JP2007156111A - Photosensitive composition, pattern forming material, photosensitive laminate, and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition excellent in dimensional stability, a pattern forming material having a photosensitive layer formed of the photosensitive composition, a photosensitive laminate, and a pattern forming method. <P>SOLUTION: The photosensitive composition comprises at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon nano-material. The photosensitive composition is comprised in a photosensitive layer for use in formation of a two-dimensional pattern on a photosensitive layer surface to be exposed by relatively scanning an exposure head and the surface to be exposed while modulating light on the basis of pattern information, or the photosensitive composition is comprised in a photosensitive layer having a minimum energy amount of exposure of 0.1-100 mJ/cm<SP>2</SP>in which when the photosensitive layer is exposed and developed, the thickness of the photosensitive layer in a portion to be exposed does not vary after the exposure and development. There are also provided the pattern forming material having a photosensitive layer formed of the photosensitive composition, the photosensitive laminate and the pattern forming method. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive composition suitable for a dry film resist (DFR) that can be patterned by exposure, a liquid resist, and the like. In particular, pattern forming materials and photosensitive laminates using the photosensitive composition, high-definition wiring patterns, permanent patterns (protective films, interlayer insulating films, solder resist patterns, etc.), color filters, pillar materials, rib materials The present invention relates to a pattern forming method such as manufacturing of liquid crystal structural members such as spacers and partition walls, manufacturing of holograms, micromachines, and proofs.

In the field of printed wiring boards, usually, a copper wiring pattern is first formed on a copper clad laminate using DFR. Further, it is soldered onto a wiring pattern on which components such as a semiconductor, a capacitor, and a resistor are formed. In this case, for example, in a soldering process such as IR reflow, in order to prevent the solder from adhering to an unnecessary part of soldering, a permanent pattern corresponding to the unnecessary part of soldering is used as a protective film and an insulating film. The method of forming is adopted. Further, a pattern forming material such as a solder resist is used as the permanent pattern of the protective film. On the other hand, a pattern forming material such as a dry film resist that does not remain as a protective film after forming a pattern of a printed wiring board is also used (for example, see Patent Document 1 and Patent Document 2).
In general, the pattern forming material is exposed to light using a mask. However, in recent years, a digital micromirror device (DMD) or the like is used from the viewpoint of productivity, resolution, and the like. Maskless exposure equipment using conventional laser light has been actively studied.

In recent years, further miniaturization has progressed, and a pattern forming material capable of forming a fine wiring pattern is desired. The finer the pattern, the smaller the line width variation, the greater the alignment error when performing high-density patterning, so the demand for line width dimensional stability is increasing. .
In response to such demands, line width dimensional stability is improved by techniques such as scattering prevention during exposure by lowering the haze value of a polyethylene terephthalate film as a support (see, for example, Patent Document 3). However, further improvements are desired in the production of stable wiring patterns.

On the other hand, a photosensitive composition containing carbon nanotubes as a pattern forming material for a printed wiring board is disclosed (for example, see Patent Document 4). In this technique, carbon nanotubes are added for the purpose of improving antistatic properties and mechanical strength.
However, the above-mentioned problem is not mentioned, and technical development for improving the line width dimensional stability and reducing the line width roughness (edge roughness) is eagerly desired.
International Publication No. 01/071428 Pamphlet JP 2004-252421 A JP 60-262156 A JP 2005-24893 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, an object of the present invention is to provide a photosensitive composition having excellent dimensional stability, a pattern forming material having a photosensitive layer formed from the photosensitive composition, a photosensitive laminate, and a pattern forming method. To do.

Means for solving the problems are as follows. That is,
<1> The photosensitive layer which forms a two-dimensional pattern on the exposed surface by performing relative scanning between the exposure head and the exposed surface of the photosensitive layer while modulating light based on the pattern information. A photosensitive composition contained in
A photosensitive composition comprising at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial.

<2> When the photosensitive layer is exposed and developed, the minimum energy amount of exposure in which the thickness of the exposed portion of the photosensitive layer does not change after exposure and development is 0.1 mJ / cm ^{2 to} 100 mJ / cm ² . A photosensitive composition contained in the photosensitive layer,
A photosensitive composition comprising at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial.

<3> Using for exposure to form a two-dimensional pattern on the exposed surface by exposing the exposed head and the exposed surface of the photosensitive layer by relative scanning while modulating light based on the pattern information. A photosensitive composition contained in the photosensitive layer,
When the photosensitive layer is exposed and developed, the minimum energy amount of exposure that does not change the thickness of the exposed portion of the photosensitive layer after exposure and development is 0.1 mJ / cm ^{2 to} 100 mJ / cm ² ,
A photosensitive composition comprising at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial.

<4> The above-described <1> to <3>, wherein the carbon-based nanomaterial is at least one selected from the group consisting of carbon nanotubes, fullerenes, and carbon microcoils. It is the photosensitive composition of description.

<5> The photosensitive composition according to any one of <1> to <4>, which contains a sensitizer.

<6> The sensitizer is selected from the group consisting of a condensed ring compound, a compound having a disubstituted aminobenzene as a partial structure, a compound having a basic nucleus, a compound having an acidic nucleus, and a fluorescent brightener. It is a photosensitive composition as described in said <5> characterized by including at least 1 sort (s).

<7> The above-described <6>, wherein the condensed ring compound includes at least one selected from the group consisting of an acridone compound, a thioxanthone compound, a coumarin compound, and an acridine compound. It is a photosensitive composition.

<8> The above <6> or <7>, wherein the compound having a disubstituted aminobenzene as a partial structure is at least one compound represented by the following general formulas (I) to (VII): It is the photosensitive composition of description.

[In General Formula (I), R ¹ , R ² , R ⁵ , and R ⁶ each independently represent either an aliphatic group or an aromatic group, and R ³ , R ⁴ , R ⁷ , R ⁸ and R ^{9 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent. R ¹ and R ² , R ⁵ and R ⁶ , R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , and R ⁶ and R ⁸ are independently bonded to each other to form a nitrogen-containing complex. A ring may be formed. ]

[In General Formula (II), R ²¹ and R ²² each independently represent either an aliphatic group or an aromatic group, and R ^{23 to} R ³⁰ each independently represent a hydrogen atom or a monovalent group. X represents one of an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, and an imino group substituted with an aliphatic group or an aromatic group. R ²¹ and R ²² , R ²¹ and R ²³ , and R ²² and R ²⁴ may be independently bonded to each other to form a nitrogen-containing heterocyclic ring, and the benzene ring condensed to the heterocyclic ring is substituted. It may have a group. ]

[In General Formula (III), R ³¹ and R ³² each independently represent either an aliphatic group or an aromatic group, and R ^{33 to} R ³⁷ each independently represent a hydrogen atom or a monovalent group. And R ³⁸ represents a monovalent substituent. R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³⁴ may be independently bonded to each other to form a nitrogen-containing heterocycle. ]

[In General Formula (IV), R ⁴¹ and R ⁴² each independently represent either an aliphatic group or an aromatic group, and R ^{43 to} R ⁴⁷ each independently represent a hydrogen atom or a monovalent group. Y represents either an oxygen atom or NR ⁴⁸ , and R ⁴⁸ represents either a hydrogen atom or a monovalent substituent. R ⁴¹ and R ⁴² , R ⁴¹ and R ⁴³ , and R ⁴² and R ⁴⁴ may be independently bonded to each other to form a nitrogen-containing heterocycle. ]

[In General Formulas (V) to (VII), Rings A to G each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and Ring A, Ring B, and Ring D and Ring E, and Ring F and Ring G may be independently bonded to each other to form a bonded ring containing N.
In the general formula (VI), the linking group L represents a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the linking groups L and N are the aromatic hydrocarbon ring and aromatic group. And n represents any integer of 2 or more.
In the general formula (VII), R represents an alkyl group which may have a substituent.
Rings A to G and linking group L may have a substituent, and these substituents may be bonded to each other to form a ring. ]

<9> The above-mentioned <6>, wherein the compound having a basic nucleus is at least one selected from the group consisting of a cyanine dye, a hemicyanine dye, a styryl dye, and a streptocyanine dye. It is a photosensitive composition of any one of <8>.

<10> The photosensitivity according to any one of <6> to <9>, wherein the compound having an acidic nucleus is at least one selected from the group consisting of a merocyanine compound and a rhodacyanine compound empty. Composition.

<11> The photosensitive composition according to any one of <6> to <10>, wherein the optical brightener is a compound having a nonionic nucleus.

<12> The photopolymerization initiator includes a halogenated hydrocarbon derivative, hexaarylbiimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, aromatic onium salt, metallocene, and acylphosphine oxide compound. The photosensitive composition according to any one of <1> to <11>, wherein the photosensitive composition is at least one radical generator selected from the group.

<13> The photosensitive composition according to any one of <1> to <12>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group. .

<14> The photosensitive composition according to any one of <1> to <12>, wherein the polymerizable compound is a monomer having at least one of an ethylene oxide group and a propylene oxide group. It is.

<15> The <1> to <14>, wherein the binder includes a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative. It is a photosensitive composition as described in above.

<16> The photosensitive composition according to any one of <1> to <15>, wherein the binder has a glass transition temperature (Tg) of 80 ° C. or higher.

<17> The photosensitive composition according to any one of <1> to <16>, wherein the binder has an acid value of 70 to 250 (mgKOH / g).

<18> including a thermal crosslinking agent,
<1>, wherein the binder contains at least one of an epoxy acrylate compound and at least one of a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. It is a photosensitive composition of any one of-<17>.

<19> including a thermal crosslinking agent,
<1>, wherein the binder is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to an anhydride group of a maleic anhydride copolymer. It is the photosensitive composition in any one of-<18>.

<20> including a thermal crosslinking agent,
And the binder is (a) maleic anhydride, (b) an aromatic vinyl monomer, (c) a vinyl monomer, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is <1 which is obtained by reacting 0.1 to 1.0 equivalent of a primary amine compound to an anhydride group of a copolymer comprising a vinyl monomer having a temperature of less than 80 ° C. The photosensitive composition according to any one of> to <19>.

<21> The thermal crosslinking agent is
<18> to <<1>, wherein the compound is at least one selected from the group consisting of 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. 20>. The photosensitive composition according to any one of 20>.

<22> The photosensitive composition according to <21>, wherein the epoxy compound is an epoxy compound in which a β-position is substituted with an alkyl group.

<23> The photosensitive composition according to <21> or <22>, wherein the melamine derivative is an alkylated methylol melamine.

<24> 30 to 90% by mass of a binder, 5 to 60% by mass of a polymerizable compound, and 0.1 to 30% by mass of a photopolymerization initiator. 23>. The photosensitive composition according to any one of 23>.

<25> A pattern forming material comprising a support and a photosensitive layer containing the photosensitive composition according to any one of <1> to <24> above provided on the support. .

<26> The pattern forming material according to <25>, wherein a cushion layer and a photosensitive layer are provided on a support in order from the side close to the support.

<27> The pattern forming material according to <25> or <26>, wherein the support includes a synthetic resin and is transparent.

<28> The pattern forming material according to any one of <25> to <27>, wherein the support has a long shape.

<29> The pattern forming material according to any one of <25> to <28>, which is long and wound in a roll shape.

<30> The pattern forming material according to any one of <25> to <29>, wherein a protective film is provided on the photosensitive layer.

<31> A photosensitive laminate comprising a substrate and a photosensitive layer containing the photosensitive composition according to any one of <1> to <24>.

<32> The photosensitive laminate according to <31>, wherein the photosensitive layer is formed of the pattern forming material according to any one of <25> to <30>. .

<33> The photosensitive laminate according to <31> or <32>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<34> A pattern forming method comprising at least an exposure step of exposing the photosensitive layer of the photosensitive laminate according to any one of <31> to <33>.

<35> After the photosensitive layer in the pattern forming material according to any one of <25> to <30> is laminated on the surface of the substrate under at least one of heating and pressing, the photosensitive layer The pattern forming method according to <34>, wherein the pattern is exposed to light.

<36> The pattern forming method according to <34> or <35>, wherein in the exposure step, exposure is performed with a laser beam having a wavelength of 350 to 415 nm.

<37> The pattern forming method according to any one of <34> to <36>, wherein in the exposure step, imagewise exposure is performed based on pattern information to be formed.

<38> In the exposure step, the photosensitive layer is arranged in a two-dimensional array of n (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means and the light irradiation means. An exposure head having a picture element portion and provided with a light modulation means capable of controlling the picture element portion according to pattern information, wherein the column direction of the picture element portion is predetermined with respect to the scanning direction of the exposure head Using an exposure head arranged to form a set inclination angle θ of
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The pattern forming method according to any one of <34> to <37>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction.

  In the pattern forming method according to <38>, the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part designating unit. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.

<39> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the joint area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. <38> The pattern forming method according to <38>, 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 pattern forming method according to the above <39>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the head-to-head connection area, the picture element part used for realizing the N-fold exposure in the head-to-head connection area is designated, so that the mounting position and attachment of the exposure head are specified. Variations in resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the angle deviation are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.

<40> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The pattern formation according to <38> or <39>, wherein the pixel part used to realize N double exposure in an area other than the inter-head connection area among the picture element parts is designated. Is the method.

  In the pattern forming method according to the above <40>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure other than the inter-head connection area, the attachment position of the exposure head is specified by designating the picture element part used for realizing the N-fold exposure in the areas other than the inter-head connection area. Variations in the resolution and density unevenness of the pattern formed in areas other than the head-to-head connection area on the exposed surface of the photosensitive layer due to the mounting angle deviation are equalized. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.

<41> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel portions in the column direction, the interval p in the column direction of the pixel portions, and the exposure head tilted. to the column direction of the pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, to be set so as to satisfy the relation theta ≧ theta _ideal The pattern forming method according to any one of <38> to <40>, which is characterized in that

<42> The pattern forming method according to any one of <38> to <41>, wherein N in N-fold exposure is a natural number of 3 or more.

  In the pattern forming method according to the above <42>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<43> Use pixel part designation means
A light spot position detecting means for detecting a light spot position on a surface to be exposed as a pixel unit generated by a picture element unit and constituting an exposure area on the surface to be exposed;
<38> to <42>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. The pattern forming method according to any one of the above items.

<44> Any one of the above <38> to <43>, wherein the used picture element part specifying means designates the use picture element part used for realizing the N double exposure in line units. The pattern forming method described in 1.

<45> The light spot position detecting means, based on the detected at least two light spot positions, the light spot column direction on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. <43> wherein the inclination angle θ ′ is specified, and the drawing element selection means selects the drawing element part so as to absorb an error between the actual inclination angle θ ′ and the set inclination angle θ. Or it is the pattern formation method as described in <44>.

