と j8—アルキルェピハロヒドリンとから誘導されたエポキシ 化合物が好ましい。 [0099] As the epoxy compound containing an epoxy group having an alkyl group at the / 3-position, for example, an epoxy compound derived from a polyvalent phenol compound and a j8-alkylepihalohydrin is preferable.
[0100] 前記 /3—アルキルェピノ、ロヒドリンとしては、特に制限はなぐ 目的に応じて適宜選 択することができ、例えば、 j8—メチルェピクロロヒドリン、 13 メチルェピブロモヒドリ ン、 13ーメチルェピフロロヒドリン等の j8—メチルェピハロヒドリン； 13ーェチルェピクロ ロヒドリン、 j8—ェチルェピブ口モヒドリン、 —ェチルェピフロロヒドリン等の —ェチ ルェピハロヒドリン； β—プロピルェピクロロヒドリン、 β—プロピルェピブ口モヒドリン、 β プロピノレエピフロロヒドリン等の β プロピノレエピハロヒドリン； βーブチノレエピク ロロヒドリン、 j8—ブチルェピブ口モヒドリン、 j8—ブチルェピフロロヒドリン等の j8—ブ チルェピハロヒドリン；などが挙げられる。これらの中でも、前記多価フエノールとの反 応性及び流動性の観点から、 β—メチルェピノ、ロヒドリンが好ましい。  [0100] The / 3-alkylepino and rhohydrin are not particularly limited and may be appropriately selected according to the purpose. For example, j8-methylepichlorohydrin, 13 methylepibromohydrin, 13- J8-methylepihalohydrin, such as methylepifluorohydrin; 13-ethylepichlorohydrin, j8-ethylepibu mouth mohydrin, —ethylepifluorohydrin, etc. —ethylepihalohydrin; β-propyle Β-Propinoreepihalohydrin such as chlorohydrin, β-propylepib mouth mohydrin, β-propinoreepifluorohydrin; β8-butinoreepichlorohydrin, j8-butylepib mouth mohydrin, j8-butylepihydrohydrin, etc. Pihalohydrin; and the like. Among these, β-methylepino and rhohydrin are preferable from the viewpoints of reactivity with the polyhydric phenol and fluidity.
[0101] 前記多価フ ノールイ匕合物としては、 1分子中に 2以上の芳香族性水酸基を含有 する化合物であれば、特に制限は無ぐ 目的に応じて適宜選択することができ、例え ば、ビスフエノール Α、ビスフエノール F、ビスフエノール S等のビスフエノール化合物、 ビフエノール、テトラメチルビフエノール等のビフエノール化合物、ジヒドロキシナフタレ ン、ビナフトール等のナフトール化合物、フエノールーホルムアルデヒド重縮合物等 のフエノールノボラック榭脂、クレゾ一ルーホルムアルデヒド重縮合物等の炭素数 1〜 10のモノアルキル置換フエノールーホルムアルデヒド重縮合物、キシレノールーホル ムアルデヒド重縮合物等の炭素数 1〜10のジアルキル置換フエノールーホルムアル デヒド重縮合物、ビスフエノール A ホルムアルデヒド重縮合物等のビスフエノール化 合物 ホルムアルデヒド重縮合物、フエノールと炭素数 1〜10のモノアルキル置換フ ェノールとホルムアルデヒドとの共重縮合物、フエノール化合物とジビュルベンゼンの 重付加物などが挙げられる。これらの中でも、例えば、流動性及び保存安定性を向 上させる目的で選択する場合には、前記ビスフエノールイ匕合物が好ましい。 [0101] 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 compounds such as bisphenol ビ ス, bisphenol F and bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, and phenol-formaldehyde polycondensates C1-C10 monoalkyl substituted phenol-formaldehyde polycondensate such as phenol novolac resin, creso-one formaldehyde polycondensate, etc. C1-C10 dialkyl substituted phenol such as xylenol-formaldehyde polycondensate Ruholmaldehyde polycondensate, bisphenol A formaldehyde Bisphenol of polycondensates such as Compounds include formaldehyde polycondensates, copolycondensates of phenol and monoalkyl-substituted phenols having 1 to 10 carbon atoms with formaldehyde, and polyadducts of phenolic compounds and dibutenebenzene. Among these, for example, when selecting for the purpose of improving fluidity and storage stability, the above-mentioned bisphenol compound is preferable.
前記 /3位にアルキル基を有するエポキシ基を含むエポキシィ匕合物としては、例え ば、ビスフエノール Aのジ一 13—アルキルグリシジルエーテル、ビスフエノール Fのジ β アルキルグリシジルエーテル、ビスフエノール Sのジー 13 アルキルグリシジ ルエーテル等のビスフエノール化合物のジー /3 アルキルグリシジルエーテル；ビフ ェノールのジー 13 アルキルグリシジルエーテル、テトラメチルビフエノールのジー 13 アルキルグリシジルエーテル等のビフエノール化合物のジー 13 アルキルグリシジ ルエーテル；ジヒドロキシナフタレンのジー /3 アルキルグリシジルエーテル、ビナフ トールのジー 13 アルキルグリシジルエーテル等のナフトール化合物の 13 アルキ ルグリシジルエーテル；フエノールーホルムアルデヒド重縮合物のポリ 13 アルキ ルグリシジルエーテル；クレゾ一ルーホルムアルデヒド重縮合物のポリ 13 アルキ ルグリシジルエーテル等の炭素数 1〜10のモノアルキル置換フエノールーホルムァ ルデヒド重縮合物のポリ 13 アルキルグリシジルエーテル；キシレノールーホルム アルデヒド重縮合物のポリ 13 アルキルグリシジルエーテル等の炭素数 1〜10の ジアルキル置換フエノールーホルムアルデヒド重縮合物のポリ 13 アルキルグリシ ジルエーテル；ビスフエノール Α—ホルムアルデヒド重縮合物のポリ 13 アルキル グリシジルエーテル等のビスフエノール化合物 ホルムアルデヒド重縮合物のポリ β アルキルグリシジルエーテル；フエノール化合物とジビュルベンゼンの重付カロ物 のポリ 13 アルキルグリシジルエーテル；などが挙げられる。  Examples of the epoxy compound containing an epoxy group having an alkyl group at the / 3-position include di-13-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and bisphenol S 13 bisphenol compounds such as alkyl glycidyl ethers / 3 alkyl glycidyl ethers; biphenols ge 13 alkyl glycidyl ethers, tetramethylbiphenol diols 13 biphenol compounds such as alkyl glycidyl ethers 13 alkyl glycidyl ethers; dihydroxy Naphthalene Gee / 3 Alkyl Glycidyl Ether, Binaphthol Gee 13 Alkyl Glycidyl Ether, etc. 13 Alkylicidyl Ethers; Phenolic Formaldehyde Polycondensate Poly 13 Alkyl glycidyl ether; poly 13 alkyl glycidyl ether of crezo-l-formaldehyde polycondensate such as poly 13 alkyl glycidyl ether, etc. monoalkyl-substituted phenol-formaldehyde polycondensate such as poly 13 alkyl glycidyl ether; xylenol-form aldehyde Poly 13 alkyl glycidyl ethers such as poly 13 alkyl glycidyl ethers of polycondensates such as dialkyl substituted phenol-formaldehyde polycondensates of poly 13 alkyl glycidyl ethers; bisphenol ポ リ -formaldehyde polycondensates of poly 13 alkyl glycidyl ethers, etc. Bisphenol compound Formaldehyde polycondensate poly β alkyl glycidyl ether; Phenol compound and dibutene benzene polycaloric poly 13 alkyl glycidyl ether.
これらの中でも、下記構造式 (I)で表されるビスフ ノールイ匕合物、及びこれとェピク ロロヒドリンなど力 得られる重合体力 誘導される β—アルキルグリシジルエーテル 、及び下記構造式 (Π)で表されるフ ノールイヒ合物 ホルムアルデヒド重縮合物の ポリ j8—アルキルグリシジルエーテルが好ましい。  Among these, the bisphenol compounds represented by the following structural formula (I), and the resulting polymer force such as epichlorohydrin, induced β-alkyl glycidyl ether, and the following structural formula (Π) Poly j8-alkyl glycidyl ether of formaldehyde polycondensate is preferred.
[化 25] 0-CH CH-CH - o- OH [Chemical 25] 0-CH CH-CH-o- OH
構造式 (I) Structural formula (I)
[化 26] [Chemical 26]
構造式 (II)
Figure imgf000049_0001
Structural formula (II)
Figure imgf000049_0001
ただし、前記構造式 (I)中、 Rは、水素原子及び炭素数 1〜6のアルキル基のいず れかを表し、 nは、 0〜20の整数を表す。  However, in the structural formula (I), R represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 20.
ただし、前記構造式 (Π)中、 Rは、水素原子及び炭素数 1〜6のアルキル基のいず れかを表し、 R"は、水素原子、及び CHのいずれかを表し、 nは、 0〜20の整数を表  However, in the structural formula (Π), R represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ″ represents either a hydrogen atom or CH, and n represents Represents an integer from 0 to 20
3  Three
す。  The
これら 13位にアルキル基を有するエポキシ基を含むエポキシィ匕合物は、 1種単独で 使用してもよいし、 2種以上を併用してもよい。また 1分子中に少なくとも 2つのォキシ ラン環を有するエポキシィ匕合物、及び j8位にアルキル基を有するエポキシ基を含む エポキシィ匕合物を併用することも可能である。  These epoxy compounds containing an epoxy group having an alkyl group at the 13-position may be used alone or in combination of two or more. 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 j8 position can be used in combination.
[0103] 前記エポキシィ匕合物の骨格としては、ビスフエノール型エポキシ榭脂、ノボラック型 エポキシ榭脂、脂環式基含有型エポキシ榭脂、及び難溶性エポキシ榭脂から選択さ れる少なくとも 1種が好ま 、。  [0103] The skeleton of the epoxy compound is at least one selected from bisphenol type epoxy resin, novolac type epoxy resin, alicyclic group-containing type epoxy resin, and poorly soluble epoxy resin. Favored ,.
[0104] 前記ォキセタンィ匕合物としては、例えば、ビス [ (3—メチルー 3—ォキセタニルメトキ シ）メチル]エーテル、ビス [ ( 3—ェチル— 3—ォキセタ -ルメトキシ)メチル]エーテル 、 1, 4 ビス [ (3—メチル 3—ォキセタ -ルメトキシ)メチル]ベンゼン、 1, 4 ビス [ ( 3 -ェチル 3—ォキセタ -ルメトキシ)メチル]ベンゼン、（ 3 -メチル 3—ォキセ タ -ル)メチルアタリレート、（3ーェチルー 3ーォキセタ -ル)メチルアタリレート、 (3- メチル 3—ォキセタ -ル)メチルメタタリレート、 ( 3 ェチル 3—ォキセタ -ル)メチ ルメタタリレート又はこれらのオリゴマーあるいは共重合体等の多官能ォキセタン類の 他、ォキセタン基を有する化合物と、ノボラック榭脂、ポリ（p ヒドロキシスチレン）、力 ルド型ビスフエノール類、カリックスァレーン類、力リックスレゾルシンアレーン類、シル セスキォキサン等の水酸基を有する榭脂など、とのエーテルィ匕合物が挙げられ、この 他、ォキセタン環を有する不飽和モノマーとアルキル (メタ）アタリレートとの共重合体 なども挙げられる。 [0104] Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxeta-lmethoxy) methyl] ether, 1, 4-bis [(3-methyl-3-oxeta-lmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxeta-lmethoxy) methyl] benzene, (3-methyl-3-oxeta-l) methyl acrylate , (3 Echiru 3 Okiseta -) methyl Atari rate, (3-methyl 3-Okiseta -) methyl meth Tari rate, (3 Echiru 3 Okiseta - Le) methylate Rume Tatari rate or oligomers thereof or copolymers In addition to polyfunctional oxetanes, compounds having an oxetane group, novolac resin, poly (p-hydroxystyrene), strength Ether type compounds such as bis-phenols, calixarenes, calixarenes, force-resorcinarenes, and silsesquioxanes having a hydroxyl group such as silsesquioxane, and other unsaturated monomers and alkyls having an oxetane ring. Examples thereof include a copolymer with (meth) acrylate.
[0105] また、前記エポキシィ匕合物や前記ォキセタンィ匕合物の熱硬化を促進するため、例 えば、アミンィ匕合物（例えば、ジシアンジアミド、ベンジルジメチルァミン、 4— (ジメチ ルァミノ）— N, N—ジメチルベンジルァミン、 4—メトキシ— N, N—ジメチルベンジル ァミン、 4—メチル— N, N—ジメチルベンジルァミン等）、 4級アンモ-ゥム塩化合物（ 例えば、トリェチルベンジルアンモ -ゥムクロリド等）、ブロックイソシァネートイ匕合物（ 例えば、ジメチルァミン等）、イミダゾール誘導体二環式アミジンィ匕合物及びその塩（ 例えば、イミダゾール、 2—メチルイミダゾール、 2—ェチルイミダゾール、 2—ェチル —4—メチルイミダゾール、 2—フエ-ルイミダゾール、 4—フエ-ルイミダゾール、 1— シァノエチル— 2—フエ-ルイミダゾール、 1— (2—シァノエチル）—2—ェチル—4 —メチルイミダゾール等）、リンィ匕合物（例えば、トリフエ-ルホスフィン等）、グアナミン 化合物（例えば、メラミン、グアナミン、ァセトグアナミン、ベンゾグアナミン等）、 S—トリ ァジン誘導体 (例えば、 2, 4—ジァミノ一 6—メタクリロイルォキシェチルー S—トリア ジン、 2—ビュル一 2, 4—ジァミノ一 S—トリァジン、 2—ビュル一 4, 6—ジァミノ一 S —トリアジン'イソシァヌル酸付カ卩物、 2, 4—ジァミノ一 6—メタクリロイルォキシェチル —S—トリァジン'イソシァヌル酸付加物等)などを用いることができる。これらは 1種単 独で使用してもよぐ 2種以上を併用してもよい。なお、前記エポキシ榭脂化合物や 前記ォキセタン化合物の硬化触媒、あるいは、これらとカルボキシル基の反応を促進 することができるものであれば、特に制限はなぐ上記以外の熱硬化を促進可能な化 合物を用いてもよい。  [0105] 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, triethylbenzylammo- Um chloride, etc.), block isocyanate compounds (for example, dimethylamine), imidazole derivative bicyclic amidine compounds and their salts (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) —4-Methylimidazole, 2-Phenolimidazole, 4-Phenolimidazole, 1-Cyanethyl—2-Fuel-Loimi Dazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc., phosphorus compounds (eg, triphenylphosphine), guanamine compounds (eg, melamine, guanamine, acetateguanamine, benzoguanamine, etc.), S-triazine derivatives (eg 2,4-diamino 1-methacryloyloxychetyl S-triazine, 2-bule 2,4-diamino S-triazine, 2-bulu 4,6-diamino 1 S-triazine'-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxychetyl-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 a compound capable of promoting thermal curing other than the above, as long as it can promote the reaction of these with a carboxyl group. May be used.
前記エポキシ化合物、前記ォキセタン化合物、及びこれらとカルボン酸との熱硬化 を促進可能な化合物の前記感光性組成物固形分中の固形分含有量は、通常 0. 01 〜 15質量％である。  The solid content in the solid content of the photosensitive composition of the epoxy compound, the oxetane compound, and a compound capable of accelerating the thermal curing of these with a carboxylic acid is usually 0.01 to 15% by mass.
[0106] また、前記熱架橋剤としては、特開平 5— 9407号公報記載のポリイソシァネートイ匕 合物を用いることができ、該ポリイソシァネートイ匕合物は、少なくとも 2つのイソシァネ 一ト基を含む脂肪族、環式脂肪族又は芳香族基置換脂肪族化合物から誘導されて いてもよい。具体的には、 2官能イソシァネート（例えば、 1, 3 フエ-レンジイソシァ ネートと 1, 4 フエ-レンジイソシァネートとの混合物、 2, 4 及び 2, 6 トルエンジ イソシァネート、 1, 3 及び 1, 4 キシリレンジイソシァネート、ビス（4 イソシァネー ト一フエ-ル)メタン、ビス（4—イソシァネートシクロへキシル)メタン、イソフォロンジィ ソシァネート、へキサメチレンジイソシァネート、トリメチルへキサメチレンジイソシァネ ート等）、該 2官能イソシァネートと、トリメチロールプロパン、ペンタリスルトール、ダリ セリン等との多官能アルコール;該多官能アルコールのアルキレンオキサイド付加体 と、前記 2官能イソシァネートとの付加体;へキサメチレンジイソシァネート、へキサメ チレン 1 , 6 ジイソシァネート及びその誘導体等の環式三量体;などが挙げられる [0106] Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is composed of at least two isocyanates. It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing a monoto group. Specifically, bifunctional isocyanates (eg, mixtures of 1,3 and 1,4-phenolic diisocyanates, 2,4 and 2,6 toluene diisocyanates, 1,3 and 1,4 xylates) Range isocyanate, bis (4-isocyanate monophenyl) methane, bis (4-isocyanatecyclohexyl) methane, isophorone di-socyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Polyfunctional alcohols of the bifunctional isocyanates and trimethylolpropane, pentalysitol, dariserine, etc .; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; Cyclic trimers such as diisocyanate, hexamethylene 1,6 diisocyanate and its derivatives Body; etc.