<46> 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 pattern forming method according to <45>, wherein the pattern forming method is any one of a maximum value and a minimum value.

<47> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <45, wherein the pixel part from the first line to the T-th line is selected as a used pixel part in a line element (where m represents a natural number of 2 or more). > Or <46>.

<48> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part from line (T + 1) to m-th line is specified as an unused picture element part, and the unused picture element part is specified. The pattern forming method according to any one of <45> to <47>, wherein the pixel part excluding the element part is selected as a use pixel part.

<49> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part rows, the pixel part selection unit,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) Ideal It is one of means for selecting a pixel part to be used so that the area of an underexposed area is minimized and an overexposed area does not occur with respect to typical N double exposure. It is a pattern formation method of any one of said <43>-<48>.

<50> In the connection region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The pattern forming method according to any one of <43> to <49>, wherein the pattern forming method is any one of the above.

<51> The pattern forming method according to <50>, wherein the unused pixel parts are specified in units of rows.

<52> In order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, N (n-1) pixel part columns for N multiple exposures The pattern forming method according to any one of <38> to <51>, wherein the reference exposure is performed using only the picture element portion that constitutes the element.

  In the pattern forming method according to the above <52>, in order to specify the used pixel part in the used pixel part specifying unit, out of the usable pixel parts, -1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<53> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, for each N-exposure N, a pixel part line is formed every 1 / N lines. The pattern forming method according to any one of <38> to <52>, wherein the reference exposure is performed using only the picture element portion.

  In the pattern forming method according to the above <53>, in order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, 1 / N of N double exposure Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<54> The above-mentioned <38> used pixel portion 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 portion selecting means. It is a pattern formation method of any one of>-<53>.

<55> The pattern forming method according to any one of <38> to <54>, wherein N in N-exposure is a natural number of 3 or more and 7 or less.

<56> The <38> to <38>, wherein the pattern information is converted so that a dimension of a predetermined part of the pattern represented by the pattern information matches a dimension of a corresponding part that can be realized by the designated used pixel part. <55> The pattern forming method according to any one of the above.

<57> The pattern forming method according to any one of <34> to <56>, further including a development step of developing the photosensitive layer after the exposure step.

<58> The pattern forming method according to <57>, further comprising at least one of an etching treatment step and a plating treatment step after the development step.

<59> The pattern forming method according to <58>, wherein a wiring pattern is formed.

<60> The pattern forming method according to <57>, further including a curing treatment step of performing a curing treatment on the photosensitive layer after the development step.

<61> The pattern forming method as described in <60>, wherein the curing treatment step is at least one of whole surface exposure or whole surface heating performed at 120 to 200 ° C.

  In the pattern forming method according to the above <61>, curing of the resin in the photosensitive composition is promoted in the overall exposure process. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.

<62> The pattern forming method according to <61>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed on the photoreceptor laminate.

  ADVANTAGE OF THE INVENTION According to this invention, the conventional problem can be solved, the photosensitive composition excellent in dimensional stability, the pattern formation material which has the photosensitive layer formed with this photosensitive composition, a photosensitive laminated body, and a pattern A forming method can be provided.

  The present invention is a photosensitive composition, a pattern forming material obtained by laminating a photosensitive layer made of the photosensitive composition, a photosensitive laminate, and a pattern forming method, which will be described below in order.

(Photosensitive composition)
The photosensitive composition of the present invention includes at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial.
The photosensitive composition of the present invention is a two-dimensional pattern on the surface to be exposed by exposing the exposure head and the surface to be exposed of the photosensitive layer to relative scanning while modulating light based on pattern information. When the photosensitive layer is exposed and developed, the minimum energy amount of exposure that does not change the thickness of the exposed portion of the photosensitive layer after exposure and development is 0.1 mJ. / Cm ^{2 to} 100 mJ / cm ² of the photosensitive layer.

Preferably, the minimum energy amount is 0.1 to 40 mJ / cm ² , and more preferably 0.5 to 30 mJ / cm ² .
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 100 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes. A method for setting the minimum energy amount within the above range will be described in the description of each component of the photosensitive composition.

Here, “the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development” is so-called development sensitivity, for example, when the photosensitive layer is exposed. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure and the thickness of the cured layer generated by the development process following the exposure.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the thickness of the cured layer and the thickness of the photosensitive layer before the exposure are within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring machine (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

The study by the present inventors has revealed that when the photosensitive composition of the present invention is used, the sensitivity fluctuation is small even when the exposure is performed while changing the environmental temperature. That is, when the exposure amount is the same, the photosensitive composition of the present invention has a smaller variation in the line width dimension of the pattern than the conventional photosensitive composition.
Although this mechanism has not been clarified, the photosensitive composition of the present invention contains a carbon-based nanomaterial, so that the specific heat increases and it is less susceptible to external environmental factors such as environmental temperature fluctuations. I guess it.

  In particular, when forming a two-dimensional pattern on the exposed surface by performing relative scanning between the exposure head and the exposed surface of the photosensitive layer while modulating light based on the pattern information, the exposure is performed. Since the apparatus includes a plurality of exposure laser spots, the laser spot diameter on the photosensitive composition varies due to lens manufacturing accuracy, lens attachment errors, and the like. As described above, in the photosensitive layer that forms a two-dimensional pattern on the exposed surface by performing relative scanning between the exposure head and the exposed surface of the photosensitive layer while performing light modulation based on the pattern information. However, the exposed pattern, for example, the line width may vary, and the variation is likely to become larger due to the influence of the environmental temperature. However, when the photosensitive composition of the present invention is contained in the photosensitive layer, it becomes difficult to be affected by external environmental factors such as fluctuations in environmental temperature, so that the variation in line width is reduced and good results can be obtained.

In addition, in a photosensitive layer having a minimum exposure energy amount of 0.1 mJ / cm ^{2 to} 100 mJ / cm ² in which the thickness of the exposed portion of the photosensitive layer does not change after exposure and development, exposure is performed at a low exposure energy. As a result, the power of the exposure machine is susceptible to fluctuations and line width variations are likely to occur. However, when the photosensitive composition of the present invention is contained in the photosensitive layer, it becomes difficult to be affected by external environmental factors such as fluctuations in environmental temperature, so that the variation in line width is reduced and good results can be obtained.

As the photosensitive composition, a photosensitive composition as a circuit forming resist used when forming a wiring pattern or the like, and a permanent pattern such as a protective film, an interlayer insulating film, or a solder resist pattern are used. And a photosensitive composition as a solder resist.
In the following, the composition will be described in detail by taking a circuit forming resist as an example of a wiring pattern, and the composition will be described in detail by taking a solder resist as an example of a permanent pattern, but the photosensitive composition of the present invention is used for forming a circuit. It is not limited to resist or solder resist.

[Circuit forming resist]
The photosensitive composition as the circuit forming resist includes at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial, and other components appropriately selected such as a sensitizer as necessary. including.

<Carbon-based nanomaterials>
In the present invention, the carbon-based nanomaterial refers to a nano-sized substance composed of carbon atoms, and examples thereof include carbon nanotubes, fullerenes, and carbon microcoils. The structural features and physical properties of carbon-based nanomaterials are detailed in “Latest Carbon Black Technology Encyclopedia” (published by Technical Information Church). Among these, carbon nanotubes are preferable from the viewpoint of ease of changing thermal characteristics and physical characteristics.
A carbon type nanomaterial may be used by single type, or may use multiple types together.

  The carbon nanotube is a cylindrical hollow fiber material in which the tube portion is made of carbon atoms. In general, the outer diameter is about 1 to 100 nm, the length is more than 100 times the diameter, and the cylindrical surface is composed of a hexagonal lattice of graphite. Carbon nanotubes have various three-dimensional structures depending on how the cylinder is wound, and metal nanotubes and semiconductor nanotubes exist due to such three-dimensional structures.

  The shape of the carbon nanotube that can be applied to the present invention is not particularly limited, and the cylindrical layer may be a single-wall nanotube or a multi-wall nanotube. The end of the single-walled nanotube may be closed or open.

  A known method can be appropriately applied as a method for producing the carbon nanotube. In general, the method for producing carbon nanotubes can include a method in which graphite is made apart at a high temperature and a method in which only carbon is collected by pyrolyzing a substance containing carbon. Typical examples of the former method include an arc discharge method and a laser ablation method, and the latter method includes a chemical vapor synthesis method. The generated sample contains unnecessary amorphous carbon and fullerene as impurities. Since these are easily oxidized, it is preferable to purify the sample by baking or boiling in an oxidizing agent.

  Depending on the production method, carbon nanotubes are high aspect ratio materials, and the produced carbon nanotubes often have a complex intertwined structure. These may be dispersed by ultrasonic dispersion or the like, but it is also preferable to perform a pulverization process under predetermined conditions to process the carbon nanotubes shorter than when they are generated. The pulverization method is not limited, and dry pulverization methods such as shearing and grinding, water containing a dispersant and a surfactant, and a method of dispersing in an organic solvent containing a dispersant are employed.

  In order to make the length of the carbon nanotube about 1 μm, it is preferable to maintain a temperature of 1000 ° C. for about 1 millisecond. Further, it is preferable to apply a metal catalyst that forms an alloy with carbon such as Fe, Ni, Co, and Pd.

  For details of other carbon nanotubes, refer to “Basics and Applications of Carbon Nanotubes” (Riichiro Saito, Hissunori Shinohara), Baifukan (2004).

Examples of easily available carbon nanotubes include, for example, Graphite Fibrils · Grades BN (manufactured by Hyperion Catalysis International), Carbolex-AP (manufacturer: Carbolex Inc., distributor: Wako Pure Chemical Industries, Ltd.), Manufacturing method: laser method), SCI-SWNT (manufacturer: Strem Chemicals Inc., distributor: Wako Pure Chemical Industries, Ltd., manufacturing method: arc method), ROS-SWNT (manufacturer: Rossetter Holding Ltd., manufacturing method: Arc method), CNI-SWNT (manufacturer: Carbon Nanotech. Inc., manufacturing method: HiPco method), and the like.
Others, Bucky USA (USA), Carbon Solutions (USA), Guangzhou Yorkpoint Energy (China), Hyperion Catalysis (USA), Iljin Nanotech (Korea), Materials & Electrochemical Research Corp (USA), Mitsui Carbon Nano Corporation Manufactured by Institute (Japan), NanoCarbolab (Russia), Nanos (USA), Nanolab (USA), Nanoledge (France), Rosetta Holding (Cyprus), Showa Denko Inorganic Materials (Japan), Sun Nanotech (China), etc. Can be mentioned.

Examples of fullerene that can be applied to the present invention include C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C _{82, and the} like, and these may be used alone or in combination of two or more. A known method can be appropriately applied as a method for producing fullerene. For details on fullerenes, see “Fullerenes and Carbon Nanotubes” (published by Dia Research Martech Inc.).

The carbon microcoil is made of carbon, for example, having a fiber diameter of 0.01 to 2 μm, a coil outer diameter of 2 to 10 times the fiber diameter, and 5 / coil outer diameter (μm) to 50 / per 10 μm. It is a coiled fiber having a coil outer diameter (μm).
The carbon microcoil is obtained by a gas phase decomposition reaction of a carbon-containing gas.

The content of the carbon-based nanomaterial in the photosensitive composition as the circuit forming resist is preferably 0.0001% by mass to 10% by mass, and 0.0005% by mass with respect to the entire photosensitive composition. More preferably, it is -5 mass%, and it is still more preferable that it is 0.001 mass%-1 mass%.
If the content is less than 0.0001% by mass, it tends to be affected by external environmental factors such as fluctuations in environmental temperature, and the variation in line width may increase. On the contrary, the scattering of light increases and the variation in line width may increase.

  Since the carbon-based nanomaterial is preferably uniformly dispersed in the formed photosensitive layer, the dispersion of the carbon-based nanomaterial may be separately prepared and mixed with the photosensitive composition as a resist. preferable. Further, a carbon-based nanomaterial may be added to the photosensitive composition and then dispersed. As a carbon nanomaterial dispersion method, a carbon-based nanomaterial or a solution containing a carbon-based nanomaterial may be subjected to microwave treatment or plasma treatment in advance, bead mill dispersion, high-pressure wet dispersion, ultrasonic dispersion, Disperse using a kneader. The details of the dispersion are described in detail in “The Complete Collection of Distributed Technologies” (published by Information Association Co., Ltd.).

  Further, the carbon-based nanomaterial in the photosensitive layer may be oriented by an electric field, a magnetic field or the like.

<Binder>
As a binder in the photosensitive composition as a resist for circuit formation, for example, it is preferably swellable with an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. A vinyl copolymer having a carboxyl group is preferable from the viewpoint of solubility, suitability for synthesis, ease of adjustment of film properties, and the like. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes (eg styrene, styrene derivatives, etc.), (meth) acrylonitrile, complex substituted with vinyl groups Cyclic groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate ( 2-Acryllo Ciethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), vinyl monomers having a functional group (for example, urethane group, urea group, sulfonamide group, phenol group, imide group) and the like. Among these, the styrenes (styrene and styrene derivatives) are preferable in that a permanent pattern such as a wiring pattern can be formed with high definition and the tent property can be improved.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

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

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

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

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

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

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

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

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

  Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, specifically, a monomer having an isocyanate group and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

However, in the structural formulas (1) to (3), R ^1a represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

  Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).

However, in the structural formulas (4) to (12), R ^1b represents a hydrogen atom or a methyl group, and n, n1, and n2 each independently represents any integer of 1 or more.

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

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

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

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

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

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a mass mean molecular weight, 4,000-150 1,000 is more preferable.
When the mass average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. Examples of the case where two or more binders are used in combination include, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  In addition, as the binder, a resin soluble in an alkaline liquid described in Japanese Patent No. 2873890 can be used.

There is no restriction | limiting in particular as content of the said binder in the said photosensitive composition, Although it can select suitably according to the objective, For example, 10-90 mass% is preferable, and 20-80 mass% is more preferable, 40-80 mass% is especially preferable.
When the content is less than 10% by mass, alkali developability and adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. Stability and strength of the cured film (tent film) may be reduced. The content may be the total content of the binder and the polymer binder used in combination as necessary.

<Polymerizable compound>
There is no restriction | limiting in particular as a polymeric compound, Although it can select suitably according to the objective, For example, the monomer or oligomer which has at least any one of a urethane group (urethane bond) and an aryl group is mentioned suitably. Moreover, it is preferable that these have 2 or more types of polymeric groups.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.) and a polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable.