[0107] 更に、本発明の感光性フィルムの保存性を向上させることを目的として、前記ポリィ ソシァネート及びその誘導体のイソシァネート基にブロック剤を反応させて得られる化 合物を用いてもよい。 [0107] 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 or its derivative may be used.
前記イソシァネート基ブロック剤としては、アルコール類 (例えば、イソプロパノール 、tert ブタノール等）、ラタタム類 (例えば、 ε一力プロラタタム等）、フエノール類（ 例えば、フエノーノレ、クレゾ一ノレ、 p— tert ブチノレフエノーノレ、 p— sec ブチノレフエ ノーノレ、 p— sec ァミルフエノール、 p—ォクチルフエノール、 p ノ-ルフエノール等 )、複素環式ヒドロキシルイ匕合物（例えば、 3—ヒドロキシピリジン、 8—ヒドロキシキノリ ン等）、活性メチレン化合物（例えば、ジアルキルマロネート、メチルェチルケトキシム 、ァセチルアセトン、アルキルァセトアセテートォキシム、ァセトォキシム、シクロへキ サノンォキシム等)などが挙げられる。これらの他、特開平 6— 295060号公報記載の 分子内に少なくとも 1つの重合可能な二重結合及び少なくとも 1つのブロックイソシァ ネート基の 、ずれかを有する化合物などを用いることができる。  Examples of the isocyanate group blocking agent include alcohols (for example, isopropanol, tert-butanol, etc.), ratatas (for example, epsilon-prolactam, etc.), phenols (for example, phenol, crezo-monore, p-tert-butinolephenol) Nore, p-sec butinolevenore, p-sec amylphenol, p-octylphenol, p-norphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline) And the like, and active methylene compounds (for example, dialkyl malonate, methyl ethyl ketoxime, acetyl acetone, alkyl acetoacetonitrile, acetooxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one block isocyanate group in the molecule described in JP-A-6-295060 can be used.
[0108] また、前記熱架橋剤として、メラミン誘導体を用いることができる。該メラミン誘導体と しては、例えば、メチロールメラミン、アルキル化メチロールメラミン (メチロール基を、 メチル、ェチル、ブチルなどでエーテルィ匕した化合物）などが挙げられる。これらは 1 種単独で使用してもよいし、 2種以上を併用してもよい。これらの中でも、保存安定性 が良好で、感光層の表面硬度あるヽは硬化膜の膜強度自体の向上に有効である点 で、アルキル化メチロールメラミンが好ましぐへキサメチル化メチロールメラミンが特 に好ましい。 [0108] A melamine derivative may 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, etc.). These may be used alone or in combination of two or more. Among these, storage stability Hexamethylated methylol melamine is particularly preferred, with alkylated methylol melamine being preferred, since the surface hardness of the photosensitive layer is good and effective in improving the film strength itself of the cured film.
[0109] 前記熱架橋剤の前記感光性組成物固形分中の固形分含有量は、 1〜50質量％ が好ましぐ 3〜30質量％がより好ましい。該固形分含有量が 1質量％未満であると、 硬化膜の膜強度の向上が認められず、 50質量％を超えると、現像性の低下や露光 感度の低下を生ずることがある。  [0109] The solid content of the thermal crosslinking agent in the solid content of the photosensitive composition is preferably 1 to 50% by mass, more preferably 3 to 30% by mass. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not observed, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.
また、熱架橋剤は、反応性の点からエポキシィ匕合物が好ましい。  The thermal crosslinking agent is preferably an epoxy compound from the viewpoint of reactivity.
[0110] < (E)エラストマ一 > [0110] <(E) Elastomer>
前記エラストマ一としては、特に制限はなぐ目的に応じて適宜選択することができ 、例えば、国際公開第 04Z34147号パンフレットの [0061]〜[0073]に記載の化 合物などを使用してもよい。  The elastomer can be appropriately selected according to the purpose for which there is no particular limitation. For example, compounds described in [0061] to [0073] of International Publication No. 04Z34147 pamphlet may be used. .
[0111] く（F)フエノキシ榭脂〉 [0111] Ku (F) phenoxy rosin>
前記フ ノキシ榭脂としては、特に制限はなぐ目的に応じて適宜選択することがで き、例えば、国際公開第 04Z34147号パンフレット [0074]〜[0078]に記載の化 合物などを使用してもよい。  The phenoxy resin can be appropriately selected according to the purpose for which there is no particular limitation. For example, the compounds described in International Publication No. 04Z34147 pamphlet [0074] to [0078] are used. Also good.
[0112] く（G)増感剤 > [0112] Ku (G) Sensitizer>
前記増感剤は、前記感光層を露光し現像する場合において、該感光層の露光する 部分の厚みを該露光及び現像後にお 、て変化させな 、前記光の最小エネルギー（ 感度)を向上させる観点力 併用することが特に好ましい。  The sensitizer improves the minimum energy (sensitivity) of the light when the photosensitive layer is exposed and developed without changing the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferable to use in combination.
前記増感剤としては、前記光照射手段 (例えば、可視光線や紫外光及び可視光レ 一ザ等）に合わせて適宜選択することができる。  The sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light and visible light laser).
前記増感剤は、活性エネルギー線により励起状態となり、他の物質 (例えば、ラジカ ル発生剤、酸発生剤等）と相互作用（例えば、エネルギー移動、電子移動等)するこ とにより、ラジカルや酸等の有用基を発生することが可能である。  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 causing radicals and It is possible to generate useful groups such as acids.
前記増感剤としては、縮環系化合物、ァミノフ 二ルケトン系化合物、多核芳香族 類、酸性核を有するもの、塩基性核を有するもの、蛍光増白剤核を有するものから選 択される少なくとも 1種を含み、必要に応じて、その他の増感剤を含んでもよい。増感 剤としては、感度向上の点でさらにへテロ縮環系化合物、ァミノべンゾフエノン系化合 物が好ましぐ特にへテロ縮環系化合物が好ましい。 The sensitizer is at least selected from a condensed ring compound, an aminophenol ketone compound, a polynuclear aromatic, an acid nucleus, a basic nucleus, and a fluorescent brightener nucleus. 1 type may be included and another sensitizer may be included as needed. Sensitization As the agent, hetero-fused compounds and amaminobenzophenone compounds are more preferred from the viewpoint of improving sensitivity, and hetero-fused compounds are particularly preferred.
縮環系化合物  Fused ring compounds
前記例示化合物の中で、芳香族環ゃ複素環が縮環した化合物 (縮環系化合物)と しては、ヘテロ縮環系化合物が好ましい。前記へテロ縮環系化合物とは、環の中に ヘテロ元素を有する多環式化合物を意味し、前記環の中に、窒素原子を含むのが好 ましい。前記へテロ縮環系化合物としては、例えば、ヘテロ縮環系ケトン化合物が挙 げられる。前記へテロ縮環系ケトンィ匕合物の中でも、アタリドンィ匕合物及びチォキサン トンィ匕合物が更に好ましぐこれらの中でもチォキサントンィ匕合物が特に好ましい。 前記へテロ縮環系ケトンィ匕合物としては、具体的には、例えば、アタリドン、クロロア クリドン、 N—メチルアタリドン、 N ブチルアタリドン、 N ブチルークロロアタリドン、 などのアタリドン化合物；チォキサントン、イソプロピルチォキサントン、 2, 4 ジェチ ルチオキサントン、 1 クロロー 4 プロピルォキシチォキサントン、 QuantacureQT Xなどのチォキサントン化合物； 3—（2 べンゾフロイル） 7 ジェチルァミノタマリ ン、 3— (2 ベンゾフロイル） 7— (1—ピロリジ -ル）クマリン、 3 ベンゾィル 7— ジェチルァミノクマリン、 3—（2—メトキシベンゾィル） 7 ジェチルァミノクマリン、 3 一（4ージメチルァミノベンゾィル） 7—ジェチルァミノクマリン、 3, 3 '—カルボニル ビス（5, 7—ジ— n—プロポキシクマリン）、 3, 3，—カルボ-ルビス（7—ジェチルアミ ノクマリン）、 3—ベンゾィル 7—メトキシクマリン、 3— (2—フロイル） 7—ジェチル アミノクマリン、 3—（4ージェチルァミノシンナモイル） 7—ジェチルァミノクマリン、 7 —メトキシ一 3— (3—ピリジルカルボ-ル）クマリン、 3—ベンゾィル 5, 7—ジプロボ キシクマリン、 7 ベンゾトリアゾール 2—イルクマリン、 7 ジェチルァミノ一 4—メチ ルクマリン、また、特開平 5— 19475号、特開平 7— 271028号、特開 2002— 3632 06号、特開 2002— 363207号、特開 2002— 363208号、特開 2002— 363209号 公報等に記載のクマリンィ匕合物、などのクマリン類;などが挙げられる。  Among the exemplified compounds, a hetero condensed ring compound is preferable as a compound (condensed ring compound) in which an aromatic ring or a heterocyclic ring is condensed. The hetero-fused ring system compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ketone compound. Among the hetero-fused ketone compounds, attaridone compounds and thixanthone compounds are more preferable, and thixanthone compounds are particularly preferable. Specific examples of the hetero-fused ketone ketone compound include, for example, attaridone compounds such as attaridone, chloroacridone, N-methyl attaridone, N butyl attaridone, N butyl chloro attaridone, thixanthone, Thioxanthone compounds such as isopropyl thixanthone, 2,4 jetylthioxanthone, 1 chloro-4 propyloxy thixanthone, QuantacureQT X; 3— (2 benzofuroyl) 7 Jetylaminotamarin, 3— (2 benzofuroyl) 7— (1-Pyrrolidyl) coumarin, 3 Benzyl 7- Jetylaminocoumarin, 3 -— (2-Methoxybenzoyl) 7 Jetylaminocoumarin, 3 1 (4-Dimethylaminobenzoyl) 7— Jetylaminocoumarin, 3, 3'-carbonylbis (5,7-di-n-propoxycoumarin), 3, 3, -carbo- Rubis (7-Jetylaminocoumarin), 3-Benzyl 7-methoxycoumarin, 3- (2-Furoyl) 7-Jetylaminocoumarin, 3- (4-Jetylaminocinnamoyl) 7-Jetylaminocoumarin, 7 —Methoxy-1- (3-pyridylcarbol) coumarin, 3-benzoyl 5,7-diproxoxycoumarin, 7 benzotriazol 2-ylcoumarin, 7 Jetylamino-1-methylcoumarin, and JP-A-5-19475, Coumarins such as Coumariny compounds described in Kaihei 7-271028, JP 2002-36306 06, JP 2002-363207, JP 2002-363208, JP 2002-363209, etc. Is mentioned.
また公知の多核芳香族類 (例えば、ピレン、ペリレン、トリフエ-レン）、キサンテン類 (例えば、フルォレセイン、ェォシン、エリス口シン、ローダミン B、ローズベンガル）、シ ァニン類（例えば、インドカルボシァニン、チアカルボシァニン、ォキサカルボシァ- ン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、チアジン類（例えば 、チォニン、メチレンブルー、トルイジンブルー）、アントラキノン類（例えば、アントラキ ノン）、スクァリウム類 (例えば、スクァリウム）、などが挙げられる。 Also known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrucine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, Thiacarboxanthine, Oxacarboxin ), Merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), and the like.
[0114] 前記増感剤の含有量は、感光性フィルム用感光性組成物の全成分に対し、 0. 01 〜4質量％が好ましぐ 0. 02〜2質量％がより好ましぐ 0. 05〜1質量％が特に好ま しい。  [0114] The content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, based on all components of the photosensitive composition for photosensitive film. 05-1% by mass is particularly preferred.
前記含有量が、 0. 01質量％未満となると、感度が低下することがあり、 4質量％を 超えると、パターンの形状が悪ィ匕することがある。  When the content is less than 0.01% by mass, the sensitivity may be lowered, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.
[0115] 前記感光性組成物における前記増感剤と、光重合開始剤の含有量との質量比は、 〔(増感剤) Z (光重合開始剤)〕 = 1Z0. 1〜： LZ100であることが好ましぐ 1Z1〜1 Z50であることがより好まし!/、。 [0115] The mass ratio of the sensitizer in the photosensitive composition to the content of the photopolymerization initiator is [(sensitizer) Z (photopolymerization initiator)] = 1Z0.1 to LZ100 It is more preferable to be 1Z1 ~ 1Z50 more! / ,.
前記増感剤の含有量と、前記光重合開始剤の含有量との質量比が、上記の範囲 外であると、感度が低下し、かつ感度の経時変化が悪ィ匕することがある。  When the mass ratio of the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may decrease and the change in sensitivity over time may be adversely affected.
前記増感剤と前記光重合開始剤との組み合わせは、特にチォキサントンィ匕合物と ォキシム誘導体との組み合わせが高感度化の点で好ましい。また、前記ォキシム誘 導体には、他の中性ラジカル発生剤、少量のアミノアルキル基やアミノフヱ-ル基を 部分構造に含む光重合開始剤系化合物を併用してもよい。  The combination of the sensitizer and the photopolymerization initiator is particularly preferably a combination of a thixanthone compound and an oxime derivative from the viewpoint 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 an aminoalkyl group or aminophenyl group in a partial structure.
[0116] < (H)その他の成分 > [0116] <(H) Other ingredients>
前記その他の成分としては、例えば、熱重合禁止剤、可塑剤、着色剤 (着色顔料あ るいは染料)、体質顔料、などが挙げられ、更に基材表面への密着促進剤及びその 他の助剤類 (例えば、導電性粒子、充填剤、消泡剤、難燃剤、レべリング剤、剥離促 進剤、酸化防止剤、香料、表面張力調整剤、連鎖移動剤など)を併用してもよい。こ れらを適宜含有させることにより、目的とする感光性フィルムの安定性、写真性、膜物 性などの性質を調整することができる。  Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (colored pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other assistants. Agents (e.g., 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. Good. By appropriately containing these, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.
[0117] 熱重合禁止剤 [0117] Thermal polymerization inhibitor
前記熱重合禁止剤は、前記感光層における前記重合性化合物の熱的な重合又は 経時的な重合を防止するために添加してもよ 、。  The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
前記熱重合禁止剤としては、例えば、 4—メトキシフエノール、ハイドロキノン、アル キルまたはァリール置換ノヽイドロキノン、 tーブチルカテコール、ピロガロール、 2—ヒド ロキシベンゾフエノン、 4—メトキシ一 2 ヒドロキシベンゾフエノン、塩化第一銅、フエ ノチアジン、クロラニル、ナフチルァミン、 13 ナフトール、 2, 6 ジ tーブチルー 4 クレゾール、 2, 2，ーメチレンビス（4ーメチルー 6 t—ブチルフエノール）、ピリジン 、ニトロベンゼン、ジニトロベンゼン、ピクリン酸、 4ートルイジン、メチレンブルー、銅と 有機キレート剤反応物、サリチル酸メチル、及びフエノチアジン、ニトロソィ匕合物、 -ト ロソ化合物と A1とのキレート、などが挙げられる。 Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, and alcohol. Killed or aryl substituted nitroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy1-2hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, 13 naphthol, 2, 6 Di-t-butyl-4 cresol, 2,2, -methylenebis (4-methyl-6t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, Nitroso compounds,-Chelates of troso compounds with A1, etc.
[0118] 前記熱重合禁止剤の含有量は、前記感光層の前記重合性化合物に対して 0. 00 1〜5質量％が好ましぐ 0. 005〜2質量％がより好ましぐ 0. 01〜1質量％が特に 好ましい。 [0118] The content of the thermal polymerization inhibitor is preferably from 0.001 to 5 mass%, more preferably from 0.005 to 2 mass%, based on the polymerizable compound of the photosensitive layer. 01 to 1% by mass is particularly preferred.
前記含有量が、 0. 001質量％未満であると、保存時の安定性が低下することがあ り、 5質量％を超えると、活性エネルギー線に対する感度が低下することがある。  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.
[0119] 可塑剤 [0119] Plasticizer
前記可塑剤は、前記感光層の膜物性 (可撓性)をコントロールするために添加して ちょい。  The plasticizer should be added to control the film physical properties (flexibility) of the photosensitive layer.
前記可塑剤としては、例えば、ジメチルフタレート、ジブチルフタレート、ジイソプチ ルフタレート、ジヘプチルフタレート、ジォクチルフタレート、ジシクロへキシルフタレ ート、ジトリデシルフタレート、ブチルベンジルフタレート、ジイソデシルフタレート、ジ フエ-ルフタレート、ジァリルフタレート、ォクチルカプリールフタレート等のフタル酸ェ ステル類；トリエチレングリコールジアセテート、テトラエチレングリコールジアセテート Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisopropyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diphenyl phthalate. Phthalic acid esters such as ril phthalate and octyl capryl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate
、ジメチルダリコースフタレート、ェチノレフタリーノレエチノレグリコレート、メチルフタリー ルェチルダリコレート、ブチノレフタリーノレブチノレグリコレート、トリエチレングリコールジ カブリル酸エステル等のグリコールエステル類；トリクレジルホスフェート、トリフエ-ル ホスフェート等のリン酸エステル類； 4 トルエンスルホンアミド、ベンゼンスルホンアミ ド、 N—n—ブチルベンゼンスルホンアミド、 N—n—ブチルァセトアミド等のアミド類； ジイソブチルアジペート、ジォクチルアジペート、ジメチルセバケート、ジブチルセパ ケート、ジォクチルセパケート、ジォクチルァゼレート、ジブチルマレート等の脂肪族 二塩基酸エステル類;タエン酸トリエチル、タエン酸トリブチル、グリセリントリァセチル エステル、ラウリン酸ブチル、 4, 5 ジエポキシシクロへキサン 1, 2 ジカルボン酸 ジォクチル等、ポリエチレングリコール、ポリプロピレングリコール等のダリコール類が 挙げられる。 , Glycol esters such as dimethyl dalycose phthalate, ethino retino eno ethino glycolate, methyl phthal yl ethyl dalicolate, butino retino levino oleglycolate, triethylene glycol dicabrylate; tricresyl phosphate, Phosphate esters such as triphenyl phosphate; 4 Amides such as toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; Diisobutyl adipate, Dioctyl adipate Dibasic acid esters such as dimethyl sebacate, dibutyl sebacate, dioctyl sepacate, dioctyl azelate, dibutyl malate; triethyl taenoate, tributyl taenoate, glycerine triacetyl Examples thereof include esters, butyl laurate, 4,5 diepoxycyclohexane 1,2 dicarboxylic acid dioctyl, and the like, and darikols such as polyethylene glycol and polypropylene glycol.
[0120] 前記可塑剤の含有量は、前記感光層の全成分に対して 0. 1〜50質量％が好まし ぐ 0. 5〜40質量％がより好ましぐ 1〜30質量％が特に好ましい。  [0120] The content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive layer. preferable.
[0121] 一着色顔料  [0121] Monochromatic pigment
前記着色顔料としては、特に制限はなぐ 目的に応じて適宜選択することができ、 例えば、ビク卜! J ピュア一ブルー BO (C. I. 42595)、オーラミン（C. I. 41000)、 フアット'ブラック HB (C. I. 26150)、モノライト'エロー GT(C. I.ビグメント 'エロー 1 2)、パーマネント 'エロー GR(C. I.ピグメント 'エロー 17)、パーマネント 'エロー HR( C. I.ビグメント 'エロー 83)、パーマネント 'カーミン FBB (C. I.ビグメント 'レッド 146 )、ホスターバームレッド ESB (C. I.ピグメント 'バイオレット 19)、パーマネント 'ルビ 一 FBH (C. I.ビグメント 'レッド 11)フアステル 'ピンク Bスプラ（C. I.ビグメント 'レッド 81)モナストラル'ファースト 'ブルー（C. I.ピグメント 'ブルー 15)、モノライト'ファー スト'ブラック B (C. I.ビグメント 'ブラック 1)、カーボン、 C. I.ビグメント 'レッド 97、 C. I.ビグメント 'レッド 122、 C. I.ビグメント 'レッド 149、 C. I.ビグメント 'レッド 168、 C. I.ビグメント 'レッド 177、 C. I.ビグメント 'レッド 180、 C. I.ビグメント 'レッド 192、 C. I.ピグメント.レッド 215、 C. I.ピグメント.グリーン 7、 C. I.ピグメント.グリーン 36、 C . I.ビグメント 'ブルー 15 : 1、 C. I.ビグメント 'ブルー 15 :4、 C. I.ビグメント 'ブルー 15 : 6、 C. I.ピグメント.ブルー 22、 C. I.ピグメント.ブルー 60、 C. I.ピグメント.ブ ルー 64などが挙げられる。これらは 1種単独で用いてもよいし、 2種以上を併用しても よい。また、必要に応じて、公知の染料の中から、適宜選択した染料を使用すること ができる。  The coloring pigment is not particularly limited and can be appropriately selected according to the purpose. For example, Bikku! J Pure One Blue BO (CI 42595), Auramin (CI 41000), Fat 'Black HB (CI 26150) , Monolight 'Yellow GT (CI Pigment' Yellow 1 2), Permanent 'Yellow GR (CI Pigment' Yellow 17), Permanent 'Yellow HR (CI Pigment' Yellow 83), Permanent 'Carmine FBB (CI Pigment' Red 146) , Hoster Balm Red ESB (CI Pigment 'Violet 19), Permanent' Rubi I FBH (CI Pigment 'Red 11) Huster's' Pink B Supra (CI Pigment 'Red 81) Monastral' First 'Blue (CI Pigment' Blue 15), Monolite 'Fast' Black B (CI Pigment 'Black 1), Carbon, CI Pigment' Red 97 CI Pigment 'Red 122, CI Pigment' Red 149, CI Pigment 'Red 168, CI Pigment' Red 177, CI Pigment 'Red 180, CI Pigment' Red 192, CI Pigment.Red 215, CI Pigment.Green 7, CI Pigment Green 36, C. I. Pigment 'Blue 15: 1, CI Pigment' Blue 15: 4, CI Pigment 'Blue 15: 6, CI Pigment. Blue 22, CI Pigment. Blue 60, CI Pigment. Blue 64, etc. Is mentioned. These may be used alone or in combination of two or more. If necessary, a dye appropriately selected from known dyes can be used.
[0122] 前記着色顔料の前記感光性組成物固形分中の固形分含有量は、永久パターン形 成の際の感光層の露光感度、解像性などを考慮して決めることができ、前記着色顔 料の種類により異なる力 一般的には 0. 01〜10質量％が好ましぐ 0. 05〜5質量 %がより好ましい。  [0122] The solid content of the colored pigment in the solid content of the photosensitive composition can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during the formation of a permanent pattern. Different forces depending on the type of facial material Generally 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.
[0123] 一体質顔料 前記感光性組成物には、必要に応じて、永久パターンの表面硬度の向上、あるい は線膨張係数を低く抑えること、あるいは、硬化膜自体の誘電率や誘電正接を低く 抑えることを目的として、無機顔料や有機微粒子を添加することができる。 [0123] Solid pigment The photosensitive composition is used for the purpose of improving the surface hardness of the permanent pattern or keeping the coefficient of linear expansion low, or keeping the dielectric constant or dielectric loss tangent of the cured film low, if necessary. Inorganic pigments and organic fine particles can be added.
前記無機顔料としては、特に制限はなぐ公知のものの中から適宜選択することが でき、例えば、カオリン、硫酸バリウム、チタン酸バリウム、酸化ケィ素粉、微粉状酸化 ケィ素、気相法シリカ、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タルク、 クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、 マイ力などが挙げられる。  The inorganic pigment can be appropriately selected from known ones that are not particularly limited. For example, kaolin, barium sulfate, barium titanate, key oxide powder, fine powder oxide oxide, vapor phase method silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and my strength.
前記無機顔料の平均粒径は、 10 m未満が好ましぐ 3 m以下がより好ましい。 該平均粒径が 10 m以上であると、光錯乱により解像度が劣化することがある。 前記有機微粒子としては、特に制限はなぐ目的に応じて適宜選択することができ 、例えば、メラミン榭脂、ベンゾグアナミン榭脂、架橋ポリスチレン榭脂などが挙げられ る。また、平均粒径 0. 01〜5 /ζ πι、吸油量 100〜200m2Zg程度のシリカ、架橋榭 脂からなる球状多孔質微粒子などを用いることができる。 The average particle diameter of the inorganic pigment is preferably less than 10 m, more preferably 3 m or less. If the average particle size is 10 m or more, the resolution may deteriorate due to light scattering. The organic fine particles can be appropriately selected according to the purpose without particular limitation, and examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle size of 0.01 to 5 / ζ πι, an oil absorption of about 100 to 200 m 2 Zg, spherical porous fine particles made of a crosslinked resin, and the like can be used.
[0124] 前記体質顔料の添加量は、 1〜60質量％が好ましい。該添加量が 1質量％未満で あると、十分に線膨張係数を低下させることができないことがあり、 60質量％を超える と、感光層表面に硬化膜を形成した場合に、該硬化膜の膜質が脆くなり、永久バタ ーンを用いて配線を形成する場合にお!、て、配線の保護膜としての機能が損なわれ ることがある。  [0124] 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.
[0125] 密着促進剤  [0125] Adhesion promoter
各層間の密着性、又は感光層と基体との密着性を向上させるために、各層に公知 の 、わゆる密着促進剤を用いることができる。  In order to improve the adhesion between each layer or between the photosensitive layer and the substrate, a known adhesion promoter may be used for each layer.
[0126] 前記密着促進剤としては、例えば、特開平 5— 11439号公報、特開平 5— 34153 2号公報、及び特開平 6—43638号公報等に記載の密着促進剤が好適挙げられる 。具体的には、ベンズイミダゾール、ベンズォキサゾール、ベンズチアゾール、 2—メ ルカプトべンズイミダゾール、 2—メルカプトべンズォキサゾール、 2—メルカプトベン ズチアゾール、 3 モルホリノメチルー 1 フエ二ルートリアゾールー 2 チオン、 3— モルホリノメチル 5 フエニル ォキサジァゾール 2 チオン、 5 アミノー 3 モ ルホリノメチル チアジアゾール - 2-チオン、及び 2 メルカプト 5—メチルチオ ーチアジアゾール、トリァゾール、テトラゾール、ベンゾトリァゾール、カルボキシベン ゾトリァゾール、アミノ基含有べンゾトリァゾール、シランカップリング剤などが挙げられ る。 [0126] Preferred examples of the adhesion promoter include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3 morpholinomethyl-1 phenyroot triazole-2 thione, 3— morpholinomethyl 5 phenyl oxadiazole 2 thione, 5 amino 3 Examples include ruphorinomethyl thiadiazole-2-thione, and 2 mercapto 5-methylthiothiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.
[0127] 前記密着促進剤の含有量は、前記感光層の全成分に対して 0. 001質量％〜20 質量％が好ましぐ 0. 01〜10質量％がより好ましぐ 0. 1質量％〜5質量％が特に 好ましい。  [0127] The content of the adhesion promoter is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on all the components of the photosensitive layer. % To 5% by mass is particularly preferred.
[0128] (感光性フィルム） [0128] (Photosensitive film)
本発明の感光性フィルムとしては、支持体と、該支持体上に形成された前記本発明 の感光性組成物からなる感光層とを少なくとも有し、必要に応じて適宜熱可塑性榭 脂層等のその他の層を有することが好まし 、。  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 a thermoplastic resin layer or the like as needed. Preferred to have other layers of.
[0129] <感光層 > [0129] <Photosensitive layer>
前記感光層は、本発明の前記感光性組成物により形成される。  The photosensitive layer is formed by the photosensitive composition of the present invention.
前記感光層の前記感光性フィルムにおいて設けられる箇所としては、特に制限は なぐ 目的に応じて適宜選択することができるが、通常、前記支持体上に積層される 前記感光層の感度としては、前述のように、 0. l〜200miZcm2であることが好ま しく、 0. 2〜100mjZcm2であることがより好ましぐ 0. 5〜50miZcm2であることが 特に好ましい。 The portion provided in the photosensitive film of the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. Usually, the sensitivity of the photosensitive layer laminated on the support is as described above. as in, lay preferred that a 0. l~200miZcm 2, and particularly preferably it is 0. 2~100mjZcm 2 is more preferred instrument 0. 5~50miZcm 2.
前記感光層の厚みとしては、前述のように、 1〜： LOO mが好ましぐ 2〜50 mが より好ましぐ 4〜30 μ mが特に好ましい。  As described above, the thickness of the photosensitive layer is particularly preferably 1 to: 2 to 50 m, more preferably 4 to 30 μm, more preferably 2 to 50 m.
[0130] く支持体及び保護フィルム > [0130] Supports and protective films>
前記支持体としては、特に制限はなぐ 目的に応じて適宜選択することができるが、 前記感光層を剥離可能であり、かつ光の透過性が良好であるものが好ましぐ更に表 面の平滑性が良好であることがより好まし 、。前記支持体及び保護フィルムとしては、 具体的には、例えば、特開 2005— 258431号公報の〔0342〕〜〔0348〕に記載され ている。  The support is not particularly limited, and can be appropriately selected according to the purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance. Further, the surface is smooth. It is more preferable that the sex is good. Specific examples of the support and protective film are described in, for example, [0342] to [0348] of JP-A-2005-258431.
[0131] <その他の層 > 前記感光性フィルムにおけるその他の層としては、特に制限はなぐ 目的に応じて 適宜選択することができ、例えば、クッション層、酸素遮断層（PC層）、剥離層、接着 層、光吸収層、表面保護層などの層を有してもよい。これらの層を 1種単独で有して いてもよぐ 2種以上を有していてもよい。また、前記感光層上に保護フィルムを有し ていてもよい。 [0131] <Other layers> Other layers in the photosensitive film are not particularly limited and can be appropriately selected according to the purpose. For example, a cushion layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface You may have layers, such as a protective layer. These layers may be used alone or in combination of two or more. Further, a protective film may be provided on the photosensitive layer.
[0132] クッション層  [0132] Cushion layer
前記クッション層としては、特に制限はなぐ 目的に応じて適宜選択することができ、 アルカリ性液に対して膨潤性乃至可溶性であってもよぐ不溶性であってもよ 、。  The cushion layer is not particularly limited and may be appropriately selected depending on the purpose, and may be swellable or soluble or insoluble in an alkaline liquid.
[0133] 前記クッション層がアルカリ性液に対して膨潤性乃至可溶性である場合には、前記 熱可塑性榭脂としては、例えば、エチレンとアクリル酸エステル共重合体のケンィ匕物 、スチレンと (メタ）アクリル酸エステル共重合体のケン化物、ビュルトルエンと (メタ）ァ クリル酸エステル共重合体のケンィ匕物、ポリ (メタ)アクリル酸エステル、（メタ)アクリル 酸ブチルと酢酸ビニル等の (メタ）アクリル酸エステル共重合体等のケンィ匕物、（メタ） アクリル酸エステルと (メタ）アクリル酸との共重合体、スチレンと (メタ）アクリル酸エス テルと (メタ)アクリル酸との共重合体などが挙げられる。  [0133] When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include, for example, an ethylene / acrylate copolymer copolymer, styrene, and (meth) (Meth) such as saponified acrylate copolymer, kento of butyltoluene and (meth) acrylic ester copolymer, poly (meth) acrylate, butyl (meth) acrylate and vinyl acetate Acrylic ester copolymers, etc., (meth) acrylic acid ester and (meth) acrylic acid copolymer, styrene, (meth) acrylic acid ester and (meth) acrylic acid copolymer Etc.
[0134] この場合の熱可塑性榭脂の軟ィ匕点 (Vicat)は、特に制限はなぐ 目的に応じて適 宜選択することができる力 例えば、 80°C以下が好ましい。  [0134] The softness point (Vicat) of the thermoplastic resin in this case is a force that can be appropriately selected according to the purpose without any particular limitation. For example, 80 ° C or less is preferable.
前記軟ィ匕点が 80°C以下の熱可塑性榭脂としては、上述した熱可塑性榭脂の他、「 プラスチック性能便覧」（日本プラスチック工業連盟、全日本プラスチック成形工業連 合会編著、工業調査会発行、 1968年 10月 25日発行）による軟ィ匕点が約 80°C以下 の有機高分子の内、アルカリ性液に可溶なものが挙げられる。また、軟ィ匕点が 80°C 以上の有機高分子物質においても、該有機高分子物質中に該有機高分子物質と相 溶性のある各種の可塑剤を添加して実質的な軟ィ匕点を 80°C以下に下げることも可 能である。  In addition to the above-mentioned thermoplastic resin, the above-mentioned thermoplastic resin has a softness point of 80 ° C or less, as well as “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, Issued on October 25, 1968). Among the organic polymers whose soft spot is about 80 ° C or less, those that are soluble in alkaline liquids are listed. In addition, even in an organic polymer material having a soft softening point of 80 ° C or higher, various plasticizers compatible with the organic polymer material are added to the organic polymer material so that a substantial softness can be obtained. It is also possible to lower the point below 80 ° C.