(1) Monomer having a urethane group The monomer having a urethane group as a polymerizable compound is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. -41708, JP-A-51-37193, JP-B-5-50737, JP-B-7-7208, JP-A-2001-154346, JP-A-2001-356476, and the like. Examples thereof include adducts of a polyisocyanate compound having two or more isocyanate groups and a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, A diisocyanate such as 3,3′dimethyl-4,4′-diphenyl diisocyanate; a polyaddition product of the diisocyanate with a bifunctional alcohol (in this case, both ends are isocyanate groups); a burette or isocyanurate of the diisocyanate; Trimer; the diisocyanate or diisocyanates and trimethylolpropane, pe Taeritoritoru, polyfunctional alcohols such as glycerin, or the like adducts of other functional alcohol obtained of such these ethylene oxide adducts and the like.

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene. Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate , Tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Chryrate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane Examples include di (meth) acrylate and pentaerythritol tri (meth) acrylate. Moreover, the one terminal (meth) acrylate body of the diol body which has different alkylene oxide parts, such as a copolymer (random, a block, etc.) of ethylene oxide and propylene oxide, etc. are mentioned.

  In addition, examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Is mentioned. Among these, the compound represented by the following structural formula (13) or the structural formula (14) is preferable, and it is particularly preferable that at least the compound represented by the structural formula (14) is included from the viewpoint of tent properties. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together.

In the structural formulas (13) and (14), R ^{1c to} R ^3c each independently represents a hydrogen atom or a methyl group. X _{1c to} X _3c represent an alkylene oxide, and may be used alone or in combination of two or more.

  Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

  In the structural formulas (13) and (14), m1 to m3 each independently represents an integer of 1 to 60, preferably 2 to 30, and more preferably 4 to 15.

In the structural formulas (13) and (14), Y ^1c and Y ^2c each independently represent a divalent organic group having 2 to 30 carbon atoms, such as an alkylene group, an arylene group, an alkenylene group, or an alkynylene group. , A carbonyl group (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a hydrogen atom of the imino group substituted with a monovalent hydrocarbon group Preferred examples include imino group, sulfonyl group (—SO ₂ —) or a combination thereof, and among these, an alkylene group, an arylene group, or a combination thereof is preferable.

  The alkylene group may have a branched structure or a cyclic structure, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, trimethyl hexene. Preferable examples include a xylene group, a cyclohexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, a dodecylene group, an octadecylene group, or any of the groups shown below.

  The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and the groups shown below.

  Examples of the group in which these are combined include a xylylene group.

  The alkylene group, arylene group, or a combination thereof may further have a substituent. Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine). Atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, , Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

  In Structural Formula (14), n represents any integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of raw material supply capability for synthesizing a polymerizable monomer.

In the structural formula (14), Z ^c represents a linking group of n-valent (trivalent to hexavalent), for example, such as any of the groups shown below.

However, ^X4c represents an alkylene oxide. m4 represents any integer of 1-20. n represents an integer of 3 to 6. A represents an n-valent (trivalent to hexavalent) organic group.

  Examples of A include an n-valent aliphatic group, an n-valent aromatic group, and an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group, an oxygen atom, a sulfur atom, an imino group, and an imino group. Are preferably a combination of a substituted imino group in which the hydrogen atom is substituted with a monovalent hydrocarbon group or a sulfonyl group, an n-valent aliphatic group, an n-valent aromatic group, or an alkylene group or arylene A group in which a group and an oxygen atom are combined is more preferable, and a group in which an n-valent aliphatic group or an n-valent aliphatic group is combined with an alkylene group and / or an oxygen atom is particularly preferable.

  The number of carbon atoms of A is, for example, preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and particularly preferably an integer of 3 to 30.

The n-valent aliphatic group may have a branched structure or a cyclic structure.
As the number of carbon atoms of the aliphatic group, for example, an integer of 1 to 30 is preferable, an integer of 1 to 20 is more preferable, and an integer of 3 to 10 is particularly preferable.
The number of carbon atoms of the aromatic group is preferably an integer of 6 to 100, more preferably an integer of 6 to 50, and particularly preferably an integer of 6 to 30.

  The n-valent aliphatic group or aromatic group may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group ( Examples thereof include an acetoxy group, a butyryloxy group), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), and the like.

The alkylene group as A may have a branched structure or a cyclic structure.
The number of carbon atoms of the alkylene group is, for example, preferably an integer of 1 to 18, and more preferably an integer of 1 to 10.

The arylene group as A may be further substituted with a hydrocarbon group.
As the number of carbon atoms of the arylene group, any integer of 6 to 18 is preferable, and any integer of 6 to 10 is more preferable.

  The number of carbon atoms of the monovalent hydrocarbon group of the substituted imino group as A is preferably an integer of 1 to 18, and more preferably an integer of 1 to 10.

  Preferred examples of A are as follows.

In the (14), a plurality of the following functional groups for coupling to the Z ^c may each be the same or different.

  Examples of the compounds represented by the structural formulas (13) and (14) include compounds represented by the following structural formulas (15) to (34).

  However, in the structural formulas (15) to (34), n, n1, n2 and m each independently represent an integer of 1 to 60, and l is independently any of 1 to 20 Represents an integer, and R represents a hydrogen atom or a methyl group.

(2) Monomer having an aryl group The monomer having an aryl group as a polymerizable compound is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. And an ester or amide of an unsaturated carboxylic acid with at least one of a polyhydric alcohol compound, a polyhydric amine compound and a polyhydric amino alcohol compound.

  Examples of the polyhydric alcohol compound, polyamine compound or polyhydric amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1, 2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5,6-tetra Methyl-p-xylene-α, α′-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4- Diol, 1,1′-bi-2-naphthol, dihydroxynaphthalene, 1,1′-methylene-di-2-naphth 1,2,4-benzenetriol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methyl hydroquinone, methylene-2,4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α -(1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone and the like can be mentioned. In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolac epoxy resin and bisphenol A diglycidyl ether, phthalic acid, trimellitic acid, etc. Esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, cationically polymerizable divinyl ethers (for example, bisphenol A divinyl ether), epoxy as a polymerizable monomer Compound (for example, novolac type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl ester (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, etc.), styrene Compounds such as divinylbenzene, p-allylstyrene, p-isopropenestyrene, and the like. Among these, a compound represented by the following structural formula (35) is preferable.

In the structural formula (35), R ^4c and R ^5c each independently represent a hydrogen atom or an alkyl group.

In the structural formula (35), X ^5c and X ^6c represent an alkylene oxide group, which may be used alone or in combination of two or more. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, a group in which these are combined (which may be combined in any of random and block), Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a group combining these is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

  In the structural formula (35), m5 and m6 are each independently preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15. preferable.

In the structural formula (35), T ^c represents a divalent linking group, and examples thereof include methylene, ethylene, CH ₃ CCCH ₃ , CF ₃ CCF ₃ , CO, and SO ₂ .

In the structural formula (35), Ar ₁ and Ar ₂ each independently represent an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.

  Specific examples of the monomer having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth)). (Acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethoxy groups substituted with one phenolic OH group (For example, 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4-((Meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecae) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (e.g. 2,2-bis (2) having 2 to 20 ethoxy groups substituted with one phenolic OH group 4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxy) Pentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) pheny ) Propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, or the like, or both the polyethylene oxide skeleton and the polypropylene oxide skeleton in the same molecule as the polyether moiety Compounds (for example, compounds described in WO01 / 98832 etc., or commercially available products, Shin-Nakamura Chemical Co., Ltd., BPE-200, BPE-500, BPE-1000), bisphenol skeleton and urethane group Examples thereof include a polymerizable compound. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F or bisphenol S.

  Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include an isocyanate group and a polymerizable group in a compound having a hydroxyl group at the terminal obtained as an adduct such as bisphenol and ethylene oxide or propylene oxide, or a polyaddition product. Examples thereof include compounds (for example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.).

(3) Other polymerizable monomer In the photosensitive composition of the present invention, a polymerizable monomer other than the monomer containing the urethane group and the monomer having an aryl group is added as long as the characteristics as the pattern forming material are not deteriorated. You may use together.

  Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) And an ester of an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound.

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified Neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ) Ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-bentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Rate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate A di (meth) acrylate of an alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, a compound described in WO01 / 98832), at least one of ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate Relate and xylenol di (meth) acrylate.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meta) from the viewpoint of easy availability. ) Acrylate, di (meth) acrylate of alkylene glycol chain each having at least one ethylene glycol chain / propylene glycol chain, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, penta Erythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (Meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1, Preference is given to 5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate added with ethylene oxide, and the like.

  Examples of the ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of the ester (crotonate ester) of the crotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Can be mentioned.

  Examples of the ester of the isocrotonic acid and the aliphatic polyhydric alcohol compound (isocrotonate ester) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

  Examples of the ester of maleic acid and the aliphatic polyhydric alcohol compound (maleic acid ester) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis ( And (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, and diethylenetriamine bis (meth) acrylamide.

  In addition to the above, as the polymerizable monomer, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compound obtained by adding α, β-unsaturated carboxylic acid to glycidyl group-containing compound such as hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, Polyester acrylate and polyester (meth) acrylate as described in JP-B-6183, JP-B-49-43191 and JP-B-52-30490. Rate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) and (meth) acrylic acid, polyfunctional acrylates and methacrylates such as epoxy acrylates, Vol. 20, no. 7, photocurable monomers and oligomers described in pages 300 to 308 (1984), allyl esters (for example, diallyl phthalate, diallyl adipate, diallyl malonate, diallylamide (eg diallylacetamide, etc.), cationic polymerizable Divinyl ethers such as butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, penta Erythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (for example, butanediol-1,4-diglycidyl ester) Ter, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc. ), Oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene), epoxy compounds, oxetanes (for example, compounds described in WO01 / 22165), N-β -Hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, allyl methacrylate Different ethylenically unsaturated double bond to a compound having two or more of over preparative like, and the like.

  Examples of the vinyl esters include divinyl succinate and divinyl adipate.

  These polyfunctional monomers or oligomers may be used alone or in combination of two or more.

If necessary, the polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.
Examples of the monofunctional monomer include the compounds exemplified as the raw material of the binder, and the dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031. Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., compounds described in Japanese Patent No. 2744443, WO00 / 52529 pamphlet, Japanese Patent No. 2548016, etc. Is mentioned.

As content of the polymeric compound in the said photosensitive composition, 5-90 mass% is preferable, 15-60 mass% is more preferable, 20-50 mass% is especially preferable.
When the content is less than 5% by mass, the strength of the tent film may be reduced. When the content exceeds 90% by mass, edge fusion during storage of the pattern forming material (a bleed-out failure from the end of the roll) May get worse.
Moreover, as content of the polyfunctional monomer which has 2 or more of the said polymeric groups, 5-100 mass% is preferable with respect to all the polymeric compounds, 20-100 mass% is more preferable, 40-100 mass% Is particularly preferred.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. For example, the photopolymerization initiator has some action with the photosensitized sensitizer. A radical generator that generates and generates active radicals, and an initiator that initiates cationic polymerization according to the type of monomer may be included.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazole, oxime derivatives, organic peroxides, thio compounds, Examples include ketone compounds, aromatic onium salts, metallocenes, and acylphosphine oxide compounds. Among these, halogenated hydrocarbons having a triazine skeleton, oxime derivatives, ketone compounds, hexaarylbiimidazoles from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate. System compounds are preferred.

  Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (3-methoxyphenyl) ) Biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4-methoxyphenyl) -4 , 4 ', , 5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-Trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, compounds described in WO00 / 52529 pamphlet, and the like.

  The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

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

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

  Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.

  Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

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

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

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

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

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

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

  As an oxime derivative used suitably by this invention, the compound represented by the following specific example compound (1)-(34) is mentioned, for example.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  Examples of the metallocenes include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5- Cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. Examples thereof include compounds described in the specification of 3615455.

  Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO. Etc.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbi (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 , Coumarin compounds described in JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) Acid n-butyl, 4-dimethylaminobenzoic acid phenetic acid 4-dimethylaminobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4- Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl- 4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecyl Amines, aminofluorans (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, and the like.

  Further, vicinal polyketaldonyl compounds described in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512 are described. An aromatic acyloin compound substituted with α-hydrocarbon, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, an organoboron compound described in JP-A-2002-229194, and a radical Generator, triarylsulfonium salt (for example, salt with hexafluoroantimony or hexafluorophosphate), phosphonium salt compound (for example, (phenylthiophenyl) diphenylsulfonium salt, etc.) (effective as a cationic polymerization initiator), WO01 / 71428 Onion A salt compounds.

  The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. Examples of the combination of two or more include, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl- Combinations of s-triazine compounds, combinations of aromatic ketone compounds (such as thioxanthone) and hydrogen donors (such as dialkylamino-containing compounds and phenol compounds), combinations of hexaarylbiimidazole and titanocene, and coumarins And combinations of titanocene and phenylglycines.

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

<Sensitizer>
In the photosensitive composition of this invention, a sensitizer can be used suitably according to the wavelength used for the exposure for pattern formation. The sensitizer is used for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in the exposure of the photosensitive layer described later, or when exposing and developing the photosensitive layer, the thickness of the exposed portion of the photosensitive layer is adjusted. It is added from the viewpoint of improving the minimum energy (sensitivity) of the light that is not changed before and after. A sensitizer is excited by active energy rays and interacts with other substances (for example, radical generators, acid generators, etc.) (for example, energy transfer, electron transfer, etc.), thereby causing radicals, acids, etc. It is possible to generate useful groups.
Moreover, after exposing and developing the photosensitive layer containing the photosensitive composition, the minimum energy amount of exposure that does not change the thickness of the exposed portion of the photosensitive layer is 0.1 mJ / cm ^{2 to} 100 mJ / cm ^2. In order to do so, it is preferable to adjust the kind and addition amount of a sensitizer.

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

  For example, when the light irradiation means is combined with a 350 to 415 nm laser, the maximum absorption wavelength of the sensitizer is preferably 500 nm or less, more preferably 480 nm or less, and particularly preferably 450 nm or less.

As content of the said sensitizer, 0.01-4 mass% is preferable with respect to all the components of the photosensitive resin composition for pattern formation materials, 0.02-2 mass% is more preferable, 0.05- 1% by mass is particularly preferred.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when the content exceeds 4% by mass, the shape of the pattern may be deteriorated.

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers according to the exposure wavelength to be used. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene) ), Xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazine (Eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones ( For example, an anthro Non), squalium (for example, squalium), acridone (for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2-chloro-10-butylacrylic) Don, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 '-Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-me Xycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 7-dipropoxycoumarin, etc.), and thioxanthone compounds (thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.) and the like, and others such as JP-A-5-19475. And JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, and the like. Among these , A condensed ring compound, a compound having a disubstituted aminobenzene as a partial structure, a compound having a basic nucleus, a compound having an acidic nucleus, and at least one selected from the group consisting of fluorescent brighteners. .