[0135] また、前記クッション層がアルカリ性液に対して膨潤性乃至可溶性である場合には 、前記感光性フィルムの層間接着力としては、特に制限はなぐ 目的に応じて適宜選 択することができるが、例えば、各層の層間接着力の中で、前記支持体と前記クッシ ヨン層との間の層間接着力が、最も小さいことが好ましい。このような層間接着力とす ることにより、前記感光性フィルムから前記支持体のみを剥離し、前記クッション層を 介して前記感光層を露光した後、アルカリ性の現像液を用いて該感光層を現像する ことができる。また、前記支持体を残したまま、前記感光層を露光した後、前記感光 性フィルム力 前記支持体のみを剥離し、アルカリ性の現像液を用いて該感光層を 現像することちでさる。 [0135] 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. However, for example, it is preferable that the interlayer adhesion between the support and the cushion layer is the smallest among the interlayer adhesion of each layer. Such an interlayer adhesion force Thus, after peeling only the support from the photosensitive film and exposing the photosensitive layer through the cushion layer, the photosensitive layer can be developed using an alkaline developer. Further, after exposing the photosensitive layer while leaving the support, the photosensitive film force is peeled off, and the photosensitive layer is developed using an alkaline developer.
[0136] 前記層間接着力の調整方法としては、特に制限はなぐ目的に応じて適宜選択す ることができ、例えば、前記熱可塑性榭脂中に公知のポリマー、過冷却物質、密着改 良剤、界面活性剤、離型剤などを添加する方法が挙げられる。  [0136] The method for adjusting the interlayer adhesive force can be appropriately selected according to the purpose without any particular limitation. For example, a known polymer, supercooling substance, or adhesion improver in the thermoplastic resin can be selected. , A method of adding a surfactant, a release agent and the like.
[0137] 前記可塑剤としては、特に制限はなぐ目的に応じて適宜選択することができるが、 例えば、ポリプロピレングリコール、ポリエチレングリコール、ジォクチルフタレート、ジ へプチノレフタレート、ジブチノレフタレート、トリクレジルフォスフェート、クレジノレジフエ -ルフォスフェート、ビフエ-ルジフエ-ルフォスフェート等のアルコール類やエステ ル類；トルエンスルホンアミド等のアミド類、などが挙げられる。  [0137] The plasticizer can be appropriately selected according to the purpose without any particular limitation. For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutino phthalate, tricres. Alcohols and esters such as zircphosphate, crezinoresiphosphate and biphenyldiphosphate, amides such as toluenesulfonamide, and the like.
[0138] 前記クッション層がアルカリ性液に対して不溶性である場合には、前記熱可塑性榭 脂としては、例えば、主成分がエチレンを必須の共重合成分とする共重合体が挙げ られる。  [0138] When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is an essential copolymer component of ethylene.
前記エチレンを必須の共重合成分とする共重合体としては、特に制限はなぐ目的 に応じて適宜選択することができる力 例えば、エチレン 酢酸ビニル共重合体 (EV A)、エチレン—ェチルアタリレート共重合体 (EEA)などが挙げられる。  The copolymer having ethylene as an essential copolymer component is a force that can be appropriately selected according to the purpose without any particular limitation. For example, ethylene vinyl acetate copolymer (EV A), ethylene-ethyl acrylate. Copolymer (EEA) and the like.
[0139] 前記クッション層がアルカリ性液に対して不溶性である場合には、前記感光性フィ ルムの層間接着力としては、特に制限はなぐ目的に応じて適宜選択することができ るが、例えば、各層の層間接着力の中で、前記感光層と前記クッション層との接着力 力 最も小さいことが好ましい。このような層間接着力とすることにより、前記感光性フ イルムカゝら前記支持体及びクッション層を剥離し、前記感光層を露光した後、アルカリ 性の現像液を用いて該感光層を現像することができる。また、前記支持体を残したま ま、前記感光層を露光した後、前記感光性フィルムから前記支持体と前記クッション 層を剥離し、アルカリ性の現像液を用いて該感光層を現像することもできる。  [0139] When the cushion layer is insoluble in an alkaline liquid, the interlayer adhesive force of the photosensitive film can be appropriately selected according to the purpose without any particular limitation. Of the interlayer adhesive strength of each layer, the adhesive strength between the photosensitive layer and the cushion layer is preferably the smallest. With such an interlayer adhesive strength, the support and cushion layer are peeled off from the photosensitive film carrier, the photosensitive layer is exposed, and then the photosensitive layer is developed using an alkaline developer. be able to. Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer can be peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer. .
[0140] 前記層間接着力の調整方法としては、特に制限はなぐ目的に応じて適宜選択す ることができ、例えば、前記熱可塑性榭脂中に各種のポリマー、過冷却物質、密着改 良剤、界面活性剤、離型剤などを添加する方法、以下に説明するエチレン共重合比 を調整する方法などが挙げられる。 [0140] The method for adjusting the interlayer adhesion is appropriately selected according to the purpose for which there is no particular limitation. For example, a method of adding various polymers, supercooling substances, adhesion improvers, surfactants, mold release agents, etc. to the thermoplastic resin, adjusting the ethylene copolymerization ratio described below The method of doing is mentioned.
[0141] 前記エチレンを必須の共重合成分とする共重合体におけるエチレン共重合比は、 特に制限はなぐ 目的に応じて適宜選択することができるが、例えば、 60〜90質量 %が好ましぐ 60〜80質量％がより好ましぐ 65〜80質量％が特に好ましい。  [0141] 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. 60-80% by mass is more preferred. 65-80% by mass is particularly preferred.
前記エチレンの共重合比が、 60質量％未満になると、前記クッション層と前記感光 層との層間接着力が高くなり、該クッション層と該感光層との界面で剥離することが困 難となることがあり、 90質量％を超えると、前記クッション層と前記感光層との層間接 着力が小さくなりすぎるため、該クッション層と該感光層との間で非常に剥離しやすく 、前記クッション層を含む感光性フィルムの製造が困難となることがある。  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. If the amount exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled off. It may be difficult to produce the photosensitive film.
[0142] 前記クッション層の厚みは、特に制限はなぐ 目的に応じて適宜選択することができ る力 f列; tは、、 5〜50 111カ女子ましく、 10〜50 111カ 0り女子ましく、 15〜40 111カ に好ましい。  [0142] The thickness of the cushion layer is not particularly limited. The force f can be appropriately selected according to the purpose. F column; t is 5-50 111 girls, 10-50 111 girls. Preferably, 15-40111.
前記厚みが、 5 m未満になると、基体の表面における凹凸や、気泡等への凹凸 追従性が低下し、高精細な永久パターンを形成できないことがあり、 50 mを超える と、製造上の乾燥負荷増大等の不具合が生じることがある。  If the thickness is less than 5 m, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition permanent pattern may not be formed. Problems such as increased load may occur.
[0143] 酸素遮断層（PC層） [0143] Oxygen barrier layer (PC layer)
前記酸素遮断層は、通常ポリビュルアルコールを主成分として形成されることが好 ましぐ厚みが 0. 5〜5 μ m程度の被膜であることが好ましい。  The oxygen barrier layer is preferably a film having a thickness of preferably about 0.5 to 5 μm, and is preferably formed mainly of polybulal alcohol.
[0144] 〔感光性フィルムの製造方法〕 [Method for producing photosensitive film]
前記感光性フィルムは、例えば、次のようにして製造することができる。 まず、前記感光性組成物に含まれる材料を、水又は溶剤に溶解、乳化又は分散さ せて、感光性フィルム用の感光性組成物溶液を調製する。  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.
[0145] 前記溶媒としては、特に制限はなぐ 目的に応じて適宜選択することができ、例えば 、メタノール、エタノール、 n—プロパノール、イソプロパノール、 n—ブタノール、 sec ーブタノール、 n—へキサノール等のアルコール類；アセトン、メチルェチルケトン、メ チルイソブチルケトン、シクロへキサノン、ジイソプチルケトンなどのケトン類；酢酸ェチ ル、酢酸ブチル、酢酸 n—ァミル、硫酸メチル、プロピオン酸ェチル、フタル酸ジメ チル、安息香酸ェチル、及びメトキシプロピルアセテートなどのエステル類；トルエン、 キシレン、ベンゼン、ェチルベンゼンなどの芳香族炭化水素類；四塩ィ匕炭素、トリクロ 口エチレン、クロ口ホルム、 1, 1, 1—トリクロロェタン、塩化メチレン、モノクロ口べンゼ ンなどのハロゲンィ匕炭化水素類;テトラヒドロフラン、ジェチルエーテル、エチレンダリ コーノレモノメチノレエーテノレ、エチレングリコーノレモノェチノレエーテノレ、 1ーメトキシー 2 プロパノールなどのエーテル類；ジメチルホルムアミド、ジメチルァセトアミド、ジメチ ルスルホオキサイド、スルホランなどが挙げられる。これらは、 1種単独で使用してもよ ぐ 2種以上を併用してもよい。また、公知の界面活性剤を添加してもよい。 [0145] The solvent is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone; , Esters of butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; Halogenated hydrocarbons such as tetrasalt carbon, trichloroethylene, blackform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene; tetrahydrofuran, jetyl ether, ethylene alcohol Examples include ethers such as methylenoatenole, ethyleneglycolenoethylenoleatenole, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.
[0146] 次に、前記支持体上に前記感光性組成物溶液を塗布し、乾燥させて感光層を形 成し、感光性フィルムを製造することができる。  [0146] Next, the photosensitive composition solution is coated on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.
[0147] 前記感光性組成物溶液の塗布方法としては、特に制限はなぐ 目的に応じて適宜 選択することができる力 例えば、スプレー法、ロールコート法、回転塗布法、スリット コート法、エタストルージョンコート法、カーテンコート法、ダイコート法、グラビアコート 法、ワイヤーバーコート法、ナイフコート法等の各種の塗布方法が挙げられる。  [0147] The method for applying the photosensitive composition solution is not particularly limited. The force can be selected appropriately according to the purpose. For example, spray method, roll coating method, spin coating method, slit coating method, etatrusion. Examples of the coating method include a coating method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
前記乾燥の条件としては、各成分、溶媒の種類、使用割合等によっても異なるが、 通常 60〜 110°Cの温度で 30秒間〜 15分間程度である。  The drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
[0148] 前記感光性フィルムは、例えば、円筒状の卷芯に巻き取って、長尺状でロール状 に巻かれて保管されるのが好ま 、。 [0148] The photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored.
前記長尺状の感光性フィルムの長さは、特に制限はなぐ例えば、 10-20, OOOm の範囲力も適宜選択することができる。また、ユーザーが使いやすいようにスリットカロ ェし、 100〜1, OOOmの範囲の長尺体をロール状にしてもよい。なお、この場合には 、前記支持体が一番外側になるように巻き取られるのが好ましい。また、前記ロール 状の感光性フィルムをシート状にスリットしてもよい。保管の際、端面の保護、エッジフ ユージョンを防止する観点から、端面にはセパレーター (特に防湿性のもの、乾燥剤 入りのもの）を設置するのが好ましぐまた梱包も透湿性の低い素材を用いるのが好ま しい。  The length of the long photosensitive film is not particularly limited. For example, a range force of 10-20, OOOm can be appropriately selected. In addition, slitting may be performed for the convenience of the user, and a long body in the range of 100 to 1, OOOm may be rolled. In this case, it is preferable that the support is wound up so as to be the outermost side. The roll-shaped photosensitive film may be slit into a sheet shape. In order to protect the end face and prevent edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face. It is preferable to use it.
[0149] (感光性積層体） 前記感光性積層体は、基体上に、前記感光層を少なくとも有し、目的に応じて適宜 選択されるその他の層を積層してなる。 [0149] (Photosensitive laminate) The photosensitive laminate is formed by laminating at least the photosensitive layer on a substrate and other layers appropriately selected according to the purpose.
[0150] <基体>  [0150] <Substrate>
前記基体は、感光層が形成される被処理基体、又は本発明の感光性フィルムの少 なくとも感光層が転写される被転写体となるもので、特に制限はなぐ目的に応じて適 宜選択することができ、例えば、表面平滑性の高いものから凸凹のある表面を持つも のまで任意に選択できる。板状の基体が好ましぐいわゆる基板が使用される。具体 的には、公知のプリント配線板製造用の基板 (プリント基板)、ガラス板 (ソーダガラス 板など）、合成樹脂性のフィルム、紙、金属板などが挙げられる。  The substrate is a substrate to be processed on which a photosensitive layer is formed, or a transfer target to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is appropriately selected depending on the purpose without particular limitation. For example, it can be arbitrarily selected from those having a high surface smoothness to those having a rough surface. A so-called substrate in which a plate-like substrate is preferred 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.
[0151] 〔感光性積層体の製造方法〕 [Method for producing photosensitive laminate]
前記感光性積層体の製造方法として、第 1の態様として、前記感光性組成物を前 記基体の表面に塗布し乾燥する方法が挙げられ、第 2の態様として、本発明の感光 性フィルムにおける少なくとも感光層を加熱及び加圧の少なくとも ヽずれかを行 、な 力 転写して積層する方法が挙げられる。  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, in the photosensitive film of the present invention. A method of laminating by transferring at least one of heating and pressurizing at least one of the photosensitive layer and transferring force is mentioned.
[0152] 前記第 1の態様の感光性積層体の製造方法は、前記基体上に、前記感光性組成 物を塗布及び乾燥して感光層を形成する。 [0152] In the method for producing a photosensitive laminate of the first aspect, the photosensitive composition is applied and dried on the substrate to form a photosensitive layer.
前記塗布及び乾燥の方法としては、特に制限はなぐ目的に応じて適宜選択するこ とができ、例えば、前記基体の表面に、前記感光性組成物を、水又は溶剤に溶解、 乳化又は分散させて感光性組成物溶液を調製し、該溶液を直接塗布し、乾燥させる ことにより積層する方法が挙げられる。  The coating and drying method can be appropriately selected according to the purpose without any particular limitation. For example, the photosensitive composition is dissolved, emulsified or dispersed on the surface of the substrate in water or a solvent. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.
[0153] 前記感光性組成物溶液の溶剤としては、特に制限はなぐ目的に応じて適宜選択 することができ、前記感光性フィルムに用いたものと同じ溶剤が挙げられる。これらは[0153] The solvent of the photosensitive composition solution can be appropriately selected according to the purpose without any particular limitation, and examples thereof include the same solvents as those used for the photosensitive film. They are
、 1種単独で使用してもよぐ 2種以上を併用してもよい。また、公知の界面活性剤を 添カロしてちょい。 One type may be used alone or two or more types may be used in combination. Also, add a known surfactant.
[0154] 前記塗布方法及び乾燥条件としては、特に制限はなぐ目的に応じて適宜選択す ることができ、前記感光性フィルムに用いたものと同じ方法及び条件で行う。  [0154] The coating method and drying conditions can be appropriately selected according to the purpose without any particular limitation, and the same methods and conditions as those used for the photosensitive film are used.
[0155] 前記第 2の態様の感光性積層体の製造方法は、前記基体の表面に本発明の感光 性フィルムを加熱及び加圧の少なくともいずれかを行いながら積層する。なお、前記 感光性フィルムが前記保護フィルムを有する場合には、該保護フィルムを剥離し、前 記基体に前記感光層が重なるようにして積層するのが好ま 、。 [0155] 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. The above When the photosensitive film has the protective film, it is preferable that the protective film is peeled off and laminated so that the photosensitive layer overlaps the substrate.
前記加熱温度は、特に制限はなぐ 目的に応じて適宜選択することができ、例えば 、 15〜180°Cが好ましぐ 60〜140°Cがより好ましい。  The heating temperature is not particularly limited, and can be appropriately selected according to the purpose. For example, 15 to 180 ° C is preferable, and 60 to 140 ° C is more preferable.
前記加圧の圧力は、特に制限はなぐ 目的に応じて適宜選択することができ、例え ば、、 0. 1〜1. OMPa力好ましく、 0. 2〜0. 8MPa力 ^より好まし!/ヽ。  The pressure of the pressurization is not particularly limited, and can be appropriately selected depending on the purpose. For example, 0.1 to 1. OMPa force is preferable, 0.2 to 0.8 MPa force is more preferable! /ヽ.
[0156] 前記加熱の少なくともいずれかを行う装置としては、特に制限はなぐ 目的に応じて 適宜選択することができ、例えば、ラミネーター (例えば、大成ラミネータネ土製 VP— I I、 -チゴ一モートン (株)製 VP130)などが好適に挙げられる。  [0156] The apparatus for performing at least one of the heating is not particularly limited, and can be appropriately selected according to the purpose. For example, a laminator (for example, Taisei Laminanee VP-II,-Chigo Morton, Inc.) Preferable examples include VP130).