(1) Compound having di-substituted aminobenzene as a partial structure As a sensitizer, the compound having di-substituted aminobenzene as a partial structure is a sensitizer having an absorption maximum with respect to light in the wavelength range of 330 to 450 nm. Preferably, for example, a disubstituted aminobenzophenone compound, a disubstituted aminobenzene compound <1> having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, A di-substituted aminobenzene compound <2> having a substituent containing a sulfonylimino group at the carbon atom in the para position with respect to the amino group, and a di-substituted aminobenzene compound <3> having a carbostyryl skeleton, and Examples thereof include compounds having a structure in which at least two aromatic rings are bonded to a nitrogen atom.
By using a compound having a di-substituted aminobenzene as a partial structure, for example, the sensitivity of the photosensitive layer can be very easily adjusted to 0.1 to 100 mJ / cm ² .

-Disubstituted aminobenzophenone compounds-
As the di-substituted aminobenzophenone compound, a compound represented by the following general formula (I) is preferable.

In the general formula ^{(I), R 1, R} 2, R 5, and ^{R 6} each independently represent any one of an aliphatic group and an aromatic ^{group, R 3, R 4, R} 7 , R ⁸ , and R ^{9 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent. R ¹ and R ² , R ⁵ and R ⁶ , R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , and R ⁶ and R ⁸ are independently bonded to each other to form a nitrogen-containing complex. A ring may be formed.

  In the general formula (I), the aliphatic group represents an alkyl group, an alkenyl group, or an alkynyl group that may have a substituent, and the aromatic group has a substituent. Represents an aryl group or a heterocyclic (heterocyclic) group, and the monovalent substituent may be a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, or a thiol group. , A thioether group, a silyl group, a nitro group, a cyano group, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, each of which may have a substituent.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic oxo group in the above-mentioned substituted phosphono group. As a specific example, the above-described monoalkylphosphono group (—PO ₃ H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

  Of the compounds represented by the general formula (I), a compound represented by the following general formula (I ′) is particularly preferred.

In general formula (I ′), R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} each independently represent R ³ , R ⁴ , R ⁷ , R ⁸ , and It has the same meaning as R ⁹ to R ^12, and preferred ranges are also the same. More preferably, R ^{1 ′} and R ^{2 ′} are each independently a hydroxyl group or an alkyl group, and more preferably a hydroxyl group and an alkyl group having 1 to 18 carbon atoms. R ^{3 ′} and R ^{4 ′} are preferably an alkoxy group, and more preferably an alkoxy group having 1 to 18 carbon atoms.
In general formula (I ′), k, l, m and n each independently represent an integer of 0 to 8, and more preferably an integer of 0 to 6.

  Specific examples of the compound represented by the general formula (I) include, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and structural formulas shown below. And the like.

-Disubstituted aminobenzene compound <1>-
As the di-substituted aminobenzene compound having a heterocyclic group as a substituent at a para carbon atom relative to the amino group on the benzene ring, the heterocyclic group contains a nitrogen atom, an oxygen atom, or a sulfur atom. What is a 5-membered ring or a 6-membered ring is preferable, and the 5-membered ring which has a condensed benzene ring is more preferable, for example, the compound represented by the following general formula (II) is mentioned.

However, in said general formula (II), R <^21> and R < ²² > respectively independently represents either an aliphatic group and an aromatic group, and R < ²³ > -R < ³⁰ > respectively independently represents a hydrogen atom and X represents any of monovalent substituents, and X represents any of an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, and an imino group substituted with an aliphatic group or an aromatic group. R ²¹ and R ²² , R ²¹ and R ²³ , and R ²² and R ²⁴ may be independently bonded to each other to form a nitrogen-containing heterocyclic ring, and the benzene ring condensed to the heterocyclic ring is substituted. It may have a group.

  In the general formula (II), examples of the aliphatic group, the aromatic group, and the monovalent substituent include those shown as examples in the general formula (I).

  Specific examples of the compound represented by the general formula (II) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl). ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole, and Include compounds represented by the structural formula shown below.

  On the other hand, among disubstituted aminobenzene compounds having a heterocyclic group as a substituent at a carbon atom para to the amino group on the benzene ring, compounds other than the compound represented by the general formula (II) For example, 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p- Dimethylaminophenyl) pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-diethylaminophenyl)- 1,3,4-thiadiazole and the like can be mentioned.

-Disubstituted aminobenzene compound <2>-
As the di-substituted aminobenzene compound having a substituent containing a sulfonylimino group at the para-position carbon atom with respect to the amino group on the benzene ring, for example, a compound represented by the following general formula (III) is preferable.

However, in said general formula (III), R <^31> and R ^<32 > respectively independently represents either an aliphatic group or an aromatic group, R < ³³ > -R < ³⁷ > respectively independently represents a hydrogen atom and represents any monovalent substituent, R ³⁸ represents a monovalent substituent. R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³⁴ may be independently bonded to each other to form a nitrogen-containing heterocycle.

In the general formula (III), examples of the aliphatic group, the aromatic group, and the monovalent substituent include those shown as examples in the general formula (I).
R ³⁸ is preferably a substituted or unsubstituted aryl group, and more preferably a substituted or unsubstituted phenyl group.

  Specific examples of the compound represented by the general formula (III) include compounds represented by the structural formulas shown below.

-Disubstituted aminobenzene compound <3>-
As the disubstituted aminobenzene compound having the carbostyryl skeleton, for example, a compound represented by the following general formula (IV) is preferable.

However, the general formula ^{(IV), R 41} and ^{R 42} each independently represent any one of an aliphatic group and an aromatic ^group, R 43 ^{to R 47} are each independently a hydrogen atom, and A monovalent substituent is represented, Y represents an oxygen atom or NR ⁴⁸ , and R ⁴⁸ represents a hydrogen atom or a monovalent substituent. R ⁴¹ and R ⁴² , R ⁴¹ and R ⁴³ , and R ⁴² and R ⁴⁴ may each independently form a nitrogen-containing heterocycle.

  In the general formula (IV), examples of the aliphatic group, the aromatic group, and the monovalent substituent include those shown as examples in the general formula (I).

  Specific examples of the compound represented by the general formula (IV) include, for example, compounds described in JP-A No. 2004-221958, coumarin compounds (for example, coumarin-1, coumarin-152, coumarin-307, coumarin- 106, Coumarin-340, etc.).

  Among the compounds having a di-substituted aminobenzene represented by the general formulas (I) to (IV) as a partial structure, the compounds represented by the general formulas (I), (III) and (IV) are preferable.

-A compound having a structure in which at least two aromatic rings are bonded to a nitrogen atom-
The compound having a disubstituted aminobenzene as a partial structure is also preferably a compound having a structure in which at least two aromatic rings are bonded to a nitrogen atom. Examples of such a compound include the following general formula (V): A compound having a structure in which at least two aromatic rings represented by (VII) are bonded to a nitrogen atom is more preferable.

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

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

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

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

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

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

However, in said formula (a) and (b), m represents one or more integers.

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

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

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

Examples of the optional substituent that the rings A to G and the linking group L may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a nitro group; a cyano group; a monovalent organic group, and the like. Examples of the monovalent organic group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, a linear or branched alkyl group having 1 to 18 carbon atoms such as n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group A cycloalkyl group having 3 to 18 carbon atoms such as a straight chain or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cyclopentenyl A cycloalkenyl group having 3 to 18 carbon atoms such as a cyclohexenyl group; a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an amyloxy group , A tert-amyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, a tert-octyloxy group, etc., a linear or branched alkoxy group having 1 to 18 carbon atoms; a methylthio group, an ethylthio group , N-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, amylthio group, tert-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, tert -C1-C18 linear or branched alkyl such as octylthio group Thio group; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; vinyloxy group, propenyloxy group, hexenyloxy Table with -COR ^51; alkenylthio group linear or branched 2 to 18 carbon atoms such as vinylthio group, propenylthio group, hexenyl thio group; a straight-chain or branched alkenyloxy group having 2 to 18 carbon atoms group Carboxyl group; acyloxy group represented by —OCOR ⁵² ; amino group represented by —NR ⁵³ R ⁵⁴ ; acylamino group represented by —NHCOR ⁵⁵ ; carbamate group represented by —NHCOOR ⁵⁶ ; A carbamoyl group represented by —CONR ⁵⁷ R ⁵⁸ ; a carboxylic acid ester group represented by —COOR ⁵⁹ ; A sulfamoyl group represented by ₃ NR ⁶⁰ R ⁶¹ ; a sulfonic acid ester group represented by —SO ₃ R ⁶² ; a group represented by —C═NR ⁶³ ; and a —C═N—NR ⁶⁴ R ⁶⁵ Groups: saturated or unsaturated heterocyclic groups such as 2-thienyl group, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group, etc. Can be mentioned.

R ^{51 to} R ⁶⁵ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. Represents a group. In these substituent groups, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, alkylthio group, aryl group, aralkyl group, alkenyloxy group, and alkenylthio group are further substituted with a substituent. May be.

There are no particular restrictions on the substitution positions of these substituents in the rings A to G and the linking group L, and when there are a plurality of substituents, these may be the same or different. Also good.
Rings A to G and linking group L are unsubstituted or substituted as a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituted group. An alkenyl group which may be substituted, an aryl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, an alkenyloxy group which may be substituted, an alkenylthio which may be substituted Group, optionally substituted amino group, optionally substituted acyl group, carboxyl group, group represented by —C═NR ⁶³ , group represented by —C═N—NR ⁶⁴ R ⁶⁵ , saturated Alternatively, it is preferably substituted with an unsaturated heterocyclic group. In the case of having a substituent, examples of the substituent include a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, and an optionally substituted group. A good alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted amino group, a group represented by —C═NR ⁶³ , —C═N—NR ⁶⁴ R; A group represented by ⁶⁵ , a saturated or unsaturated heterocyclic group is preferred.

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

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

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

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

(2) Condensed compound As the sensitizer, hetero-condensed ketone compounds (acridone compounds, thioxanthone compounds, etc.) and acridine compounds are more preferable among the condensed compounds. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

--Acridone compound--
The acridone compound is preferably a compound represented by the following general formula (VIII).

In the general formula (VIII), R ^1d , R ^2d , R ^3d , R ^4d , R ^5d , R ^6d , R ^7d , and R ^8d are each independently any of a hydrogen atom and a monovalent substituent. R ^9d represents either an aliphatic group or an aromatic group.
Further, groups adjacent to each other may be bonded to form a ring.

  In the general formula (VIII), as the monovalent substituent, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, a trifluoromethyl group, a benzyl group, a sulfopropyl group, Diethylaminoethyl group, cyanopropyl group, adamantyl group, p-chlorophenethyl group, ethoxyethyl group, ethylthioethyl group, phenoxyethyl group, carbamoylethyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminoethyl group, etc.) Alkenyl group (for example, allyl group, styryl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-carboxyphenyl group, 3,5-dicarboxyphenyl group, m-sulfophenyl group, p-acetamidophenyl group) 3-caprylamidophenyl group, p-sulfa Ylphenyl group, m-hydroxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-anisyl group, o-anisyl group, p-cyanophenyl group, pN-methylureidophenyl group, m- Fluorophenyl group, p-tolyl group, m-tolyl group, etc.), heterocyclic group (eg, pyridyl group, 5-methyl-2-pyridyl group, thienyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, Fluorine atom, etc.), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, nitro group, alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-phenylethoxy) Group), aryloxy group (for example, phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, α- Naphthoxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), acylamino group (eg acetylamino group, caproylamino group etc.), sulfonyl group (eg methanesulfonyl group, benzenesulfonyl group etc.), sulfonyl Amino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), amino group (eg, diethylamino group, hydroxyamino group, etc.), alkylthio group or arylthio group (eg, methylthio group, carboxyethyl group, sulfobutylthio group) , Phenylthio group and the like), alkoxycarbonyl group (for example, methoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group and the like), and the like. These may further have a substituent.

In the general formula (VIII), R ^9d is preferably an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an acyl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, or an aryloxycarbonyl group. An aryl group, an alkenyl group, and an acyl group are particularly preferable. These may further have a substituent.

  Specific examples of the acridone compounds include N-methylacridone, 1-chloro-N-methylacridone, 1-bromo-N-methylacridone, 2-chloro-N-methylacridone, 3- Chlor-N-methylacridone, 4-chloro-N-methylacridone, 2-chloro-N- (2-phenoxyethyl) acridone, 3-chloro-N- (n-butyl) acridone, 2,3-dichloro -N-methylacridone, 2,6-dichloro-N-methylacridone, 2-chloro-6-bromo-N-methylacridone, 2-chloro-N-ethylacridone, 2-chloro-N- ( n-butyl) acridone, 2,6-dichloro-N- (n-butyl) acridone, 2,7-dichloro-N- (n-butyl) acridone, 2,7-dibromo-N- (n-butyl) a Lidon, 2-bromo-N-octylacridone, 2-chloro-N-allylacridone, 3-chloro-N-benzylacridone, 2,3-diethoxy-N- (n-butyl) acridone, 2-phenyl -N- (n-butyl) acridone, 2-ethoxycarbonyl-N- (n-butyl) acridone, N-phenylacridone, 2-phenoxycarbonyl-N- (n-butyl) acridone, 2-cyano-N- (N-butyl) acridone, 2-methylsulfonyl-N- (n-butyl) acridone, 2,7-bis (ethoxycarbonyl) -N- (n-butyl) acridone, N- (n-butyl) -1, 2-benzacridone, N- (n-butyl) -2,3-benzacridone, acridone, 2- (N, N-diethylamino) -N′-ethylacridone, 3, 6-bis (N, N-diethylamino) -N′-ethylacridone, 2-phenoxycarbonyl-N- (2-methoxyethyl) acridone, 2,4,5,7-tetrachloro-N-methylacridone, N-ethoxycarbonylmethylacridone, 3-trifluoromethyl-N- (n-hexyl) acridone, 4,5-dichloroacridone, N- (n-butyl) -3,4-benzacridone, 2-benzoyl -N- (n-hexyl) acridone, 2-phenoxy-N- (2-hydroxyethyl) acridone, 2-phenylthio-N-ethylacridone, 2-chloro-N-propargylacridone, 3-hydroxycarbonyl-N -(N-butyl) acridone, 2,3-bis (phenoxycarbonyl) -N- (n-butyl) acridone, 2,4,5, 7-tetrabromo-N-methylacridone, N-methylthioacridone, Nn-butylthioacridone, Nn-butyl-2-methoxythioacridone, Nn-butyl-2-chlorothioacridone N-butyl-2,7-dichlorothioacridone, N-ethyl-3-diethylaminothioacridone, Nn-butyl-2-benzoylthioacridone, N- (n-butyl) -1, 2-benzothioacridone, N- (2-diethylaminoethyl) -2-bromothioacridone, N-methyl-2,3-diethoxythioacridone, 10-n-butyl-9,10-dihydroacridine- 9-ylidene-ethylamine, 10-n-hexyl-9,10-dihydroacridine-9-ylidene-benzylamine, 10- (2-methoxyethyl) -9 10-dihydroacridine-9-ylidene-n-butylamine, 10-ethyl-2-benzoyl-9,10-dihydroacridine-9-ylidene-ethoxyamine, 10-n-butyl-2-methyl-9,10-dihydro Acridine-9-ylidene-aniline, 10-n-hexyl-3-chloro-9,10-dihydroacridine-9-ylidene-propanoylamide, 10-ethyl-9,10-dihydroacridine-9-ylidene-benzoyloxy Amine, 10-methyl-9,10-dihydroacridine-9-ylidene-p-toluenesulfonyloxyamine, 10-ethyl-2-phenoxycarbonyl-9,10-dihydroacridine-9-ylidene-phenylcarbamoyloxyamine, 10 -Phenyl-9,10-dihydroacridi 9-ylidene - it is like is suitably ethoxycarbonyloxy amines, among these, 2-chloro-N-(n-butyl) acridone and N- methyl acridone and the like more preferably

--Thioxanthone compound--
The thioxanthone compound is preferably a compound represented by the following general formula (IX).

In the general formula (IX), R ^1e , R ^2e , R ^3e , R ^4e , R ^5e , R ^6e , R ^7e , and R ^8e have the same ^{meanings as} R ^{1d to} R ^8d in the general formula (VIII). .
Specific examples of the thioxanthone compound include isopropylthioxanthone and 1-chloro-4-propyloxythioxanthone.

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

(3) Compound having basic nucleus As a sensitizer, the compound having a basic nucleus is not particularly limited as long as it is a compound having a basic nucleus. It can be selected appropriately according to the optical laser or the like. By using a compound having a basic nucleus, for example, the sensitivity of the photosensitive layer can be very easily adjusted to 0.1 to 100 mJ / cm ² .

Examples of the compound having a basic nucleus include cyanine dyes, hemicyanine dyes, styryl dyes, streptocyanine dyes, and the like. Each of the dyes includes bis-type, tris-type, and polymer-type dyes. Among these, cyanine dyes, hemicyanine dyes, and styryl dyes are preferable, and cyanine dyes and hemicyanine dyes are more preferable.
When the compound having a basic nucleus is a cyanine dye, the number of methine groups is preferably 1, and in the case of a hemicyanine dye, the number of methine groups is preferably 5 or less. Further, in the case of a styryl dye and having an aniline mother nucleus, the number of methine chains is preferably 4 or less.

  The basic nucleus is, for example, James, “The Theory of the Photographic Process”, 4th edition, Macmillan Publishing Company, 1977, Chapter 8. US Pat. Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862, and 4, defined by “sensitizing dye and desensitizing dye”. No. 002,480, No. 4,925,777, JP-A-3-167546, and the like.

As the basic nucleus, for example, a benzoxazole nucleus, a benzothiazole nucleus and an indolenine nucleus are preferable.
The basic nucleus is preferably a basic nucleus substituted with an aromatic group or a basic nucleus condensed with three or more rings.
Here, the number of condensed rings of the basic nucleus is, for example, 2 for the benzoxazole nucleus and 3 for the naphthoxazole nucleus. Even if the benzoxazole nucleus is substituted with a phenyl group, the number of condensed rings is 2. The basic nucleus condensed with three or more rings may be any polycyclic condensed heterocyclic basic nucleus condensed with three or more rings, but preferably a tricyclic condensed heterocyclic ring and 4 Examples thereof include cyclic condensed heterocyclic rings.

  Examples of the tricyclic condensed heterocyclic ring include naphtho [2,3-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, and naphtho [2,3-d. ] Thiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,1-d ] Imidazole, naphtho [2,3-d] selenazole, naphtho [1,2-d] selenazole, naphtho [2,1-d] selenazole, indolo [5,6-d] oxazole, indolo [6,5-d ] Oxazole, indolo [2,3-d] oxazole, indolo [5,6-d] thiazole, indolo [6,5-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6 d] oxazole, benzofuro [6,5-d] oxazole, benzofuro [2,3-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [6,5-d] thiazole, benzofuro [2,3- d] thiazole, benzothieno [5,6-d] oxazole, benzothieno [6,5-d] oxazole, benzothieno [2,3-d] oxazole and the like.

  Examples of the tetracyclic condensed ring heterocycle include anthra [2,3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,1-d] oxazole, and anthra [2,3. -D] thiazole, anthra [1,2-d] thiazole, phenanthro [2,1-d] thiazole, phenanthro [2,3-d] imidazole, anthra [1,2-d] imidazole, anthra [2,1 -D] imidazole, anthra [2,3-d] selenazole, phenanthro [1,2-d] selenazole, phenanthro [2,1-d] selenazole, carbazolo [2,3-d] oxazole, carbazolo [3,2 -D] oxazole, dibenzofuro [2,3-d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thio Sol, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, benzofuro [5,6-d] oxazole, dibenzothieno [2,3-d] Oxazole, dibenzothieno [3,2-d] oxazole, tetrahydrocarbazolo [6,7-d] oxazole, tetrahydrocarbazolo [7,6-d] oxazole, dibenzothieno [2,3-d] thiazole, dibenzothieno [3 2-d] thiazole, tetrahydrocarbazolo [6,7-d] thiazole and the like.

  More preferably, the basic nucleus condensed with three or more rings is naphtho [2,3-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3- d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [2,3- d] oxazole, indolo [5,6-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5-d] oxazole, benzofuro [2,3- d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6-d] oxazole, anthra [2,3-d Oxazole, anthra [1,2-d] oxazole, anthra [2,3-d] thiazole, anthra [1,2-d] thiazole, carbazolo [2,3-d] oxazole, carbazolo [3,2-d] Oxazole, dibenzofuro [2,3-d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] Thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3-d] oxazole, dibenzothieno [3,2-d] oxazole, and particularly preferably naphtho [2,3-d] oxazole, Naphtho [1,2-d] oxazole, naphtho [2,3-d] thiazole, indolo [5,6-d] oxazo , Indolo [6,5-d] oxazole, indolo [5,6-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [2,3-d] Thiazole, benzothieno [5,6-d] oxazole, carbazolo [2,3-d] oxazole, carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d] oxazole, dibenzofuro [3,2-d] Oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3-d] Oxazole and dibenzothieno [3,2-d] oxazole.

  Examples of the basic nucleus include basic heterocyclic rings shown below.

Here, in specific examples of the basic heterocyclic ring, each R independently represents a hydrogen atom, an aliphatic group, or an aromatic group.

Specific examples of the compound having a basic nucleus include a compound represented by the following structural formula (36). The compound having a basic nucleus is a hemicyanine dye compound and has a function of spectrally sensitizing a radical generator. Therefore, when ultraviolet to visible light corresponding to the absorption of the compound having the basic nucleus is irradiated, radical generation from the radical generator is promoted even when a radical generator having no absorption is contained in this region. can do.
As the said Hemishinian based dye compound, via a Y ^f moiety in the following structural formula (36), bis-type, it may be a tris-type, or polymer-type dyes.

In the structural formula (36), R _1f represents an aliphatic group or an aromatic group. When R _1f represents an aliphatic group, examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable.

  The aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

In the structural formula (36), examples of the alkyl group represented by R _1f include linear, branched, and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, 1-20 are more preferable. The preferred range of the number of carbon atoms in the alkyl part of the substituted alkyl group is the same as in the case of the alkyl group. Further, the alkyl group may be an alkyl group having a substituent or an unsubstituted alkyl group.

In the structural formula (36), the alkyl group represented by R _1f includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and a dodecyl group. , Octadecyl group, cyclohexyl group, cyclopentyl group, neopentyl group, isopropyl group, isobutyl group and the like.

In the structural formula (36), examples of the substituent of the substituted alkyl group represented by R _1f include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, An alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), an alkylsulfonylaminocarbonyl group, arylsulfonylaminocarbonyl group, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group having 30 or less carbon atoms, An acylaminosulfonyl group having 30 or less carbon atoms, an alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), an alkylthio group having 30 or less carbon atoms (for example, Methylthio group, ethylthio Group, methylthioethylthioethyl group, etc.), aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl having 30 or less carbon atoms Group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl) Group), carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, Morpholinosulfonyl group, piperidinosulfonyl Etc.), an aryl group having 30 or less carbon atoms (eg, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (eg, amino group, alkylamino group, dialkylamino group) Arylamino group, diarylamino group, acylamino group, etc.), substituted ureido group, substituted phosphono group, heterocyclic group and the like. Here, the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in a salt state. At that time, examples of the cation forming the salt include G ⁺ described later.

In Structural Formula (36), examples of the alkenyl group represented by R _1f include linear, branched, and cyclic alkenyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 30. 2 to 20 are more preferable. The alkenyl group may be a substituted alkenyl group having a substituent or an unsubstituted alkenyl group, and the preferred range of the number of carbon atoms in the alkenyl part of the substituted alkenyl group is the same as that of the alkenyl group. . Examples of the substituent of the substituted alkenyl group include the same substituents as those of the substituted alkyl group.

In Structural Formula (36), examples of the alkynyl group represented by R _1f include linear, branched, and cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2 to 30. 2 to 20 are more preferable. The alkynyl group may be a substituted alkynyl group having a substituent or an unsubstituted alkynyl group, and the preferred range of the number of carbon atoms in the alkynyl part of the substituted alkynyl group is the same as in the case of the alkynyl group. . Examples of the substituent for the substituted alkynyl group include the same substituents as those for the substituted alkyl group.

In the structural formula (36), examples of the aralkyl group represented by R _1f include linear, branched, and cyclic aralkyl groups. The number of carbon atoms of the aralkyl group is 7 to 35. 7-25 are more preferable. The aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group, and the preferred range of the number of carbon atoms in the aralkyl part of the substituted aralkyl group is the same as in the case of the aralkyl group. . Examples of the substituent for the substituted aralkyl group include the same substituents as those for the substituted alkyl group.

In Structural Formula (36), when R _1f represents an aromatic group, examples of the aromatic group include an aryl group and a substituted aryl group. As a carbon atom number of an aryl group, 6-30 are preferable and 6-20 are more preferable. The preferred range of the number of carbon atoms in the aryl part of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group represented by R _1f include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. Examples of the substituent for the substituted aryl group include the same substituents as those for the substituted alkyl group.

In the structural formula (36), L _1f and L _2f each independently represent a methine group which may have a substituent, and when L _1f and L _2f represent a methine group having a substituent, A substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring.

  Examples of the substituent of the methine group include a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an acylamino group, etc.), a substituted oxy group (for example, a hydroxy group, Alkoxy groups, acyloxy groups, aryloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, etc.), substituted mercapto groups (eg, alkyl mercapto groups, aryl mercapto groups, etc.), halogen atoms, aliphatic groups, aromatic groups Can be mentioned.

Examples of the halogen atom which is a substituent of the methine group include a fluorine atom, a bromine atom and a chlorine atom. The aliphatic group and the aromatic group include an aliphatic group represented by the R _1f. Is synonymous with an aromatic group. Moreover, as a substituent of a substituted amino group, a substituted oxy group, and a substituted mercapto group, it is synonymous with the substituent of the substituted alkyl group represented by said R _1f .

In the structural formula (36), the methine group represented by L _1f and L _2f is an unsubstituted methine group, or a substituent substituted with a halogen atom or an aliphatic group when having a substituent, or Particularly preferred are those in which substituents are bonded to each other to form a cyclopentene ring or a cyclohexene ring.

  In Structural Formula (36), m represents 0, 1, 2, or 3.

In the structural formula (36), Z _1f represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring may be condensed with an aromatic ring or a heterocyclic ring. The nitrogen-containing heterocyclic ring and the aromatic ring or heterocyclic ring condensed to the nitrogen-containing heterocyclic ring may have a substituent. Examples of the nitrogen-containing heterocycle include an oxazole ring, a thiazole ring, a selenazole ring, a pyrrole ring, a pyrroline ring, an imidazole ring, and a pyridine ring. A 5-membered ring is preferred over a 6-membered ring. The nitrogen-containing heterocycle may be condensed with an aromatic ring (benzene ring or naphthalene ring), and the nitrogen-containing heterocycle and the condensed ring may further have a substituent. As an example of a substituent, the thing similar to the substituent of the substituted alkyl represented by said R _1f can be mentioned.

Y ^f in the structural formula (36) represents N (R _31f ) R _32f , OR _33f , or S (O) _n R _34f , where R _31f , R _32f , R _33f , and R _34f are Each independently represents a hydrogen atom or a monovalent substituent, and n represents 0, 1 or 2.

_Examples of the monovalent substituent represented by R _31f , R _32f , and R _33f include an aliphatic group, an aromatic ring group, a heterocyclic group, C (O) _p R _35f , and S (O) _q R _36f. Can be mentioned. Here, R _35f and R _36f each independently represent a hydrogen atom, an aliphatic group, an aromatic ring group, a heterocyclic group or N (R _37f ) R _38f , and R _37f and R _38f each independently represent hydrogen An atom, an aliphatic group, an aromatic ring group, a heterocyclic group, COR _39f or SO ₂ R _40f is represented, and R _39f and R _40f represent a hydrogen atom, an aliphatic group, an aromatic ring group, and a heterocyclic group. P and q each independently represent 1 or 2. The monovalent substituent represented by R _34f has the same _meaning as R _36f above.

The aliphatic group and aromatic ring group represented by R _{31f to} R _{40f have the same meanings} as the aliphatic group and aromatic ring group represented by R _1f in the structural formula (36).

_Examples of the heterocyclic group represented by R _{31f to} R _40f include a heterocyclic group having a substituent and an unsubstituted heterocyclic group. Examples of the heterocyclic group include nitrogen-containing, oxygen-containing, and sulfur-containing heterocycles, such as pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, acridine ring. , Furan ring, pyrrole ring, pyrazole ring, imidazole ring, pyrroline ring, oxazole ring, thiazole ring, oxadiazole ring, thiazoline ring, thiophene ring, indole ring and the like. Examples of the substituent of the heterocyclic group having a substituent include the same substituents as in the case of the substituted alkyl group. Among them, the ^{Y f} of the structural formula (36) in, in that it can more _{sensitivity, N (R 31f) R 32f} is preferred.