[0157] 本発明の感光性フィルム及び前記感光性積層体は、前記本発明の感光性組成物 を用いるため、感度が良好で、かつ生保存性に優れ、高精細にパターンを形成可能 であるため、保護膜、層間絶縁膜、及びソルダーレジストパターン等の永久パターン 、などの各種パターン形成用、カラーフィルタ、柱材、リブ材、スぺーサ一、隔壁など の液晶構造部材の製造用、ホログラム、マイクロマシン、プルーフなどのパターン形 成用などに好適に用いることができ、特に、プリント基板の永久パターン形成用に好 適に用いることができる。  [0157] Since the photosensitive film of the present invention and the photosensitive laminate use the photosensitive composition of the present invention, the sensitivity is good, the raw storage property is excellent, and a pattern can be formed with high definition. Therefore, for the formation of various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, for the manufacture of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, etc. It can be suitably used for pattern formation of micromachines, proofs, etc., and can be particularly suitably used for permanent pattern formation of printed circuit boards.
[0158] 特に、本発明の感光性フィルムは、該フィルムの厚みが均一であるため、永久パタ ーンの形成に際し、永久パターン (保護膜、層間絶縁膜、ソルダーレジストなど)を薄 層化しても、高加速度試験 (HAST)においてイオンマイグレーションの発生がなぐ 耐熱性、耐湿性に優れた高精細な永久パターンが得られるため、基材への積層がよ り精細に行われる。  [0158] In particular, since the photosensitive film of the present invention has a uniform thickness, a permanent pattern (such as a protective film, an interlayer insulating film, or a solder resist) is formed into a thin layer when forming a permanent pattern. However, ion migration does not occur in the high acceleration test (HAST), and a high-definition permanent pattern with excellent heat resistance and moisture resistance can be obtained.
[0159] (パターン形成装置及び永久パターン形成方法）  (Pattern forming apparatus and permanent pattern forming method)
本発明のパターン形成装置は、前記感光層を備えており、光照射手段と光変調手 段とを少なくとも有する。  The pattern forming apparatus of the present invention includes the photosensitive layer and includes at least a light irradiation unit and a light modulation unit.
[0160] 本発明の永久パターン形成方法は、露光工程を少なくとも含み、更に、現像工程、 硬化処理工程等のその他の工程を含むことが好ま 、。 [0160] The permanent pattern forming method of the present invention preferably includes at least an exposure step and further includes other steps such as a development step and a curing treatment step.
なお、本発明の前記パターン形成装置は、本発明の前記永久パターン形成方法の 説明を通じて明らかにする。 [0161] <露光工程 > In addition, the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention. [0161] <Exposure process>
前記露光工程は、本発明の感光性フィルムにおける感光層に対し、露光を行うェ 程である。本発明の前記感光性フィルム、及び基材の材料については上述の通りで ある。  In the exposure step, the photosensitive layer in the photosensitive film of the present invention is exposed. The photosensitive film and the base material of the present invention are as described above.
[0162] 前記露光の対象としては、前記感光性フィルムにおける感光層である限り、特に制 限はなく、目的に応じて適宜選択することができ、例えば、上述のように、基材上に感 光性フィルムを加熱及び加圧の少なくとも ヽずれかを行!ヽながら積層して形成した積 層体に対して行われることが好ま 、。  [0162] The subject of the exposure is not particularly limited as long as it is the photosensitive layer in the photosensitive film, and can be appropriately selected depending on the purpose. It is preferable that this is performed on a laminated body formed by laminating the optical film while performing at least one of heating and pressing.
[0163] 前記露光としては、特に制限はなぐ目的に応じて適宜選択することができ、デジタ ル露光、アナログ露光等が挙げられる力 これらの中でもデジタル露光が好ましい。  [0163] The exposure can be appropriately selected according to the purpose without any particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
[0164] 前記アナログ露光としては、特に制限はなぐ目的に応じて適宜選択することができ 、例えば、所定のパターンを有するネガマスクを介して、高圧水銀灯、超高圧水銀灯 、キセノンランプなどで露光を行なう方法が挙げられる。  [0164] The analog exposure can be appropriately selected depending on the purpose without any particular limitation. For example, exposure is performed 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. A method is mentioned.
[0165] 前記デジタル露光としては、特に制限はなぐ目的に応じて適宜選択することがで き、例えば、形成するパターン形成情報に基づいて制御信号を生成し、該制御信号 に応じて変調させた光を用いて行うことが好ましぐ例えば、前記感光層に対し、光照 射手段、及び前記光照射手段からの光を受光し出射する n個（ただし、 nは 2以上の 自然数)の 2次元状に配列された描素部を有し、パターン情報に応じて前記描素部 を制御可能な光変調手段を備えた露光ヘッドであって、該露光ヘッドの走査方向に 対し、前記描素部の列方向が所定の設定傾斜角度 Θをなすように配置された露光 ヘッドを用い、前記露光ヘッドについて、使用描素部指定手段により、使用可能な前 記描素部のうち、 N重露光 (ただし、 Nは 2以上の自然数）に使用する前記描素部を 指定し、前記露光ヘッドについて、描素部制御手段により、前記使用描素部指定手 段により指定された前記描素部のみが露光に関与するように、前記描素部の制御を 行い、前記感光層に対し、前記露光ヘッドを走査方向に相対的に移動させて行う方 法が好ましい。  [0165] The digital exposure can be appropriately selected according to the purpose without any particular restriction. For example, a control signal is generated based on pattern formation information to be formed, and modulated according to the control signal. For example, it is preferable to use light. For example, n light (where n is a natural number of 2 or more) two-dimensional light receiving means and receiving light from the light irradiating means. An exposure head having light modulation means capable of controlling the drawing unit according to pattern information, the drawing unit being arranged in a scanning direction of the exposure head. The exposure head is arranged so that the column direction of the predetermined inclination angle Θ is set, and, for the exposure head, N-exposure (N double exposure) of the usable pixel parts by the used pixel part designating means. Where N is a natural number of 2 or more) Specify the element part, and control the element part of the exposure head so that only the element part specified by the used element part specifying unit is involved in the exposure by the element part control means. It is preferable that the exposure head is moved relative to the photosensitive layer in the scanning direction.
[0166] 本発明において「N重露光」とは、前記感光層の被露光面上の露光領域の略すベ ての領域において、前記露光ヘッドの走査方向に平行な直線が、前記被露光面上 に照射された N本の光点列 (画素列）と交わるような設定による露光を指す。ここで、「 光点列 (画素列）」とは、前記描素部により生成された描素単位としての光点 (画素） の並びうち、前記露光ヘッドの走査方向となす角度がより小さい方向の並びを指すも のとする。なお、前記描素部の配置は、必ずしも矩形格子状でなくてもよぐたとえば 平行四辺形状の配置等であってもよ 、。 In the present invention, “N double exposure” refers to a straight line parallel to the scanning direction of the exposure head on the exposed surface in almost all of the exposed region on the exposed surface of the photosensitive layer. Refers to exposure with a setting that intersects the N light spot rows (pixel rows) irradiated to the. 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 The arrangement of the picture element portions does not necessarily have to be a rectangular lattice, for example, an arrangement of parallelograms.
ここで、露光領域の「略すベての領域」と述べたのは、各描素部の両側縁部では、 描素部列を傾斜させたことにより、前記露光ヘッドの走査方向に平行な直線と交わる 使用描素部の描素部列の数が減るため、かかる場合に複数の露光ヘッドをつなぎ合 わせるように使用したとしても、該露光ヘッドの取付角度や配置等の誤差により、走査 方向に平行な直線と交わる使用描素部の描素部列の数がわずかに増減することが あるため、また、各使用描素部の描素部列間のつなぎの、解像度分以下のごくわず かな部分では、取付角度や描素部配置等の誤差により、走査方向と直交する方向に 沿った描素部のピッチが他の部分の描素部のピッチと厳密に一致せず、走査方向に 平行な直線と交わる使用描素部の描素部列の数が ± 1の範囲で増減することがある ためである。なお、以下の説明では、 Nが 2以上の自然数である N重露光を総称して 「多重露光」という。さらに、以下の説明では、本発明の露光装置又は露光方法を、 描画装置又は描画方法として実施した形態について、「N重露光」及び「多重露光」 に対応する用語として、「N重描画」及び「多重描画」という用語を用いるものとする。 前記 N重露光の Nとしては、 2以上の自然数であれば、特に制限はなぐ目的に応 じて適宜選択することができる力 3以上の自然数が好ましぐ 3以上 7以下の自然数 力 り好ましい。  Here, the “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 picture element parts in the used picture element part decreases, even if it is used to connect multiple exposure heads in such a case, scanning will occur due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersects a straight line parallel to the direction may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is less than the resolution. In the small part, due to errors such as the mounting angle and pixel part placement, the pixel part pitch along the direction perpendicular to the scanning direction does not exactly match the pixel part pitch of the other part, and scanning is not possible. The number of pixel parts in the used pixel part that intersects a straight line parallel to the direction increases or decreases within the range of ± 1. Because there is. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Furthermore, in the following description, “N double exposure” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” with respect to 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-exposure is a natural number of 2 or more, a force that can be appropriately selected according to the purpose for which there is no particular limitation, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .
[0167] 本発明の永久パターン形成方法に係るパターン形成装置の一例については、例え ば、特開 2006— 284842号公報の [0028]〜[0139]及び [0185]〜[0191] に記載されて ヽる手段が挙げられる。  [0167] An example of the pattern forming apparatus according to the permanent pattern forming method of the present invention is described in, for example, JP-A-2006-284842, [0028] to [0139] and [0185] to [0191]. A means of scolding is mentioned.
[0168] く現像工程 > [0168] Development process>
前記現像としては、前記感光層の未露光部分を除去することにより行われる。  The development is performed by removing an unexposed portion of the photosensitive layer.
前記未硬化領域の除去方法としては、特に制限はなぐ目的に応じて適宜選択す ることができ、例えば、現像液を用いて除去する方法などが挙げられる。 [0169] 前記現像液としては、特に制限はなぐ 目的に応じて適宜選択することができるが、 例えば、アルカリ性水溶液、水系現像液、有機溶剤などが挙げられ、これらの中でも 、弱アルカリ性の水溶液が好ましい。該弱アルカリ水溶液の塩基成分としては、例え ば、水酸化リチウム、水酸化ナトリウム、水酸ィ匕カリウム、炭酸リチウム、炭酸ナトリウム 、炭酸カリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、リン酸ナト リウム、リン酸カリウム、ピロリン酸ナトリウム、ピロリン酸カリウム、硼砂などが挙げられる The method for removing the uncured region can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a method using a developer. [0169] The developer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include an alkaline aqueous solution, an aqueous developer, an organic solvent, and the like. Among these, a weakly alkaline aqueous solution is used. preferable. Examples of the base component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and phosphoric acid. Sodium, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax, etc.
[0170] 前記弱アルカリ性の水溶液の pHは、例えば、約 8〜12が好ましぐ約 9〜： L 1がより 好ましい。前記弱アルカリ性の水溶液としては、例えば、 0. 1〜5質量％の炭酸ナトリ ゥム水溶液又は炭酸カリウム水溶液などが挙げられる。 [0170] The pH of the weakly alkaline aqueous solution is more preferably, for example, about 9 to about 8 to 12: L1. Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.
前記現像液の温度は、前記感光層の現像性に合わせて適宜選択することができる 力 例えば、約 25〜40°Cが好ましい。  The temperature of the developer is a force that can be appropriately selected according to the developability of the photosensitive layer. For example, about 25 to 40 ° C. is preferable.
[0171] 前記現像液は、界面活性剤、消泡剤、有機塩基 (例えば、エチレンジァミン、エタノ ールァミン、テトラメチルアンモ -ゥムハイドロキサイド、ジエチレントリァミン、トリェチ レンペンタミン、モルホリン、トリエタノールアミン等)や、現像を促進させるため有機溶 剤（例えば、アルコール類、ケトン類、エステル類、エーテル類、アミド類、ラタトン類 等)などと併用してもよい。また、前記現像液は、水又はアルカリ水溶液と有機溶剤を 混合した水系現像液であってもよぐ有機溶剤単独であってもよ 、。  [0171] The developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) In order to accelerate development, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination. 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.
[0172] 前記パターンの形成においては、例えば、硬化処理工程、エッチング工程、メツキ 工程などを含んでいてもよい。これらは、 1種単独で使用してもよぐ 2種以上を併用 してちよい。  [0172] The formation of the pattern may include, for example, a curing process, an etching process, a plating process, and the like. These may be used alone or in combination of two or more.
[0173] <硬化処理工程 >  [0173] <Curing treatment process>
前記パターンの形成方法が、保護膜、層間絶縁膜、ソルダーレジストパターン等の 永久パターンや、カラーフィルタの形成を行う永久パターン形成方法である場合には 、前記現像工程後に、感光層に対して硬化処理を行う硬化処理工程を備えることが 好ましい。  When the pattern forming method is a permanent pattern forming method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter, the photosensitive layer is cured after the developing step. It is preferable to provide the hardening process process which processes.
前記硬化処理工程としては、特に制限はなぐ 目的に応じて適宜選択することがで きるが、例えば、全面露光処理、全面加熱処理などが好適に挙げられる。 [0174] 前記全面露光処理の方法としては、例えば、前記現像後に、前記永久パターンが 形成された前記積層体上の全面を露光する方法が挙げられる。該全面露光により、 前記感光層を形成する感光性組成物中の榭脂の硬化が促進され、前記永久パター ンの表面が硬化される。 The curing treatment step is not particularly limited and can be appropriately selected depending on the purpose. For example, a full exposure process, a full heat treatment, and the like are preferable. [0174] Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. By this overall exposure, curing of the resin in the photosensitive composition forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
前記全面露光を行う装置としては、特に制限はなぐ目的に応じて適宜選択するこ とができる力 例えば、超高圧水銀灯などの UV露光機、キセノンランプ使用の露光 機、レーザ露光機などが好適に挙げられる。露光量は、通常 10miZcm2〜2, 000 mjz cm ある。 As the apparatus for performing the entire surface exposure, a force that can be appropriately selected according to the purpose without particular limitation.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, etc. are suitable. Can be mentioned. The exposure dose is usually 10 miZcm 2 to 2,000 mjz cm.
[0175] 前記全面加熱処理の方法としては、前記現像の後に、前記永久パターンが形成さ れた前記積層体上の全面を加熱する方法が挙げられる。該全面加熱により、前記永 久パターンの表面の膜強度が高められる。  [0175] Examples of the method of the entire surface heat treatment 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.
前記全面加熱における加熱温度は、 120〜250°Cが好ましぐ 120〜200°Cがより 好ましい。該加熱温度が 120°C未満であると、加熱処理による膜強度の向上が得ら れないことがあり、 250°Cを超えると、前記感光性組成物中の樹脂の分解が生じ、膜 質が弱く脆くなることがある。  The heating temperature in the entire surface heating is preferably 120 to 250 ° C, more preferably 120 to 200 ° C. If the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment. If the heating temperature exceeds 250 ° C, the resin in the photosensitive composition may be decomposed, resulting in film quality. May be weak and brittle.
前記全面加熱における加熱時間は、 10〜120分が好ましぐ 15〜60分がより好ま しい。  The heating time in the whole surface heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.
前記全面加熱を行う装置としては、特に制限はなぐ公知の装置の中から、目的に 応じて適宜選択することができ、例えば、ドライオーブン、ホットプレート、 IRヒーター などが挙げられる。  The apparatus for performing the entire surface heating can be appropriately selected according to the purpose from known apparatuses that are not particularly limited, and examples thereof include a dry oven, a hot plate, and an IR heater.
[0176] 前記パターンの形成方法は、 405nmのレーザ露光による直接描画において、酸素 による感光層の感度低下防止が必要とされる各種パターンの形成などに使用するこ とができ、高密度化と高生産性とを両立したパターンの形成に好適に使用することが できる。  [0176] 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 at 405 nm. It can be suitably used to form a pattern that is compatible with productivity.
[0177] 前記永久パターン形成方法においては、前記永久パターン形成方法により形成さ れる永久パターンが、前記保護膜又は前記層間絶縁膜であると、配線を外部からの 衝撃や曲げ力も保護することができ、特に、前記層間絶縁膜である場合には、例え ば、多層配線基板やビルドアップ配線基板などへの半導体や部品の高密度実装に 有用である。 [0177] 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, it is possible to protect the wiring from external impact and bending force. In particular, in the case of the interlayer insulating film, for example, for high-density mounting of semiconductors and components on a multilayer wiring board or a build-up wiring board. Useful.
[0178] 本発明の前記永久パターン形成方法は、本発明の前記感光性組成物を用いるた め、保護膜、層間絶縁膜、及びソルダーレジストパターン等の永久パターン、などの 各種パターン形成用、カラーフィルタ、柱材、リブ材、スぺーサ一、隔壁等の液晶構 造部材の製造、ホログラム、マイクロマシン、プルーフなどの製造に好適に使用するこ とができ、特に、プリント基板の永久パターン形成用に好適に使用することができる。 実施例  [0178] Since the method for forming a permanent pattern of the present invention uses the photosensitive composition of the present invention, a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern is used. It can be suitably used for the manufacture of liquid crystal structural members such as filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., especially for the formation of permanent patterns on printed circuit boards. Can be suitably used. Example
[0179] 以下、本発明の実施例について説明するが、本発明は下記実施例に何ら限定され るものではない。  [0179] Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.
[0180] (実施例 1) [0180] (Example 1)
感光性組成物の調製  Preparation of photosensitive composition
感光性組成物の調製  Preparation of photosensitive composition
各成分を下記の量で配合して、感光性組成物溶液を調製した。  Each component was mix | blended in the following quantity and the photosensitive composition solution was prepared.
〔感光性組成物溶液の各成分量〕  [Each component amount of photosensitive composition solution]
•KAYARAD ZFR— 1492H (ビスフエノール F型エポキシアタリレート、濃度 66% 日本ィ匕薬 (株)製）… 46. 8質量部 • KAYARAD ZFR— 1492H (Bisphenol F-type epoxy acrylate, concentration 66%, manufactured by Nippon Gyaku Co., Ltd.)… 46. 8 parts by mass
'ジペンタエリスリトールへキサアタリレート（重合性ィ匕合物） · · · 9質量部  'Dipentaerythritol hexaatalylate (polymerizable compound) · · · 9 parts by mass
'ィルガキュア 819 (I— 1、光重合開始剤） · · · 6質量部  'Irgacure 819 (I—1, photoinitiator) · · · 6 parts by mass
•下記構造式 (1)で表される増感剤 (S— 1) · · · 0. 5質量部  • Sensitizer (S—1) represented by the following structural formula (1) 0.5 mass part
•ェポトート ΖΧ— 1059 (熱架橋剤、東都化成社製） · · · 6質量部  • Epototo ΖΧ— 1059 (thermal crosslinking agent, manufactured by Tohto Kasei Co., Ltd.) · · · 6 parts by mass
•ェポトート ΥΡ— 50 (フエノキシ榭脂、東都化成社製） · · ·4質量部  • Epototo ΥΡ— 50 (Phenoxy resin, manufactured by Tohto Kasei) · · · 4 parts by mass
'熱硬化剤（ジシアンジアミド） · · ·0. 77質量部  'Thermosetting agent (dicyandiamide) ··· 0.77 parts by mass
'フッ素系界面活性剤 (メガファック F— 176,大日本インキ化学工業 (株)製、 30質量 %2—ブタノン溶液） · · ·0. 2質量部  'Fluorosurfactant (Megafac F-176, manufactured by Dainippon Ink and Chemicals, 30 mass% 2-butanone solution) ··· 0.2 parts by mass
'硫酸バリウム分散液 (堺化学工業社製、 Β— 30) · · · 80質量部  'Barium sulfate dispersion (manufactured by Sakai Chemical Industry Co., Ltd., Β-30) · · · 80 parts by mass
•メチルェチルケトン. . .30質量部 なお、前記硫酸バリウム分散液は、硫酸バリウム (堺ィ匕学社製、 B30) 28. 5質量部 と、 KAYARAD ZFR- 1492H (ビス F型エポキシアタリレート、濃度 66% 日本化 薬 (株）製） 15. 6質量部と、酢酸ノルマルプロピル 28. 2質量部と、フタロシア-ングリ ーン 0. 2質量部を予め混合した後、モーターミル M— 200 (アイガー社製)で、直径 1 . Ommのジルコユアビーズを用い、周速 9mZsにて 3. 5時間分散して調製した。実 施例 1における熱架橋剤の架橋基とバインダーの酸性基の割合は、熱架橋基 Z酸 性基 =0. 5/1. 0 = 0. 5である。 • Methyl ethyl ketone ... 30 parts by mass The barium sulfate dispersion is composed of 28.5 parts by weight of barium sulfate (manufactured by Zhi-Gakusha, B30) and KAYARAD ZFR-1492H (bis F-type epoxy acrylate, concentration 66% Nippon Kayaku Co., Ltd.) 15. After mixing 6 parts by mass, 28.2 parts by weight of normal propyl acetate, and 0.2 parts by weight of phthalocyanine green, the motor mill M-200 (manufactured by Eiger) was used. And then dispersed for 3.5 hours at a peripheral speed of 9 mZs. The ratio of the crosslinking group of the thermal crosslinking agent to the acidic group of the binder in Example 1 is thermal crosslinking group Z acidic group = 0.5 / 1.0 = 0.5.
[化 27]  [Chemical 27]
Figure imgf000070_0001
Figure imgf000070_0001
[0181] 感光性積層体の調製  [0181] Preparation of photosensitive laminate
次に、前記基体として、プリント基板としての配線形成済みの銅張積層板 (スルーホ ールなし、銅厚み 12 m)の表面に化学研磨処理を施して調製した。該銅張積層板 上に、前記感光性組成物をスクリーン印刷法により、 120メッシュのテトロンスクリーン を用いて、乾燥後厚みが 30 mとなるように塗布し、 80°Cで 15分間熱風循環式乾 燥機で乾燥させて感光層を形成し、前記銅張積層板と、前記感光層とがこの順に積 層された感光性積層体を調製した。  Next, as the substrate, a surface of a copper-clad laminate (no through-hole, copper thickness 12 m) on which a wiring was formed as a printed board was prepared by chemical polishing treatment. On the copper clad laminate, the photosensitive composition is applied by a screen printing method using a 120 mesh Tetron screen so that the thickness after drying is 30 m, and a hot air circulation type at 80 ° C. for 15 minutes. A photosensitive layer was formed by drying with a dryer, and a photosensitive laminate in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared.
[0182] 前記感光性積層体について、それぞれ以下の方法により、感度、解像度、保存安 定性、及びエッジラフネスの評価を行った。最短現像時間以外の結果を、表 1に示す  [0182] The photosensitive laminate was evaluated for sensitivity, resolution, storage stability, and edge roughness by the following methods. Table 1 shows the results other than the shortest development time.
[0183] <最短現像時間の評価 > [0183] <Evaluation of shortest development time>
前記銅張積層板上の前記感光層の全面に 30°Cの 1質量％炭酸ナトリウム水溶液 を 0. 15MPaの圧力にてスプレーし、炭酸ナトリウム水溶液のスプレー開始力 銅張 積層板上の感光層が溶解除去されるまでに要した時間を測定し、これを最短現像時 間とした。  Spraying the entire surface of the photosensitive layer on the copper clad laminate with a 1 mass% sodium carbonate aqueous solution at 30 ° C at a pressure of 0.15 MPa, the spray initiation force of the sodium carbonate aqueous solution. The photosensitive layer on the copper clad laminate is The time required for dissolution and removal was measured, and this was taken as the shortest development time.
なお、最短現像時間は 20秒であった。  The shortest development time was 20 seconds.
[0184] <感度の評価 > 前記調製した感光性積層体における感光層に対し、以下に説明するパターン形成 装置を用いて、 0. lruJ/cm2から 21/2倍間隔で lOOruJ/cm2までの光エネルギー 量の異なる光を照射して 2重露光し、前記感光層の一部の領域を硬化させた。室温 にて 10分間静置した後、銅張積層板上の感光層の全面に、 30°Cの 1質量％炭酸ナ トリウム水溶液をスプレー圧 0. 15MPaにて前記最短現像時間の 2倍の時間スプレ 一し、未硬化の領域を溶解除去して、残った硬化領域の厚みを測定した。次いで、 光の照射量と、硬化層の厚さとの関係をプロットして感度曲線を得た。該感度曲線か ら、硬化領域の厚みが露光前の感光層と同じ 30 mとなった時の光エネルギー量を 、感光層を硬化させるために必要な光エネルギー量とした。 [0184] <Evaluation of sensitivity> The photosensitive layer in the photosensitive laminate prepared above by using a pattern forming apparatus described below, from 0. lruJ / cm 2 until lOOruJ / cm 2 at 2 1/2 times the interval of light energy of different light 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 on the entire surface of the photosensitive layer on the copper-clad laminate at a spray pressure of 0.15 MPa, twice the minimum development time. After spraying, 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 amount of light irradiation and the thickness of the cured layer. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 m as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.
[0185] < <パターン形成装置 > > [0185] << Pattern forming device >>
前記光照射手段として特開 2005— 258431号公報に記載の合波レーザ光源と、 前記光変調手段として図 2に概略図を示した主走査方向にマイクロミラー 58が 1024 個配列されたマイクロミラー列が、副走査方向に 768組配列された内、 1024個 X 25 6列のみを駆動するように制御した DMD36と、図 1A及び図 1Bに示した光を前記感 光性フィルムに結像する光学系とを有する露光ヘッド 30を備えたパターン形成装置 10を用いた。  A combined laser light source described in JP-A-2005-258431 as the light irradiation 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 modulation means However, among the 768 pairs arranged in the sub-scanning direction, DMD36 controlled to drive only 1024 x 256 6 rows and the optical for imaging the light shown in FIGS. 1A and 1B on the photosensitive film A pattern forming apparatus 10 having an exposure head 30 having a system was used.
[0186] 各露光ヘッド 30すなわち各 DMD36の設定傾斜角度としては、使用可能な 1024 列 X 256行のマイクロミラー 58を使用してちょうど 2重露光となる角度 Θ よりも若干  [0186] The tilt angle of each exposure head 30, that is, each DMD 36, is slightly larger than the angle Θ where double exposure is performed using the available 1024 rows x 256 rows micromirror 58
ideal  ideal
大き 、角度を採用した。この角度 0  Adopted the size and angle. This angle 0
idealは、 N重露光の数 N、使用可能なマイクロミラ 一 58の列方向の個数 s、使用可能なマイクロミラー 58の列方向の間隔 p、及び露光 ヘッド 30を傾斜させた状態においてマイクロミラーによって形成される走査線のピッ チ δに対し、下記式 1、  Ideally, N is the number of double exposures N, the number of micromirrors that can be used 58 s in the row direction, the spacing p of the micromirrors 58 that can be used in the row direction p, and the micromirrors with the exposure head 30 tilted. For the pitch δ of the scanning line to be formed, the following formula 1,
spsin θ ≥Ν δ (式 1)  spsin θ ≥Ν δ (Equation 1)
iaeal  iaeal
により与えられる。本実施形態における DMD36は、上記のとおり、縦横の配置間 隔が等しい多数のマイクロミラー 58が矩形格子状に配されたものであるので、 pcos θ = δ (式 2)  Given by. As described above, the DMD 36 in the present embodiment is configured by arranging a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals in a rectangular lattice shape, so that pcos θ = δ (Equation 2)
ideal  ideal
であり、上記式 1は、  And the above equation 1 is
stan Q =N (式 3) であり、 s = 256、 N = 2であるので、角度 0 は約 0. 45度である。したがって、設 stan Q = N (Formula 3) Since s = 256 and N = 2, the angle 0 is about 0.45 degrees. Therefore,
ideal  ideal
定傾斜角度 0としては、たとえば 0. 50度を採用した。  As the constant inclination angle 0, for example, 0.50 degrees was adopted.
[0187] まず、 2重露光における解像度のばらつきと露光むらを補正するため、被露光面の 露光パターンの状態を調べた。結果を図 3に示した。図 3においては、ステージ 14を 静止させた状態で感光性フィルム 12の被露光面上に投影される、露光ヘッド 30 と [0187] First, the state of the exposure pattern on the surface to be exposed 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 exposure head 30 projected onto the exposed surface of the photosensitive film 12 with the stage 14 stationary.
12 12
30 が有する DMD36の使用可能なマイクロミラー 58からの光点群のパターンを示 30 shows the pattern of light spots from the micromirror 58 that can be used for DMD36.
21  twenty one
した。また、下段部分に、上段部分に示したような光点群のパターンが現れている状 態でステージ 14を移動させて連続露光を行った際に、被露光面上に形成される露 光パターンの状態を、露光エリア 32 と 32 について示した。なお、図 3では、説明 did. In addition, the exposure pattern formed on the exposed surface when the stage 14 is moved and continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. This is shown for exposure areas 32 and 32. In Figure 3, the explanation
12 21  12 21
の便宜のため、使用可能なマイクロミラー 58の 1列おきの露光パターンを、画素列群 Aによる露光パターンと画素列群 Bによる露光パターンとに分けて示した力 実際の 被露光面上における露光パターンは、これら 2つの露光パターンを重ね合わせたも のである。  For convenience, the exposure pattern for every other column of the micromirrors 58 that can be used is divided into the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B. The actual exposure on the exposed surface The pattern is a superposition of these two exposure patterns.
[0188] 図 3に示したとおり、露光ヘッド 30 と 30 の間の相対位置の、理想的な状態から  [0188] As shown in FIG. 3, the relative position between the exposure heads 30 and 30 from the ideal state.
12 21  12 21
のずれの結果として、画素列群 Aによる露光パターンと画素列群 Bによる露光パター ンとの双方で、露光エリア 32 と 32 の前記露光ヘッドの走査方向と直交する座標  As a result of the shift, the coordinates orthogonal to the scanning direction of the exposure head in the exposure areas 32 and 32 in both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B.
12 21  12 21
軸上で重複する露光領域にお!、て、理想的な 2重露光の状態よりも露光過多な領域 が生じていることが判る。  It can be seen that there are overexposed areas in the overlapping exposure areas on the axis than in the ideal double exposure state.
[0189] 前記光点位置検出手段としてスリット 28及び光検出器の組を用い、露光ヘッド 30 [0189] As the light spot position detecting means, a set of a slit 28 and a photodetector is used, and an exposure head 30
12 ついては露光エリア 32 内の光点 P (l， 1)と P (256， 1)の位置を、露光ヘッド 30  12, the positions of the light spots P (l, 1) and P (256, 1) in the exposure area 32
12 21 については露光エリア 32 内の光点 P (l， 1024)と P (256， 1024)の位置を検出し  For 12 21, the positions of light spots P (l, 1024) and P (256, 1024) within the exposure area 32 are detected.
21  twenty one
、それらを結ぶ直線の傾斜角度と、露光ヘッドの走査方向とがなす角度を測定した。  The angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head was measured.
[0190] 実傾斜角度 Θ 'を用いて、下記式 4 [0190] Using the actual inclination angle Θ ', the following equation 4
ttan 0 (式 4)  ttan 0 (Equation 4)
の関係を満たす値 tに最も近い自然数 Tを、露光ヘッド 30 と 30 のそれぞれについ  The natural number T that is closest to the value t that satisfies this relationship is assigned to each of the exposure heads 30 and 30.
12 21  12 21
て導出した。露光ヘッド 30 については T= 254、露光ヘッド 30 については Τ= 25  Derived. T = 254 for exposure head 30, 、 = 25 for exposure head 30
12 21  12 21
5がそれぞれ導出された。その結果、図 4において斜線で覆われた部分 78及び 80を 構成するマイクロミラーが、本露光時に使用しないマイクロミラーとして特定された。 [0191] その後、図 4において斜線で覆われた領域 78及び 80を構成する光点以外の光点 に対応するマイクロミラーに関して、同様にして図 4において斜線で覆われた領域 82 及び網掛けで覆われた領域 84を構成する光点に対応するマイクロミラーが特定され 、本露光時に使用しないマイクロミラーとして追加された。 5 were 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. [0191] Thereafter, with respect to the micromirror corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered by the oblique lines in FIG. 4, the regions 82 and shaded areas in FIG. Micromirrors corresponding to the light spots constituting the covered region 84 were identified and added as micromirrors not used during the main exposure.
これらの露光時に使用しないものとして特定されたマイクロミラーに対して、前記描 素部素制御手段により、常時オフ状態の角度に設定する信号が送られ、それらのマ イク口ミラーは、実質的に露光に関与しな 、ように制御した。  For the micromirrors identified as not used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel unit control means, and these microphone mirrors are substantially It was controlled so that it was not involved in exposure.
これにより、露光エリア 32 と 32 のうち、複数の前記露光ヘッドで形成された被露  As a result, the exposure areas formed by a plurality of the exposure heads in the exposure areas 32 and 32.
12 21  12 21
光面上の重複露光領域であるヘッド間つなぎ領域以外の各領域にお!、て、理想的 な 2重露光に対して露光過多となる領域、及び露光不足となる領域の合計面積を最 小とすることができる。  Minimize the total area of overexposed and underexposed areas for ideal double exposure in each area other than the head-to-head connection area, which is the overlapping exposure area on the optical surface. It can be.