In the structural formula (36), X ⁻ represents a group capable of forming an anion. Examples of the anions include halogen ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonate ions, ethyl sulfate ions, 1,5-disulfonaphthalenedione, PF ₆ ⁻ , BF ₄ ⁻ , And ClO ₄ ^{— and the} like. Further, X ^- it may be a substituents replacing a substitutable position either cation sites of the structural formula (36), in that case, the compound represented by the structural formula (36) Forms an internal salt.

  Among the compounds represented by the structural formula (36), a compound represented by the following structural formula (37) or the structural formula (38) is preferable in terms of superior sensitivity.

In the structural formulas (37) and (38), R _11f and R _21f each independently represent an aliphatic group or an aromatic group. In the structural formula (37) and the structural formula (38), L _11f , L _12f , L _21f , and L _22f each independently represent a methine group optionally having a substituent, and L _11f , L _12f , When L _21f and L _22f represent a methine group having a substituent, the substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. The benzene ring Z _11f in the structural formula (37) may be condensed with another benzene ring, and the benzene ring Z _11f and those condensed rings may have a substituent. Z _21f in the structural formula (38) represents an atomic group forming a heterocyclic ring, and the heterocyclic ring may have a substituent. In the structural formula (37) and the structural formula (38), Y _11f and Y _21f each independently represent -CR _28f R _29f- , -NR _30f- , -O-, -S-, or Se-, R _28f , R _29f , and R _30f each independently represent a hydrogen atom, an aliphatic group, or an aromatic group, and R _28f and R _29f may be an atomic group that is bonded to each other to form a ring. In Structural Formula (37) and Structural Formula (38), m represents 0, 1, 2, or 3. X ⁻ represents a group capable of forming an anion.
The structural formula (37) and structural formula (38), the ^{Y f} is synonymous with ^{Y f} of the structural formula (36).

R _11f and R _21f in the structural formula (37) and the structural formula (38) have the same _meanings as R _{1f in the} structural formula (36), respectively, and preferred examples thereof are also the same. L _11f , L _12f and L _21f , L _22f have the same _{meanings as} L _1f and L _2f in the structural formula (36), respectively, and preferred examples are also the same.

The benzene ring Z _11f in the structural formula (37) may be condensed with another benzene ring, and the benzene ring Z _11f and those condensed rings may have a substituent. Examples of the substituent include the same substituents as those of the substituted alkyl represented by R _1f in the structural formula (36). Among these, an electron-withdrawing substituent is preferable because sensitivity can be improved. An electron-withdrawing substituent is one having a positive Hammett σ (sigma) value. Among these electron-withdrawing groups, those having a value of σm (sigma meta) or σp (sigma para) are preferably 0.2 or more, and more preferably 0.4 or more.

  Examples of the electron-withdrawing substituent include a halogen group, acyloxy group, acyl group, carbamoyl group, sulfamoyl group, aryl group, alkoxycarbonyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group, Examples include arylsulfonyl group, cyano group, nitro group, halomethyl group (for example, trifluoromethyl group), carboxyl group, sulfo group, phosphono group and the like.

Z _21f in the structural formula (38) represents an atomic group forming a heterocyclic ring, and the heterocyclic ring may have a substituent. Examples of the substituent include the same substituents as those of the substituted alkyl represented by R _1f in the structural formula (36). Examples of the atomic group Z _21f that forms such a heterocyclic ring include the following atomic groups.

Here, R represents an aliphatic group or an aromatic group.

Y _11f and Y _21f in the structural formula (37) and the structural formula (38) each independently represent a sulfur atom, an oxygen atom, C (R _33f ) R _34f , a selenium atom, or a tellurium atom, and R _33f and R _34f independently represents a hydrogen atom, an aliphatic group, or an aromatic group, and R _33f and R _34f may be an atomic group that is bonded to each other to form a ring. The aliphatic group and the aromatic group are respectively synonymous with the aliphatic group and the aromatic group represented by R _1f in the structural formula (36), and the aliphatic group is particularly an alkyl group or a substituted alkyl group. Is preferred. Y _11f and Y _21f are preferably an oxygen atom, a sulfur atom, and C (R _33f ) R _34f , particularly preferably a sulfur atom and C (R _33f ) R _34f , and R _33f and R _34f are preferably alkyl groups.

In Structural Formula (37) and Structural Formula (38), m is preferably 1 or 2, and particularly preferably 1. X ⁻ represents a group capable of forming an anion, and has the same meaning as X ⁻ in the structural formula (36), and preferred examples thereof are also the same.

  Specific examples (exemplary compounds) of the compounds represented by the structural formulas (36) to (38) are shown below, but the invention is not limited thereto.

  The compounds represented by the structural formulas (36) to (38) may be used alone or in combination of two or more.

  Examples of the compound having a basic nucleus further include compounds represented by the following structural formulas (39) to (44).

In the structural formula (39), L _5A , L _6A , L _7A , L _8A , L _9A , L _10A , and L _11A represent a methine group. In the structural formula (39), p ₃ and p ₄ represent 0 or 1. In the structural formula (39), n ₁ represents 0, ₁ , 2, 3 or 4. In the structural formula (39), Z _3A and Z _4A represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, these rings may be condensed. In the structural formula (39), R _3A and R _{4A each} represents an aliphatic group, an aromatic group, or a heterocyclic group. In the structural formula (39), M ₁ represents a counter ion for charge balance, and m ₁ represents a number of 0 or more necessary for neutralizing the charge of the molecule. However, R _3A , R _4A , Z _3A , Z _4A , L _{5A to} L _11A have no anionic substituent when the structural formula (39) is a cationic dye, and the structural formula (39) is a betaine dye. In the case of having one anionic substituent.

In the structural formula (40), L _12A , L _13A , L _14A and L _15A represent a methine group. In the structural formula (40), p ₅ represents 0 or 1. In the structural formula (40), n ₂ represents 0, 1, ₂ , 3 or 4. In the structural formula (40), Z _5A and Z _6A represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, these rings may be condensed. In the structural formula (40), R _5A and R _6A represent an aliphatic group, an aromatic group, or a heterocyclic group. In the structural formula (40), M ₁ and m ₁ have the same meanings as the structural formula (39). However, R _5A , R _6A , Z _5A , Z _6A , L _{12A to} L _15A have a cationic substituent when the structural formula (40) is a cationic dye, and the structural formula (40) is a betaine dye. In this case, it has one cationic substituent and one anionic substituent, and when the structural formula (40) is a nonionic dye, it does not have a cationic substituent and an anionic substituent.

In the structural formula (41), L _16A , L _17A , L _18A , L _19A , L _20A , L _21A , L _22A , L _23A , and L _24A represent a methine group. p ₆ and p ₇ each independently represents 0 or 1. In the structural formula (41), n ₃ and n ₄ represent 0, 1, 2, 3 or 4. In the structural formula (41), Z _7A , Z _8A and Z _9A represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, a ring may be condensed in Z _7A and Z _9A . In the structural formula (41), R _7A , R _8A and R _9A each independently represent an aliphatic group, an aromatic group, or a heterocyclic group. In the structural formula (41), M ₁ and m ₁ have the same meanings as the structural formula (39). However, R _7A , R _8A , R _9A , Z _7A , Z _8A , Z _9A , L _{16A to} L _24A have no anionic substituent when the structural formula (41) is a cationic dye, and the structural formula When (41) is a betaine dye, it has one anionic substituent.

In the structural formula (42), L _25A , L _26A , L _27A , L _28A , L _29A , L _30A and L _31A represent a methine group. In the structural formula (42), p ₈ and p ₉ each independently represents 0 or 1. In the structural formula (42), n ₅ represents 0, 1, 2, 3 or 4. In the structural formula (42), Z _10A and Z _11A represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, these rings may be condensed. R _10A and R _{11A each} represents an aliphatic group, an aromatic group, or a heterocyclic group. In the structural formula (42), M ₂ represents a counter ion for charge balance, and m ₂ represents a number of 0 or more necessary for neutralizing the charge of the molecule. However, R _10A and R _11A have an anionic substituent.

In the structural formula (43), L _32A , L _33A , L _34A and L _35A represent a methine group. In the structural formula (43), p ₉ each independently represents 0 or 1. In the structural formula (43), n ₆ represents 0, 1, 2, 3 or 4. In the structural formula (43), Z _12A and Z _13A represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, these rings may be condensed. In the structural formula (43), R _12A and R _13A each independently represent an aliphatic group, an aromatic group, or a heterocyclic group. In the structural formula _{(43), M 2, m} 2 is the same meaning as _M 2, _{m 2} of the structural formula (42). However, at least one of R _12A and R _13A has an anionic substituent.

In the structural formula (44), L _36A , L _37A , L _38A , L _39A , L _40A , L _41A , L _42A , L _43A , and L _44A represent a methine group. In the structural formula (44), p ₁₀ and p ₁₁ each independently represent 0 or 1. In the structural formula (44), n ₇ and n ₈ each independently represents 0, 1, 2, 3 or 4. In the structural formula (44), Z _14A , Z _15A and Z _16A represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, a ring may be condensed in Z _14A and Z _15A . In the structural formula (44), R _14A , R _15A and R _16A represent an aliphatic group, an aromatic group, or a heterocyclic group. In the structural formula _{(44), M 2, m} 2 is the same meaning as _M 2, _{m 2} of the structural formula (42). However, at least two of R _14A , R _15A and R _16A have an anionic substituent.

However, when the compounds of the structural formulas (39), (40) and (41) are used alone, at least one of R _3A and R _4A , preferably both have a group having an aromatic ring, R _5A and R _A group having at least one of _6A , preferably both having an aromatic ring, and at least one, preferably two, more preferably three of R _7A , R _8A and R _9A having an aromatic ring Group.

When the compounds of the structural formulas (39), (40) and (41) and the compounds of the structural formulas (42), (43) and (44) are used in combination, R _{3A to} R _9A and R of the combined dyes of _10A to R _16A, at least one is a group having an aromatic ring, preferably two of the group having an aromatic ring, more preferably three of the group having an aromatic ring, particularly preferably Four or more are groups having an aromatic ring.

Specific examples (exemplary compounds) of the compounds represented by the structural formulas (39) to (41) are shown below, but the invention is not limited thereto.

  Specific examples (exemplary compounds) of the compounds represented by the structural formulas (42) to (44) are shown below, but the invention is not limited thereto.

  The compound having a basic nucleus not only improves the sensitivity of the photosensitive layer, but also has a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation.

(4) Compound having an acidic nucleus The compound having an acidic nucleus as a sensitizer is not particularly limited as long as it is a compound having an acidic nucleus. ) Can be selected as appropriate. By using a compound having an acidic nucleus, for example, the sensitivity of the photosensitive layer can be very easily adjusted to 0.1 to 100 mJ / cm ² .
Examples of the compound having an acidic nucleus include a merocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, a rhodacyanine dye, and an oxonol dye. Among these, a merocyanine dye and a rhodacyanine dye are preferable, and a merocyanine dye is more preferable. preferable.

Examples of the acidic nucleus include, for example, “The Theory of the Photographic Process” edited by James, 4th edition, Macmillan Publishing Co., Ltd., 1977, Chapter 8, “The Theory of the Photographic Process”. Sensitizing dyes and desensitizing dyes ", U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002. No. 4,480, No. 4,925,777, JP-A-3-167546, and the like.
When the acidic nucleus is acyclic, the end of the methine bond is malononitrile, alkanesulfonylacetonitrile, cyanomethylbenzofuranyl ketone, cyanomethylphenyl ketone, malonic acid ester, acylaminomethyl-substituted ketones, etc. A group such as an active methylene compound is preferred.
5- or 6-membered nitrogen containing carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms when the atomic group necessary to form the acidic nucleus is cyclic A heterocyclic ring is preferably formed. Examples of the nitrogen-containing heterocyclic ring include 2-pyrazolin-5-one, pyrazolidine-3, 5-dione, imidazolin-5-one, hydantoin, 2-thiohydantoin, 4 -Thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazolin-5-one, 2-thiooxazoline-2, 4-dione, isoxazolin-5-one, 2-thiazoline-4-one, thiazolidine-4 -One, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiof 3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo- 6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolo [ 1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiol Down-1,1-dioxide, and 3-Jishianomechin 2,3 nuclei dihydrobenzo [d] thiophene-1,1-dioxide and the like.

  Examples of the acidic nucleus include the acidic heterocycles shown below.

Here, R represents a hydrogen atom, an aliphatic group, or an aromatic group each independently.

  Specific examples of the compound having an acidic nucleus include compounds represented by the following structural formulas (45) to (52).

In the structural formula (45), L _{1B to} L _4B represent a methine group. In the structural formula (45), p ₁ represents 0 or 1. In the structural formula (45), n ₁ represents 0, ₁ , 2, 3 or 4. In the structural formula (45), Z _1B and Z _2B represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, these rings may be condensed. The ring may be either an aromatic ring or a non-aromatic ring. An aromatic ring is preferred, and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring.
In the structural formula (45), R _1B and R _2B each independently represent an alkyl group, an aryl group, or a heterocyclic group. In the structural formula (45), M ₁ represents a counter ion for charge balance, and m ₁ represents a number of 0 or more necessary for neutralizing the charge of the molecule.
However, R _1B , R _2B , Z _1B , Z _2B , L _{1B to} L _4B have a cationic substituent when the structural formula (45) is a cationic dye, and the structural formula (45) is a betaine dye. In this case, it has one cationic substituent and one anionic substituent, and when the structural formula (45) is a nonionic dye, it does not have a cationic substituent and an anionic substituent.
The cationic dye may be any dye as long as the charge of the dye excluding the counter ion is cationic, but is preferably a dye having no anionic substituent. The anionic dye may be any dye as long as the charge of the dye excluding the counter ion is anionic, but is preferably a dye having one or more anionic substituents. The betaine dye is a dye that has a charge in the molecule but forms an inner salt, and the molecule does not have a charge as a whole. The nonionic dye is a dye having no charge in the molecule.
The anionic substituent is a substituent having a negative charge, for example, a proton dissociable acidic group dissociated by 90% or more between pH 5-8. Specifically, for example, sulfo group, carboxyl group, sulfato group, phosphoric acid group, boric acid group, alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), acylsulfuric group. Examples include a famoylalkyl group (for example, acetylsulfamoylmethyl group) and an alkylsulfonylsulfamoylalkyl group (for example, methanesulfonylsulfamoylmethyl group). More preferred are a sulfo group and a carboxyl group. Particularly preferred is a sulfo group.
Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.
When the compound of the structural formula (45) is used alone, R _1B in the structural formula (45) is preferably a group having an aromatic ring.