[0192] <解像度の評価 > [0192] <Resolution evaluation>
前記最短現像時間の評価方法と同じ方法及び条件で前記感光性積層体を作製し 、室温（23°C、 55%RH)にて 10分間静置した。得られた感光性積層体の感光層上 から、前記パターン形成装置を用いて、ライン Zスペース = 1Z1でライン幅 10〜： LO 0 mまで 1 μ m刻みで各線幅の露光を行う。この際の露光量は、前記感光層を硬化 させるために必要な光エネルギー量である。室温にて 10分間静置した後、銅張積層 板上の感光層の全面に 30°Cの 1質量％炭酸ナトリウム水溶液をスプレー圧 0. 15M Paにて前記最短現像時間の 2倍の時間スプレーし、未硬化領域を溶解除去する。こ の様にして得られた硬化榭脂パターン付き銅張積層板の表面を光学顕微鏡で観察 し、硬化榭脂パターンのラインにッマリ、ョレ等の異常が無ぐかつスペース形成可能 な最小のライン幅を測定し、これを解像度とした。該解像度は数値が小さいほど良好 である。  The photosensitive laminate was produced 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 is carried out for each line width in increments of 1 μm from the line Z space = 1Z1 to the line width 10 to: LO 0 m using the pattern forming apparatus. The amount of exposure at this time is the amount of light energy necessary to cure 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 0.1MPa for twice the minimum development time. Then, the uncured region is dissolved and removed. The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope. The line width was measured and used as the resolution. The smaller the numerical value, the better the resolution.
[0193] <保存安定性の評価 1 >  [0193] <Evaluation of storage stability 1>
前記感光性積層体を 40°Cの乾燥促進条件 (相対湿度 50%)の下、 1日間保管した 。 1日後に前記と同様にして、感度及び解像度を測定し、下記基準に基づいて、経 時安定性の評価を行った。  The photosensitive laminate was stored for 1 day under drying acceleration conditions (relative humidity 50%) at 40 ° C. One day later, in the same manner as described above, sensitivity and resolution were measured, and aging stability was evaluated based on the following criteria.
〔評価基準〕 〇：感度及び解像度の変化がほとんどなぐ経時安定性に優れる。 〔Evaluation criteria〕 ◯: Excellent temporal stability with almost no change in sensitivity and resolution.
△:感度及び解像度が低下し、現像が困難となり、経時安定性に劣る。  Δ: Sensitivity and resolution decrease, development becomes difficult, and stability over time is inferior.
X：感度及び解像度が著しく低下し、経時安定性に極めて劣る、あるいは、保存 することができない。  X: Sensitivity and resolution are remarkably reduced, stability with time is extremely inferior, or storage is impossible.
[0194] <エッジラフネスの評価 >  [0194] <Evaluation of edge roughness>
前記感光性積層体に、前記パターン形成装置を用いて、前記露光ヘッドの走査方 向と直交する方向の横線パターンが形成されるように照射して 2重露光し、前記感光 層の一部の領域を前記解像度の測定と同様にしてパターンを形成した。得られたパ ターンのうち、ライン幅 50 mのラインの任意の 5箇所について、レーザ顕微鏡 (VK - 9500、キーエンス (株)製;対物レンズ 50倍）を用いて観察し、視野内のエッジ位 置のうち、最も膨らんだ箇所（山頂部)と、最もくびれた箇所 (谷底部)との差を絶対値 として求め、観察した 5箇所の平均値を算出し、これをエッジラフネスとした。該エッジ ラフネスは、値が小さい程、良好な性能を示すため好ましい。  Using the pattern forming apparatus, the photosensitive laminate is irradiated with double exposure so that a horizontal line pattern in a direction orthogonal to the scanning direction of the exposure head is formed, and a part of the photosensitive layer is exposed. A pattern was formed in the same manner as in the measurement of the resolution. Of the obtained patterns, any five points on a line with a line width of 50 m were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and the edge position in the field of view was observed. The absolute value of the difference between the most swollen part (mountain peak) and the narrowest part (valley bottom part) was calculated, and the average value of the five observed points was calculated as the edge roughness. The edge roughness is preferably as the value is small, since it exhibits good performance.
[0195] (実施例 2)  [0195] (Example 2)
感光性フィルムの製造  Production of photosensitive film
実施例 1で得られた感光性組成物溶液を、前記支持体としての厚み 16 m、幅 30 Omm、長さ 200mの PET (ポリエチレンテレフタレート）フィルム上に、バーコ一ター で塗布し、 80°C熱風循環式乾燥機中で乾燥して、厚み 30 mの感光層を形成した o次いで、該感光層の上に、保護フィルムとして、膜厚 20 μ m、幅 310mm、長さ 210 mのポリプロピレンフィルムをラミネーシヨンにより積層し、前記感光性フィルムを製造 した。  The photosensitive composition solution obtained in Example 1 was applied to a PET (polyethylene terephthalate) film having a thickness of 16 m, a width of 30 Omm, and a length of 200 m as the support with a bar coater, and 80 ° C. A photosensitive layer having a thickness of 30 m was formed by drying in a hot air circulation dryer. Next, a polypropylene film having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was formed as a protective film on the photosensitive layer. Were laminated by lamination to produce the photosensitive film.
[0196] 感光性積層体の調製  [0196] Preparation of photosensitive laminate
次に、前記基体として実施例 1と同じ銅張積層板上に、前記感光性フィルムの感光 層が前記銅張積層板に接するようにして前記感光性フィルムにおける保護フィルムを 剥がしながら、真空ラミネーター（二チゴーモートン (株)社製、 VP130)を用いて積層 させ、前記銅張積層板と、前記感光層と、前記ポリエチレンテレフタレートフィルム (支 持体)とがこの順に積層された感光性積層体を調製した。  Next, on the same copper-clad laminate as in Example 1 as the substrate, the photosensitive film of the photosensitive film is in contact with the copper-clad laminate, and the protective film on the photosensitive film is peeled off, and a vacuum laminator ( A photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) are laminated in this order. Prepared.
圧着条件は、真空引きの時間 40秒、圧着温度 70°C、圧着圧力 0. 2MPa、加圧時 間 10秒とした。 Crimping conditions are: vacuuming time 40 seconds, crimping temperature 70 ° C, crimping pressure 0.2 MPa, under pressure The interval was 10 seconds.
[0197] 前記感光性積層体にっ ヽて、感度、解像度、保存安定性、及びエッジラフネスの 評価を行った。なお、解像度、保存安定性における経時安定性 (前記保存安定性の 評価 1)、及びエッジラフネスについては、実施例 1と同様にして評価を行った。感度 については、下記のようにして評価を行った。保存安定性については、前記経時安 定性のほかにも、下記に示す方法で評価を行った。結果を表 1に示す。  [0197] The photosensitive laminate was evaluated for sensitivity, resolution, storage stability, and edge roughness. The resolution, storage stability over time (evaluation of storage stability 1), 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.
[0198] <感度の評価 >  [0198] <Evaluation of sensitivity>
前記調製した感光性積層体における感光性フィルムの感光層に対し、前記支持体 側から、実施例 1で説明したパターン形成装置により実施例 1と同様にして前記感光 層の一部の領域を硬化させた。室温にて 10分間静置した後、前記感光性積層体か ら前記支持体を剥がし取り、実施例 1と同様にして感光層を硬化させるために必要な 光エネルギー量を測定した。  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. I let you. After standing at room temperature for 10 minutes, the support was peeled from the photosensitive laminate, and the amount of light energy required to cure the photosensitive layer was measured in the same manner as in Example 1.
[0199] <保存安定性の評価 2 >  [0199] <Evaluation of storage stability 2>
前記感光性フィルムをワインダ一で巻き取り、感光性フィルム原反ロールを製造した 得られた前記感光性フィルム原反ロールを同軸スリツターにてスリットして、長さ 300 mm、内径 76mmの ABS榭脂製円筒状巻き芯に、 250mm幅で 150m巻き取り、感 光性フィルムロールを作製した。  The photosensitive film was wound up with a winder to produce a photosensitive film raw roll. The obtained photosensitive film raw roll was slit with a coaxial slitter, and was 300 mm in length and 76 mm in inner diameter. A cylindrical roll core was wound up to 150 m in a width of 250 mm to produce a photosensitive film roll.
こうして得られた前記感光性フィルムロールを、黒色ポリエチレン製の筒状袋 (膜厚 ： 80 m、水蒸気透過率： 25gZm2' 24hr以下）に包み、ポリプロピレン製ブッシュを 巻き芯の両端に押し込んだ。 The photosensitive film roll thus obtained was wrapped in a black polyethylene cylindrical bag (film thickness: 80 m, water vapor transmission rate: 25 gZm 2 '24 hr or less), and a polypropylene bush was pushed into both ends of the winding core.
前記ブッシュで両端を塞いだロール状のサンプルを 25°C、 55%RHで 21日間保 存後、端面融着の有無を観察し、下記基準で保存安定性の評価を行なった。  The roll-shaped sample with both ends closed with the bush was stored at 25 ° C and 55% RH for 21 days, and then observed for end face fusion, and the storage stability was evaluated according to the following criteria.
〔評価基準〕  〔Evaluation criteria〕
〇：端面融着が確認されず、積層体が良好に使用できる状態。  A: End face fusion is not confirmed, and the laminate can be used satisfactorily.
△：端面の一部に光沢があり、若干量の端面融着が起きて 、る状態 (使用限界)。 X：端面全面に光沢があり、端面融着が多量に発生している状態。  Δ: A part of the end face is glossy, and a slight amount of end face fusion occurs (use limit). X: State where the entire end face is glossy and a large amount of end face fusion occurs.
[0200] (実施例 3) 実施例 1にお ヽて、感光性組成物溶液中のィルガキュア 819 (1- 1,光重合開始剤 ) 6質量部を、下記構造式 (2)で表されるォキシム誘導体 (1— 2、光重合開始剤) 2質 量部に変更したこと以外は、実施例 1と同様にして、感光性組成物溶液を調製した。 該感光性組成物溶液を用いて、実施例 2と同様にして、感光性フィルムを形成し、感 光性積層体を調製した。 [0200] (Example 3) In Example 1, 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the oxime derivative (1-2, photopolymerization) represented by the following structural formula (2). Polymerization 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
[化 28]  [Chemical 28]
構造式（2)
Figure imgf000076_0001
Structural formula (2)
Figure imgf000076_0001
[0201] 前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 2に示す。  [0201] The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 2.
[0202] (実施例 4) [0202] (Example 4)
実施例 1にお ヽて、感光性組成物溶液中のィルガキュア 819 (1- 1,光重合開始剤 ) 6質量部を、下記構造式 (3)で表される化合物 (1— 3、光重合開始剤） 1質量部及 び N—フエニルダリシン (添加剤） 0. 5質量部に変更したこと以外は、実施例 1と同様 にして、感光性組成物溶液を調製した。該感光性組成物溶液を用いて、実施例 2と 同様にして、感光性フィルムを形成し、感光性積層体を調製した。  In Example 1, 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-3, photopolymerization) represented by the following structural formula (3). Initiator) 1 part by weight and N-phenyldaricin (additive) A photosensitive composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 0.5 part by weight. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
[化 29]  [Chemical 29]
〇
Figure imgf000076_0002
Yes
Figure imgf000076_0002
[0203] 前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  [0203] The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0204] (実施例 5) [0204] (Example 5)
実施例 1にお ヽて、感光性組成物溶液中のィルガキュア 819 (1- 1,光重合開始剤 ) 6質量部を、下記構造式 (4)で表される化合物 (1—4、光重合開始剤) 2質量部に変 更したこと以外は、実施例 1と同様にして、感光性組成物溶液を調製した。該感光性 組成物溶液を用いて、実施例 2と同様にして、感光性フィルムを形成し、感光性積層 体を調製した。 In Example 1, 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-4, photopolymerization) represented by the following structural formula (4). 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. Photosensitivity Using the composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
[化 30]
Figure imgf000077_0001
[Chemical 30]
Figure imgf000077_0001
[0205] 前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  [0205] The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0206] (実施例 6) [0206] (Example 6)
実施例 1にお ヽて、感光性組成物溶液中のィルガキュア 819 (1- 1,光重合開始剤 ) 6質量部を、下記構造式 (5)で表される化合物 (1— 5、光重合開始剤) 2質量部に変 更したこと以外は、実施例 1と同様にして、感光性組成物溶液を調製した。該感光性 組成物溶液を用いて、実施例 2と同様にして、感光性フィルムを形成し、感光性積層 体を調製した。  In Example 1, 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-5, photopolymerization) represented by the following structural formula (5). 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
[化 31]
Figure imgf000077_0002
[Chemical 31]
Figure imgf000077_0002
[0207] 前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  [0207] The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0208] (実施例 7) [0208] (Example 7)
実施例 1にお ヽて、感光性組成物溶液中のィルガキュア 819 (1- 1,光重合開始剤 ) 6質量部を、下記構造式 (6)で表される化合物 (1— 6、光重合開始剤) 2質量部に変 更したこと以外は、実施例 1と同様にして、感光性組成物溶液を調製した。該感光性 組成物溶液を用いて、実施例 2と同様にして、感光性フィルムを形成し、感光性積層 体を調製した。  In Example 1, 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-6, photopolymerization) represented by the following structural formula (6). 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
[化 32] 構造式 (6)[Chemical 32] Structural formula (6)
Figure imgf000078_0001
Figure imgf000078_0001
[0209] 前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  [0209] The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0210] (実施例 8) [0210] (Example 8)
実施例 1にお ヽて、感光性組成物溶液中のィルガキュア 819 (1- 1,光重合開始剤 ) 6質量部を、下記構造式 (7)で表される化合物 (1— 7、光重合開始剤) 3質量部に変 更したこと以外は、実施例 1と同様にして、感光性組成物溶液を調製した。該感光性 組成物溶液を用いて、実施例 2と同様にして、感光性フィルムを形成し、感光性積層 体を調製した。  In Example 1, 6 parts by mass of Irgacure 819 (1-1, photopolymerization initiator) in the photosensitive composition solution was added to the compound (1-7, photopolymerization) represented by the following structural formula (7). Initiator) 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 the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
[化 33]
Figure imgf000078_0002
[Chemical 33]
Figure imgf000078_0002
[0211] 前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  [0211] The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0212] (実施例 9) [0212] (Example 9)
実施例 3において、前記パターン形成装置の代わりに、これと同様なパターンを有 するガラス製ネガマスクを別途作製し、このネガマスクを感光性積層体上に接触させ て超高圧水銀灯で 40miZcm2の露光量で露光した。 In Example 3, instead of the pattern forming apparatus, a glass negative mask having a pattern similar to the above was prepared separately, and this negative mask was brought into contact with the photosensitive laminate, and an exposure amount of 40 miZcm 2 was obtained with an ultrahigh pressure mercury lamp. And exposed.
前記露光方法を用いたこと以外は、実施例 2と同様にして、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  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.
[0213] (実施例 10) [0213] (Example 10)
実施例 2において、前記式 3に基づき N= lとして設定傾斜角度 Θを算出し、前記 式 4に基づき ttan Θ ' = 1の関係を満たす値 tに最も近 、自然数 Tを導出し、 N重露 光 (N= l)を行ったこと以外は、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。 [0214] (実施例 11) In Example 2, the set inclination angle Θ is calculated with N = l based on Equation 3 above, and the natural number T is derived closest to the value t satisfying the relationship of ttan Θ ′ = 1 based on Equation 4 above. The sensitivity, resolution, storage stability 1 and 2, and edge roughness were evaluated in the same manner as in Example 2 except that exposure (N = 1) was performed. The results are shown in Table 1. [0214] (Example 11)
実施例 3にお!/、て、感光性組成物溶液中の KAYARAD ZFR— 1492H (ビスフ ェノール F型エポキシアタリレート）を、 KAYARAD ZFR— 1492Hを KAYARAD In Example 3 !, KAYARAD ZFR— 1492H (bisphenol F type epoxy acrylate) in the photosensitive composition solution and KAYARAD ZFR— 1492H in KAYARAD
ZAR- 1413H (ビスフエノール A型エポキシアタリレート、濃度 66% 日本化薬社 製）に変更したこと以外は、実施例 3と同様にして、感光性組成物溶液を調製した。 該感光性組成物溶液を用いて、実施例 2と同様にして、感光性フィルムを形成し、感 光性積層体を調製した。 A photosensitive composition solution was prepared in the same manner as in Example 3 except that ZAR-1413H (bisphenol A type epoxy acrylate, concentration 66%, manufactured by Nippon Kayaku Co., Ltd.) was used. Using this photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。なお、実施例 11 における熱架橋剤の架橋基とバインダーの酸性基の割合は、熱架橋基 Z酸性基 = 0. 5/1. 0 = 0. 5である。  The photosensitive laminate was evaluated in the same manner as in Example 2 for 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 Z acidic group = 0.5 / 1.0 = 0.5.