In the structural formula (46), L _{5B to} L _8B represent a methine group. In the structural formula (46), p ₂ represents 0 or 1. In the structural formula (46), n ₂ represents 0, 1, ₂ , 3 or 4. In the structural formula (46), Z _3B and Z _4B represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, these rings may be condensed. The ring may be either an aromatic ring or a non-aromatic ring. An aromatic ring is preferred, and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring.
In the structural formula (46), R _3B and R _4B each independently represent an alkyl group, an aryl group, or a heterocyclic group. In the structural formula (46), M ₂ represents a counter ion for charge balance, and m ₂ represents a number of 0 or more necessary to neutralize the charge of the molecule.
However, at least one of R _3B and R _{4B in} the structural formula (46) has an anionic substituent.

The structural formulas (45) and (46) will be described in more detail.
Examples of the nitrogen-containing heterocycle include a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a selenazoline nucleus, a selenazole nucleus, a benzoselenazole nucleus, and a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline Nuclei, imidazo [4,5-b] quinoxaline nuclei, oxadiazole nuclei, thiadiazole nuclei, tetrazole nuclei, pyrimidine nuclei, and the like. Preferred are benzothiazole nuclei, benzoxazole nuclei, and 3,3-dialkylindo. Renin nucleus (eg 3,3-dimethylindolenine) Benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, and 3-isoquinoline nucleus, benzothiazole nucleus, benzoxazole nucleus, 3, 3 -Dialkylindolenin nucleus (for example, 3,3-dimethylindolenine) and benzimidazole nucleus are preferred, benzoxazole nucleus, benzothiazole nucleus and benzimidazole nucleus are more preferred, benzoxazole nucleus and benzothiazole nucleus are particularly preferred .

When the substituent on the nitrogen-containing heterocyclic ring is V, the substituent represented by V is not particularly limited. For example, a halogen atom (for example, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxy group, and the like. Group, phosphate group, sulfo group, hydroxy group, carbamoyl group (for example, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), sulfamoyl group (for example, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), nitro group, alkoxy Groups (eg methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), aryloxy groups (eg phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), acyl groups (eg acetyl, benzoyl, trichloroacetyl), An acyloxy group (e.g. Tiloxy, benzoyloxy), acylamino groups (eg acetylamino), sulfonyl groups (eg methanesulfonyl, ethanesulfonyl, benzenesulfonyl), sulfinyl groups (eg methanesulfinyl, ethanesulfinyl, benzenesulfinyl), sulfonylamino groups (eg methanesulfonylamino) , Ethanesulfonylamino, benzenesulfonylamino), amino group, substituted amino group (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino), ammonium group (eg, trimethylammonium, triethylammonium), hydrazino group (eg, trimethylhydra) Dino group), ureido group (eg ureido group, N, N-dimethylureido group), imide group (eg succinimide group), alkyl Thio group (for example, methylthio, ethylthio, propylthio), arylthio group (for example, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, 2-benzyloxy) Carbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), unsubstituted alkyl groups (eg methyl, ethyl, propyl, butyl), substituted alkyl groups (eg hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetyl) Aminomethyl, and also here an unsaturated hydrocarbon group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (eg vinyl group, ethynyl group 1-cyclyl). Lohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group}, a substituted or unsubstituted aryl group (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), and substituted or unsubstituted heterocyclic groups (for example, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl), etc. Among these, an alkyl group, an aryl group, an alkoxy group, a halogen atom, aromatic ring condensation, a sulfo group, a carboxy group, and a hydroxy group are preferable.
In addition, a structure in which a ring (an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a quinoline ring) is condensed can also be used.
On the substituent represented by V, the V may be further substituted.

The substituent V on Z _{1B in the} structural formula (45) and Z _{3B in the} structural formula (46) is preferably an aromatic group or aromatic ring condensation.
Examples of the aromatic group include a hydrocarbon aromatic group and a heteroaromatic group. These are groups having a polycyclic condensed ring structure in which a hydrocarbon aromatic ring and a polycyclic condensed ring obtained by condensing heteroaromatic rings, or a combination of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. It may be substituted with the substituent V or the like. The aromatic ring contained in the aromatic group includes benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine , Indole, benzofuran, benzothiophene, isobenzofuran, quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxathiin, phenothiazine, phenazine, etc. Can be mentioned.

Z _{2B in the} structural formula (45) and Z _{4B in the} structural formula (46) represent an atomic group necessary for forming an acidic nucleus, such as hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid, etc. Hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid are preferred, and 2-thiohydantoin, 4-thio More preferred are hydantoin, 2-oxazolin-5-one, rhodanine, and barbituric acid.

R _1B and R _{2B in} the structural formula (45) and R _3B and R _{4B in} the structural formula (46) are each independently an alkyl group, an aryl group, and a heterocyclic group. An unsubstituted alkyl group having 1 to 18 carbon atoms (preferably 1 to 7, particularly preferably 1 to 4 carbon atoms) (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl) A substituted alkyl group having 1 to 18 carbon atoms (preferably 1 to 7, particularly preferably 1 to 4 carbon atoms) {for example, an alkyl group substituted with V as a substituent. Preferably, an aralkyl group (for example, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (for example, allyl group), a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (for example, carboxymethyl) , 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), an aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (eg 3-phenoxycarbonylpropyl), acyloxyalkyl group For example, 2-acetyloxyethyl), acylalkyl groups (for example, 2-acetylethyl), carbamoylalkyl groups (for example, 2-morpholinocarbonylethyl), sulfamoylalkyl groups (for example, N, N-dimethylsulfamoylmethyl), sulfo An alkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfo Alkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), heterocycle-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) Ethyl, tetrahydrofurfuryl), alkylsulfoni A carbamoylalkyl group (eg methanesulfonylcarbamoylmethyl group), an acylcarbamoylalkyl group (eg acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (eg acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (eg methane) A sulfonylsulfamoylmethyl group)}, an unsubstituted aryl group having 6 to 20 carbon atoms (preferably 6 to 10, more preferably 6 to 8) (for example, phenyl group, 1-naphthyl group), 6 to 20 carbon atoms ( Preferably 6 to 10 and more preferably 6 to 8) substituted aryl groups (for example, aryl groups substituted with the above-mentioned V as examples of substituents, specifically, p-methoxyphenyl group, p-methyl) (A phenyl group, p-chlorophenyl group, etc. are mentioned.) An unsubstituted heterocyclic group having 1 to 20 carbon atoms (preferably 3 to 10, more preferably 4 to 8) (for example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl group, 3- Isoxazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 2-oxazolyl group, 2-thiazolyl group, 2-pyridazyl group, 2-pyrimidyl group, 3-pyrazyl group, 2- (1,3,5-triazolyl group) , 3- (1,2,4-triazolyl) group, 5-tetrazolyl group), a substituted heterocyclic group having 1 to 20 carbon atoms (preferably 3 to 10, more preferably 4 to 8) (for example, the substituent V And the like, and specific examples thereof include 5-methyl-2-thienyl group, 4-methoxy-2-pyridyl group and the like.

R _1B and R _{2B in} the structural formula (45) are preferably groups having an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, which further include a hydrocarbon aromatic ring, a polycyclic condensed ring obtained by condensing heteroaromatic rings, an aromatic hydrocarbon ring, and It may be a polycyclic fused ring combined with an aromatic heterocycle, and may be substituted with the substituent V or the like.

The group having the aromatic ring as R _1B and R _{2B in} the structural formula (45) can be represented by -Lb-A ₁ . Here, Lb represents a single bond or a linking group. A ₁ represents an aromatic group. The linking group for Lb is preferably composed of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom.
Specific examples of the linking group represented by Lb include alkylene groups (eg, methylene, ethylene, propylene, butylene, pentylene), arylene groups (eg, phenylene, naphthylene), alkenylene groups (eg, ethenylene, propenylene), and alkynylene. Group (for example, ethynylene, propynylene), amide group, ester group, sulfoamide group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Va)-(Va is Represents a hydrogen atom or a monovalent substituent, which includes V described above, a heterocyclic divalent group (for example, 6-chloro-1,3,5-triazine-2, 4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group) Include linking groups 100 following combinations carbons configured 0 or more, it is preferred carbon atom number is 1 to 20.
The linking group may further have a substituent represented by V and may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring).

  Examples of the linking group include alkylene groups having 1 to 10 carbon atoms (for example, methylene, ethylene, propylene, butylene), arylene groups having 6 to 10 carbon atoms (for example, phenylene and naphthylene), and alkenylene having 2 to 10 carbon atoms. One or more groups (eg, ethenylene, propenylene), alkynylene groups having 2 to 10 carbon atoms (eg, ethynylene, propynylene), ether groups, amide groups, ester groups, sulfoamide groups, sulfonate ester groups It is preferably a divalent linking group having 1 to 10 carbon atoms configured in combination. These may be substituted with V.

The Lb is a linking group that may perform energy transfer or electron transfer through a through-bond interaction. The through-bond interaction includes a tunnel interaction and a super-exchange interaction, and among them, a through-bond interaction based on the super-exchange interaction is preferable. Through-bond and super-exchange interactions are interactions defined by Shammai Speiser, Chem. Rev. 96, 1960-1963, 1996. . Examples of the linking group capable of energy transfer or electron transfer by such an interaction are described in Shamai Speiser, Chem. Rev. 96, 1967-1969, 1996. Those are preferred.

Specific examples of R _1B and R _{2B in} the structural formula (45) include alkyl groups having a hydrocarbon aromatic ring such as aralkyl groups (for example, benzyl, 2-phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), aryloxyalkyl groups (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl, 2- (4-biphenyloxy) ethyl, 2- (o, m or p-halophenoxy)) Ethyl, 2- (o, m or p-methoxyphenoxy) ethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl) and the like are preferable. Examples of the alkyl group having a heteroaromatic ring include 2- (2-pyridyl) ethyl, 2- (4-pyridyl) ethyl, 2- (2-furyl) ethyl, 2- (2-thienyl) ethyl, 2- (2-Pyridylmethoxy) ethyl is preferred. As the hydrocarbon aromatic group, 4-methoxyphenyl, phenyl, naphthyl, biphenyl and the like are preferable. As the heteroaromatic group, a 2-thienyl group, 4-chloro-2-thienyl, 2-pyridyl, 3-pyrazolyl and the like are preferable.
Moreover, the alkyl group which has the above-mentioned substituted or unsubstituted hydrocarbon aromatic ring or a heteroaromatic ring is more preferable, and the alkyl group which has the above-mentioned substituted or unsubstituted hydrocarbon aromatic ring is especially preferable.

As R _3B and R _{4B in} the structural formula (46), a group having an aromatic ring is preferable, and at least one of them preferably has an anionic substituent.
Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. These include a hydrocarbon aromatic ring and a polycyclic condensed ring obtained by condensing heteroaromatic rings, or an aromatic hydrocarbon ring. And an aromatic heterocycle may be combined, and may be substituted with the substituent V or the like. As the aromatic ring, those shown as examples of the aromatic ring in the explanation of the aromatic group are preferable.

The group having an aromatic ring as R _3B and R _{4B in} the structural formula (46) can be represented by -Lc-A ₂ . Here, Lc represents a single bond or a linking group. A ₂ represents an aromatic group. Preferred examples of the linking group for Lc include the linking groups described above for Lb and the like. Preferred examples of the aromatic group for A ₂ include those mentioned above as examples of the aromatic group. Lc or A ₂ is preferably substituted with at least one anionic substituent.
As the alkyl group having a hydrocarbon aromatic ring, an aralkyl group substituted with any of a sulfo group, a phosphoric acid group, and a carboxyl group (for example, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3- Phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4′-sulfo-4-biphenyl) ethyl, 4-phosphobenzyl), sulfo group, phosphorus An aryloxycarbonylalkyl group (3-sulfophenoxycarbonylpropyl) substituted with either an acid group or a carboxyl group, an aryloxyalkyl group substituted with any of a sulfo group, a phosphate group, or a carboxyl group (for example, 2 -(4-sulfophenoxy) ethyl, 2- (2-phosphophenoxy) ethyl, 4,4-diph Enoxy-3-sulfobutyl) and the like are preferable.

Examples of the alkyl group having a heteroaromatic ring include 3- (2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl, 2- (2-thienyl) -2-sulfo. Propyl and the like are preferable. As the hydrocarbon aromatic group, an aryl group substituted with any of a sulfo group, a phosphate group and a carboxyl group (for example, 4-sulfophenyl, 4-sulfonaphthyl), and as the heteroaromatic group, a sulfo group, phosphorus A heterocyclic group substituted with either an acid group or a carboxyl group (for example, a 4-sulfo-2-thienyl group, a 4-sulfo-2-pyridyl group) and the like are preferable.
In addition, an alkyl group having a hydrocarbon aromatic ring or a heteroaromatic ring substituted by any of the sulfo group, phosphate group, and carboxyl group is more preferable, and any of the sulfo group, phosphate group, and carboxyl group is preferred. Are particularly preferred alkyl groups having a substituted hydrocarbon aromatic ring, such as 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, and 4-phenyl-4-sulfobutyl. Most preferred.

L _{1B to} L _4B in the structural formula (45) and L _{5B to} L _8B in the structural formula (46) each independently represent a methine group, and preferably an unsubstituted methine group.
The methine group may have a substituent, and examples of the substituent include V. A substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted carbon number An aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 to carbon atoms 15, more preferably a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-dimethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), 1 to 15 carbon atoms, preferably carbon An alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (for example, methoxy, ethoxy), 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, Preferably an amino group having 4 to 10 carbon atoms (for example, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, More preferably, it is an alkylthio group having 1 to 5 carbon atoms (for example, methylthio, ethylthio), an arylthio group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (for example, phenylthio, p-methyl). Phenylthio) and the like. The may form the other methine groups and rings, or, _Z 1B _{to Z} 4B _{respectively,} can also form a ring with R 1B _{to R 4B.}

M _{1 in the} structural formula (45) and M _{2 in the} structural formula (46) are formulas to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Is included. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (for example, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (for example, p-toluenesulfonate ion, p- Chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

In Structural Formulas (47) to (49), Z _{5B to} Z _10B represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring. In the structural formula (48), D and D ′ represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus. In the structural formulas (47) to (49), R _{5B to} R _8B and R _10B each independently represent an alkyl group. In Structural Formula (49), R _9B represents an alkyl group, an aryl group, or a heterocyclic group. In Structural Formulas (47) to (49), L _{9B to} L _28B represent a methine group. In the structural formulas (47) to (49), M _{3 to} M ₅ represent charge neutralization counter ions, and m _{3 to} m ₅ are numbers of 0 or more necessary for neutralizing charges in the molecule. In Structural Formulas (47) to (49), n ₃ , n ₅ , n ₆ , n ₈ and n ₁₁ are 0 or 1, and n ₄ , n ₇ , n ₉ and n ₁₀ are each 0 or more Is an integer.