[0215] (実施例 12) [0215] (Example 12)
実施例 3にお!/、て、感光性組成物溶液中の KAYARAD ZFR— 1492H (ビスフ ェノール F型エポキシアタリレート）を、下記バインダー（前記一般式（2)で表される化 合物を原料としたバインダー）に変更したこと以外は、実施例 3と同様にして、感光性 組成物溶液を調製した。該感光性組成物溶液を用いて、実施例 2と同様にして、感 光性フィルムを形成し、感光性積層体を調製した。  In Example 3, KAYARAD ZFR-1492H (bisphenol F-type epoxy acrylate) in the photosensitive composition solution was used as a raw material from the following binder (compound represented by the general formula (2)). A photosensitive composition solution was prepared in the same manner as in Example 3 except that the binder composition was changed to a binder. Using the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2 to prepare a photosensitive laminate.
前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0216] バインダーの調製 [0216] Preparation of binder
ェポトート YDPF— 1000 (東都化成社製） 200質量部、アクリル酸 36質量部、メチ ルハイドロキノン 0. 2質量部、プロピレングリコールモノメチルエーテルモノアセテート 60質量部を反応容器にとり、 90°Cで攪拌することにより反応をおこなった。続いて、 内温を 60°Cまで冷却し、トリフエ-ルホスフィン 1質量部を加えて 100°Cで 3時間攪拌 した。つぎにテトラヒドロ無水フタル酸 50質量部とプロピレングリコールモノメチルエー テルモノアセテート 94質量部をカ卩え、 85°Cで 6時間攪拌し、濃度 65%のバインダー を得た。  Epototo YDPF-1000 (manufactured by Tohto Kasei) 200 parts by weight, 36 parts by weight of acrylic acid, 0.2 part by weight of methyl hydroquinone, 60 parts by weight of propylene glycol monomethyl ether monoacetate are placed in a reaction vessel and stirred at 90 ° C. The reaction was carried out. 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%.
[0217] (比較例 1) 実施例 1にお 、て、感光性組成物溶液中のィルガキュア 819 6質量部を、ィルガ キュア 907 3質量部に変更したこと以外は、実施例 1と同様にして、感光性組成物 溶液を調製し、感光性積層体を調製した。 [0217] (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 photosensitive laminate was prepared.
前記感光性積層体について、実施例 1と同様にして、感度、解像度、保存安定性 1 、及びエッジラフネスの評価を行った。結果を表 1に示す。  The photosensitive laminate was evaluated in the same manner as in Example 1 for sensitivity, resolution, storage stability 1 and edge roughness. The results are shown in Table 1.
[0218] (比較例 2) [0218] (Comparative Example 2)
比較例 1の感光性組成物溶液 (ィルガキュア 819 6質量部を、ィルガキュア 907 3質量部に変更）を用いたこと以外は、実施例 2と同様にして、感光性フィルムを形成 し、感光性積層体を調製した。  A photosensitive film was formed in the same manner as in Example 2 except that the photosensitive composition solution of Comparative Example 1 (changed from 6 parts by mass of Irgacure 819 to 3 parts by mass of Irgacure 907) was used. The body was prepared.
前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0219] (比較例 3) [0219] (Comparative Example 3)
実施例 1にお 、て、感光性組成物溶液中の KAYARAD ZFR- 1492H (ビスフ ェノール F型エポキシアタリレート）を、リポキシ PR— 300 (タレゾールノボラック型ェポ キシアタリレート、濃度 65%、昭和高分子社製）に変更したこと以外は、実施例 1と同 様にして、感光性組成物溶液を調製し、感光性積層体を調製した。  In Example 1, KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate) in the photosensitive composition solution was added to lipoxy PR-300 (taresol novolak type epoxide talate, concentration 65%, Showa A photosensitive composition solution was prepared in the same manner as in Example 1 except that the product was changed to “manufactured by Kobunshi Co., Ltd.” to prepare a photosensitive laminate.
前記感光性積層体について、実施例 1と同様にして、感度、解像度、保存安定性 1 、及びエッジラフネスの評価を行った。結果を表 1に示す。  The photosensitive laminate was evaluated in the same manner as in Example 1 for sensitivity, resolution, storage stability 1 and edge roughness. The results are shown in Table 1.
[0220] (比較例 4) [0220] (Comparative Example 4)
比較例 3の感光性組成物溶液 (KAYARAD ZFR— 1492Hを、リポキシ PR— 30 0に変更）を用いたこと以外は、実施例 2と同様にして、感光性フィルムを形成し、感 光性積層体を調製した。  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. The body was prepared.
前記感光性積層体について、実施例 2と同様にして、感度、解像度、保存安定性 1 及び 2、並びにエッジラフネスの評価を行った。結果を表 1に示す。  The photosensitive laminate was evaluated in the same manner as in Example 2 for sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 1.
[0221] [表 1] 感度 解像度 保存 保存 [0221] [Table 1] Sensitivity Resolution Save Save
(mJ/ cm ) ( U m) 安定性 1 安定性 2 ネス 実施例 1 98 45 〇 - 1.6 実施例 2 54 35 〇 〇 1.4 実施例 3 49 35 〇 〇 1.4 実施例 4 41 35 〇 〇 1.4 実施例 5 43 35 〇 〇 1.4 実施例 6 44 35 〇 〇 1.4 実施例 7 43 35 〇 〇 1.4 実施例 8 45 35 〇 〇 1.4 実施例 9 - 35 〇 〇 1.5 実施例 10 54 35 〇 〇 2.1 実施例 11 47 35 〇 〇 1.4 実施例 12 48 35 〇 〇 1.4 比較例 1 130 45 X - 1.6 比較例 2 70 35 X 〇 1.4 比較例 3 110 50 Δ - 1.6 比較例 4 65 40 Δ Δ 1.4 表 1の結果より、本発明の感光性組成物及び本発明の感光性フィルムを用いた実 施例 1〜12では、高感度で保存安定性に優れ、高解像度なパターンを形成できるこ とが半 ljつた。  (mJ / cm) (U m) Stability 1 Stability 2 Nest Example 1 98 45 ○-1.6 Example 2 54 35 ○ ○ 1.4 Example 3 49 35 ○ ○ 1.4 Example 4 41 35 ○ ○ 1.4 Example 5 43 35 ○ ○ 1.4 Example 6 44 35 ○ ○ 1.4 Example 7 43 35 ○ ○ 1.4 Example 8 45 35 ○ ○ 1.4 Example 9-35 ○ ○ 1.5 Example 10 54 35 ○ ○ 2.1 Example 11 47 35 ○ ○ 1.4 Example 12 48 35 ○ ○ 1.4 Comparative Example 1 130 45 X-1.6 Comparative Example 2 70 35 X ○ 1.4 Comparative Example 3 110 50 Δ-1.6 Comparative Example 4 65 40 Δ Δ 1.4 From the results in Table 1, In Examples 1 to 12 using the photosensitive composition of the present invention and the photosensitive film of the present invention, it was semi-lj that high sensitivity, excellent storage stability, and a high resolution pattern could be formed.
産業上の利用可能性 Industrial applicability
本発明の感光性組成物は、高感度で、生保存性及び取り扱!/、性に優れ、高精細な パターンを形成することができ、パッケージ基板を含むプリント配線基板等の製造に 好適なパターン、あるいは、半導体分野における高精細な永久パターンにおける永 久パターン (層間絶縁膜、保護膜、ソルダーレジストパターンなど)の形成用として広 く用いることができ、本発明の感光性フィルムの形成、永久パターン形成方法、プリン ト基板の形成に好適に用いることができる。  The photosensitive composition of the present invention is highly sensitive, excellent in preservability and handling properties, can form high-definition patterns, and is suitable for production of printed wiring boards including package substrates. It can be widely used for the formation of permanent patterns (interlayer insulating film, protective film, solder resist pattern, etc.) in patterns or high-definition permanent patterns in the semiconductor field. It can be suitably used for a pattern formation method and formation of a print substrate.
本発明の感光性フィルムは、本発明の感光性組成物を用いることにより、高感度で 、生保存性及び取り扱い性に優れ、高精細なパターンを形成することができ、ノ^ケ ージ基板を含むプリント配線基板等の製造に好適なパターン、あるいは、半導体分 野における高精細な永久パターンにおける永久パターン (層間絶縁膜、保護膜、ソ ルダーレジストパターンなど）の形成用として広く用いることができ、本発明の永久パ ターン形成方法、プリント基板の形成に好適に用いることができる。  By using the photosensitive composition of the present invention, the photosensitive film of the present invention can form a high-definition pattern with high sensitivity, excellent raw storage and handling properties, and a non-cage substrate. Can be widely used for forming patterns suitable for the manufacture of printed wiring boards and the like, or permanent patterns (interlayer insulating films, protective films, solder resist patterns, etc.) in high-definition permanent patterns in the semiconductor field. The permanent pattern forming method of the present invention can be suitably used for forming a printed circuit board.
本発明の永久パターン形成方法は、本発明の感光性組成物または感光性フィルム を用いることにより、高感度で、生保存性及び取り扱い性に優れ、高精細なパターン が形成できるので、パッケージ基板を含むプリント配線基板等の製造に好適なパター ン、あるいは、半導体分野における高精細な永久パターン (層間絶縁膜、保護膜、ソ ルダーレジストパターンなど）を高精細に、かつ、効率よく形成可能であるため、高精 細な露光が必要とされる各種パターンの形成などに好適に使用することができ、特に 本発明のプリント基板の形成に好適に使用することができる。 The method for forming a permanent pattern of the present invention is the photosensitive composition or photosensitive film of the present invention. By using, high-definition patterns can be formed with high sensitivity, excellent raw storage and handling, so patterns suitable for manufacturing printed circuit boards including package substrates, or high-definition in the semiconductor field Can be formed with high definition and efficiency, such as various patterns that require high-precision exposure, and can be used to form various permanent patterns (interlayer insulation film, protective film, solder resist pattern, etc.). In particular, it can be suitably used for forming the printed circuit board of the present invention.

Claims

請求の範囲 The scope of the claims
[1] (A)ビスフ ノール骨格を部分構造に有するエポキシィ匕合物 (a)と、不飽和基含有 モノカルボン酸 (b)との反応物に、飽和基及び不飽和基のいずれかを含有する多塩 基酸化合物 (c)を反応させて得られるバインダーと、（B)重合性化合物と、（C)光重 合開始剤としてァシルホスフィンォキシド化合物及びォキシム誘導体のいずれかと、 を少なくとも含むことを特徴とする感光性組成物。  [1] (A) A reaction product of an epoxy compound (a) having a bisphenol skeleton in a partial structure and an unsaturated group-containing monocarboxylic acid (b) contains either a saturated group or an unsaturated group At least a binder obtained by reacting the polybasic acid compound (c), (B) a polymerizable compound, and (C) any of an acyl phosphine oxide compound and an oxime derivative as a photopolymerization initiator. A photosensitive composition comprising the composition.
[2] (A)バインダー力 下記一般式（1)及び一般式（2)のいずれかで表されるエポキシ 化合物（a)と、不飽和基含有モノカルボン酸 (b)との反応物に、飽和基及び不飽和 基の ヽずれかを含有する多塩基酸化合物 (c)を反応させて得られる光硬化性榭脂 である請求項 1に記載の感光性組成物。  [2] (A) Binder strength A reaction product of an epoxy compound (a) represented by any one of the following general formula (1) and general formula (2) with an unsaturated group-containing monocarboxylic acid (b), 2. The photosensitive composition according to claim 1, which is a photocurable resin obtained by reacting a polybasic acid compound (c) containing either a saturated group or an unsaturated group.
[化 1] 一般式（1 )
Figure imgf000083_0001
[Chemical formula 1] General formula (1)
Figure imgf000083_0001
ただし、前記一般式（1)中、 Xは、水素原子及びグリシジル基のいずれかを表し、 R は、メチレン基及びイソプロピリデン基のいずれかを表す。 nは、 1以上の整数を表す  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
[化 2] [Chemical 2]
—般式（2)
Figure imgf000083_0002
—General formula (2)
Figure imgf000083_0002
ただし、前記一般式（2)中、 R1は、水素原子及びメチル基のいずれかを表し、 R2及 び R3は、アルキレン基を表し、 m及び nは、 m+nが 2〜50となる正の整数を表し、 p は、正の整数を表す。 However, In the general formula (2), R 1 represents a hydrogen atom or a methyl group, R 2及beauty R 3 represents an alkylene group, m and n, m + n is 2 to 50 Represents a positive integer, and p represents a positive integer.
[3] 感度が、 0. l〜200mjZcm2である請求項 1から 2のいずれかに記載の感光性組 成物。 [3] sensitive, photosensitive group composition as claimed in any one of claims 1 to 2 which is 0. l~200mjZcm 2.
[4] (D)熱架橋剤を、更に含む請求項 1から 3のいずれかに記載の感光性組成物。 [5] ォキシム誘導体が、下記一般式 (3)及び一般式 (4)の 、ずれかで表される部分構 造を有する請求項 1から 4のいずれかに記載の感光性組成物。 [4] The photosensitive composition according to any one of claims 1 to 3, further comprising (D) a thermal crosslinking agent. [5] The photosensitive composition according to any one of claims 1 to 4, wherein the oxime derivative has a partial structure represented by any of the following general formulas (3) and (4).
[化 3]  [Chemical 3]
Ar \c(Y1) = N-0-Y2) —般式（3) Ar \ c (Y 1 ) = N-0-Y 2 ) — General formula (3)
/ m  / m
[化 4]  [Chemical 4]
Ar -( cO-C(Y1 ) = N-0-Y2) —般式（4) Ar-(cO-C (Y 1 ) = N-0-Y 2 ) — General formula (4)
\ I m  \ I m
ただし、前記一般式 (3)及び (4)中、 Arは、芳香族基、及び複素環基のいずれか を表し、 Y1は、水素原子、及び一価の置換基のいずれかを表し、 Y2は、脂肪族基、 芳香族基、複素環基、 COY3, COHowever, in the general formulas (3) and (4), Ar represents either an aromatic group or a heterocyclic group, Y 1 represents any one of a hydrogen atom and a monovalent substituent, Y 2 is an aliphatic group, aromatic group, heterocyclic group, COY 3 , CO
Figure imgf000084_0001
Figure imgf000084_0001
及び Υ5は、脂肪族基、芳香族基、及び複素環基のいずれかを表し、 mは、 1以上の 整数を表す。 And 5 represents an aliphatic group, an aromatic group, or a heterocyclic group, and m represents an integer of 1 or more.
[6] (D)熱架橋剤の架橋基と (A)バインダーの酸性基との割合が、熱架橋基 Z酸性基  [6] The ratio of (D) the crosslinking group of the thermal crosslinking agent to (A) the acidic group of the binder is the thermal crosslinking group Z acidic group
=0. 3〜3. 0である請求項 4から 5のいずれかに記載の感光性組成物。  The photosensitive composition according to any one of claims 4 to 5, wherein = 0.3 to 3.0.
[7] 支持体と、該支持体上に請求項 1から 6のいずれかに記載の感光性組成物力 な る感光層と、該感光層上に保護フィルムと、を少なくとも有してなることを特徴とする感 光性フィルム。  [7] It comprises at least a support, a photosensitive layer serving as a photosensitive composition according to any one of claims 1 to 6 on the support, and a protective film on the photosensitive layer. Characteristic light sensitive film.
[8] 長尺状であり、ロール状に巻かれてなる請求項 7に記載の感光性フィルム。  [8] The photosensitive film according to [7], which is long and wound in a roll.
[9] 基体上に、請求項 1から 6のいずれかに記載の感光性組成物からなる感光層を有 することを特徴とする感光性積層体。  [9] A photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of claims 1 to 6 on a substrate.
[10] 感光層が、請求項 7から 8のいずれかに記載の感光性フィルムにより形成された請 求項 9に記載の感光性積層体。 [10] The photosensitive laminate according to claim 9, wherein the photosensitive layer is formed of the photosensitive film according to any one of claims 7 to 8.
[11] 請求項 9から 10のいずれかに記載の感光性積層体における感光層に対して、露光 を行うことを少なくとも含むことを特徴とする永久パターン形成方法。 [11] A method for forming a permanent pattern, comprising at least exposing the photosensitive layer in the photosensitive laminate according to any one of claims 9 to 10.
[12] 露光が、 350〜415nmの波長のレーザ光を用いて行われる請求項 11に記載の永 久パターン形成方法。 12. The permanent pattern forming method according to claim 11, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
[13] 請求項 11から 12のいずれかに記載の永久パターン形成方法により、永久パターン が形成されることを特徴とするプリント基板。  [13] A printed circuit board, wherein a permanent pattern is formed by the method for forming a permanent pattern according to any one of claims 11 to 12.
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JP5107231B2 (en) 2012-12-26
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