The structural formulas (47) to (49) will be described in more detail.
In structural formulas (47) to (49), R _{5B to} R _8B and R _10B are preferably an unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl) , Octadecyl), or a substituted alkyl group {as the substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, bromine), a hydroxy group, or an alkoxycarbonyl group having 8 or less carbon atoms (for example, Methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (for example, phenoxy, p-tolyloxy), acyl having 3 or less carbon atoms Oxy group (for example, acetyloxy, propionyloxy), acyl group having 8 or less carbon atoms (for example, acetyl, propionyl, benzoyl, mesyl), carbamoyl group (for example, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl) Sulfamoyl group (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl group having 10 or less carbon atoms (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) And an alkyl group having a carbon number of 18 or less substituted with. Preferably an unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group) ), A sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group), methanesulfonylcarbamoylmethyl group.

In structural formulas (47)-(49), M ₃ m ₃ , M ₄ m ₄ and M ₅ m ₅ are present in the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Or included in an expression to indicate absence. Whether a certain dye is a cation, an anion, or has a net ionic charge depends on its auxiliary color groups and substituents. Typical cations are inorganic or organic ammonium ions and alkali metal ions, while the anions may be specifically inorganic or organic anions, such as halogen anions (eg fluorine ions, Chlorine ions, bromine ions, iodine ions), substituted aryl sulfonate ions (eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ions (eg, 1,3-benzene disulfonate ion, 1, 5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetic acid Ion, trifluoromethane Preferably sulfonic acid ion and the like, ammonium ion, an iodine ion, a p- toluenesulfonic acid ion.

As the nucleus formed by Z _{5B to} Z _8B and Z _10B , a thiazole nucleus {thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), Benzothiazole nucleus (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylthiobenzothiazole, 5-methylbenzothiazole 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, Tylthiobenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6- Dimethylbenzothiazole, 5,6-dimethylthiobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [ 2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1- d] thiazole, 8-methoxy Naphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole)}, thiazoline nucleus (eg thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (eg , Oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole) 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzo Xazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzo Oxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d ] Oxazole, 5-nitronaphtho [2,1-d] oxazole)}, oxazoline nucleus (eg, 4,4-dimethyloxazoline), selenazole nucleus {selenazole nucleus (eg, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzo Selenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (eg, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole) )}, Selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus {tellazole nucleus (eg, tellurazole, 4-methyltellazole, 4-phenyltellazole), benzotelrazole nucleus (eg, benzotelrazole) 5-chlorobenzotellazole, -Methylbenzotellazole, 5,6-dimethylbenzotellazole, 6-methoxybenzotellazole), naphthotelrazole nucleus (for example, naphtho [2,1-d] tellazole, naphtho [1,2-d] tellazole) }, Tellurazoline nucleus (for example, tellurazoline, 4-methyltellazoline), 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5) -Cyanoindolenin, 3,3-dimethyl-6-nitroindolenin, 3,3-dimethyl-5-nitroindolenin, 3,3-dimethyl-5-methoxyindolenin, 3,3,5-trimethylindolenin 3,3-dimethyl-5-chloroindolenine), imidazole nucleus {imidazole nucleus (eg 1-al Ruimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (eg 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzo) Imidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6- Chloro-5-cyanobenzozoimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1- Arylbenzoy Midazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthimidazole nucleus (e.g. Alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), and the aforementioned alkyl group has 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, isopropyl An unsubstituted alkyl group such as butyl or hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl) is preferable. Particularly preferred are a methyl group and an ethyl group. The aforementioned aryl groups represent phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, Pyridine nucleus (eg 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (eg 2-quinoline, 3-methyl-2-pyridine) Quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4- Quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (eg 6-nitro-1- Soquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (eg, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus. However, in the general formula, when n ₄ is 1, neither Z _5B nor Z _6B is an oxazole nucleus or an imidazole nucleus. The nucleus formed by Z _{5B to} Z _8B and Z _10B is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus, or a 4-quinoline nucleus.

  In the structural formula (48), D and D ′ each represent an atomic group necessary for forming an acidic nucleus, but may take the form of an acidic nucleus of any general merocyanine dye. Preferred substituents involved in the resonance of D are, for example, a carbonyl group, a cyano group, a sulfonyl group, and a sulfenyl group. Said D 'represents the remaining atomic group required in order to form an acidic nucleus. When D and D 'are cyclic, they form a 5- or 6-membered heterocycle consisting of carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. Specifically, 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5 ON, 2-thiooxazolidine-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodamine, thiazolidine-2,4- Dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, indazolin-3-one, 2- Oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3 2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,4-dione, barbituric acid, 2-thiobarbituric acid, chroman- Examples include nuclei of 2,4-dione, indazolin-2-one, or pyrido [1,2-a] pyrimidine-1,3-dione. Among these, 3-alkyl rhodanine, 3-alkyl-2-thiooxazolidine-2,4-dione, and 3-alkyl-2-thiohydantoin are preferable.

The substituent bonded to the nitrogen atom contained in the nucleus and R _9B in the structural formula (49) are a hydrogen atom, an alkyl having 1 to 18 carbons (preferably 1 to 7 and particularly preferably 1 to 4). Groups {eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl}, substituted alkyl groups (eg aralkyl groups (eg benzyl, 2-phenylethyl), hydroxyalkyl groups (eg 2- Hydroxyethyl, 3-hydroxypyr), a carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2- Methoxyethoxy) ethyl), sulfoalkyl group (eg 2-sulfoethyl) 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl groups (for example, 3- Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxy Methyl, 2-methanesulfonylaminoethyl), allyl group, aryl group (eg, phenyl, 2-naphthyl), substituted aryl group (eg, 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl), Heterocyclic groups (eg 2-pyridyl, 2-thiazolyl), preferred . More preferably, an unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl, sulfoalkyl group ( For example, 2-sulfoethyl).

In Structural Formula (49), the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z _9B is at an appropriate position from the cyclic heterocyclic ring represented by D and D ′ in Structural Formula (48). , An oxo group, or a thiooxo group. More preferably, the thiooxo group of the rhodanine nucleus is removed.

L _{9B to} L _28B in the structural formulas (47) to (49) are a methine group or a substituted methine group {eg, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted Aryl group (for example, phenyl, o-carboxyphenyl), heterocyclic group (for example, barbituric acid), halogen atom (for example, chlorine atom, bromine atom), alkoxy group (for example, methoxy, ethoxy), amino group (for example, N , N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino), alkylthio groups (for example, methylthio, ethylthio), etc.}, and form rings with other methine groups May be.
L _9B , L _13B , L _14B and L _{15B in} the structural formula (47), L _18B and L _19B in the structural formula (48), and L _25B and L _26B in the structural formula (49) are not present. A substituted methine group is preferred. Trimethine, pentamethine and heptamethine dyes are formed by L _9B , L _10B and L _{11B in the} structural formula (47). Although it is repeated when the unit n ₃ of L _9B and L _{10B in} the structural formula (47) is 2 or 3, it does not have to be the same.

In Structural Formula (50), L _{29B to} L _31B each independently represent a methine group which may have a substituent. When these represent a methine group having a substituent, the substituents are bonded to each other. An unsaturated aliphatic ring or an unsaturated heterocyclic ring may be formed. In the structural formula (50), Z _11B represents an atomic group forming a 5-membered or 6-membered heterocycle, and the heterocycle may be condensed with an aromatic ring or a heterocycle, and the 5-membered Alternatively, the 6-membered heterocyclic ring and the aromatic ring or heterocyclic ring condensed to the heterocyclic ring may have a substituent. In the structural formula (50), Y ^B represents N (R _11B ) R _12B , OR _13B , or S (O) _n R _14B , and R _{11B to} R _14B each independently represent a hydrogen atom or a monovalent group. Represents a substituent, and n represents 0, 1 or 2. In the structural formula (50), q represents 0, 1, 2, or 3.
The specific example (exemplary compound No. 1-62) of a compound represented by the said Structural formula (50) is shown.

In the structural formula (51), R _18B and R _19B each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
In the structural formula (51), Q _{1 to} Q ₃ each independently represent an oxygen atom or a sulfur atom. Here, Q ₁ and Q ₂ are preferably oxygen atoms, and Q ₃ is preferably a sulfur atom.
L _{32B to} L _34B each independently represents a methine group which may have a substituent. When these represent a methine group having a substituent, the substituents are bonded to each other to form an unsaturated aliphatic ring or an unsaturated ring. A saturated heterocyclic ring may be formed.
Y _2B represents an aromatic group or a heterocyclic group, and n ₁₂ represents 0, 1, 2, or 3.

In the structural formula (51), R _18B and R _19B each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. When R _18B and R _19B represent an aliphatic group, examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable. The aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

  Examples of the alkyl group include linear, branched and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. The preferred range of the number of carbon atoms in the alkyl part of the substituted alkyl group is the same as in the case of the alkyl group. Further, the alkyl group may be either a substituted alkyl group or an unsubstituted alkyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group, cyclopentyl group, neopentyl group, An isopropyl group, an isobutyl group, etc. are mentioned.

  Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, carbon number 30 The following alkoxy groups (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio groups having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methylthioethylthioethyl group, etc.) An aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryloxy A carbonyloxy group, an acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, Carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group) Etc.), an aryl group having 30 or less carbon atoms For example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group) Etc.), substituted ureido groups, substituted phosphono groups, heterocyclic groups and the like. Here, the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in a salt state.

  Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups. The number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20. The preferred range of the number of carbon atoms in the alkenyl part of the substituted alkenyl group is the same as in the case of the alkenyl group. The alkenyl group may be a substituted alkenyl group or an unsubstituted alkenyl group. Examples of the substituent of the substituted alkenyl group include the same substituents as those of the substituted alkyl group.

  Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 35, and more preferably 7 to 25. The preferred range of the number of carbon atoms in the aralkyl part of the substituted aralkyl group is the same as in the case of the aralkyl group. Further, the aralkyl group may be any of an aralkyl group having a substituent and an unsubstituted aralkyl group. Examples of the substituent for the substituted aralkyl group include the same substituents as those for the substituted alkyl group.

When R _18B and R _19B in the structural formula (51) represent an aromatic group, examples of the aromatic group include an aryl group and a substituted aryl group. As a carbon atom number of an aryl group, 6-30 are preferable and 6-20 are more preferable. The preferred range of the number of carbon atoms in the aryl part of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. Examples of the substituent for the substituted aryl group include the same substituents as those for the substituted alkyl group.

When R _18B and R _19B in the structural formula (51) represent a heterocyclic group, examples of the heterocyclic group include a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and the heterocyclic group The number of carbon atoms is preferably 4-13. Examples of the heterocyclic group include nitrogen-containing, oxygen-containing, and sulfur-containing heterocycles, and more specifically, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, quinoline ring, isoquinoline ring, quinoxaline. Ring, acridine ring, furan ring, pyrrole ring, pyrazole ring, imidazole ring, pyrroline ring, oxazole ring, thiazole ring, oxadiazole ring, thiazoline ring, thiophene ring, indole ring and the like. Examples of the substituent of the heterocyclic group having a substituent include the same substituents as in the case of the substituted alkyl group.

Among the above, as R _18B and R _19B in the structural formula (51), an unsubstituted alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n -Hexyl group, octyl group, octadecyl group and the like) or a substituted alkyl group is preferable. Among the substituted alkyl groups, a substituted oxyalkyl group (for example, methoxyethyl group, phenoxyethyl group and the like) and a substituted oxycarbonylalkyl group (for example, butoxycarbonylmethyl group, phenoxyethoxycarbonylmethyl group and the like) are particularly preferable. R _18B and R _19B may be bonded to other adjacent substituents to form a ring, and examples of the ring include a 5-membered or 6-membered heterocycle. .

L _{32B to} L _34B in the structural formula (51) each independently represent a methine group which may have a substituent, and have an odd number of methine groups in the structure. When L _{32B to} L _34B in the structural formula (51) represent a methine group having a substituent, examples of the substituent include a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an aryl group). Amino groups, diarylamino groups, acylamino groups, etc.), substituted oxy groups (eg, hydroxy groups, alkoxy groups, acyloxy groups, aryloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, etc.), substituted mercapto groups (eg, Alkyl mercapto group, aryl mercapto group, etc.), halogen atom, aliphatic group, aromatic group, etc., and these substituents may be bonded to form an unsaturated aliphatic ring or unsaturated heterocyclic ring. Unsaturated aliphatic rings are preferred over heterocycles. The ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cyclopentene ring or a cyclohexene ring. Examples of the halogen atom include a fluorine atom, a bromine atom, and a chlorine atom. Examples of the aliphatic group and aromatic group include an aliphatic group and an aromatic group in R _18B and R _19B in the structural formula (51). It is synonymous with the case of group. Moreover, as a substituent of a substituted amino group, a substituted oxy group, and a substituted mercapto group, it is synonymous with the substituent of the substituted alkyl group represented by said R _<18B> and R _<19B> in the said Structural formula (51).

In the structural formula (51), the methine group represented by L _{32B to} L _34B is an unsubstituted methine group, or a substituent substituted with a halogen atom or an aliphatic group when having a substituent, or Particularly preferred are those in which substituents are bonded to each other to form a cyclopentene ring or a cyclohexene ring. In the structural formula (51), n ₁₂ represents 0, 1, 2, or 3.

In the structural formula (51), Y _2B represents an aromatic group or a heterocyclic group. Here, the aromatic group and the heterocyclic group are synonymous with the aromatic group and the heterocyclic group in R _18B and R _19B in the structural formula (51), and preferred examples thereof are also the same. Y _2B in the structural formula (51) is particularly preferably an aromatic group from the viewpoint of photosensitivity.

In the structural formula (52), R _20B and R _21B each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Q _{4 to} Q ₆ each independently represent an oxygen atom or a sulfur atom. Represents. L _{35B to} L _37B each independently represent a methine group optionally having a substituent, and when these represent a methine group having a substituent, the substituents are bonded to each other to form an unsaturated aliphatic ring or A saturated heterocyclic ring may be formed. Y _3B represents the following group (1), and n ₁₃ represents 0, 1, 2, or 3.
R _20B and R _21B in the structural formula (52) are R _18B and R _19B in the structural formula (51), and Q _{4 to} Q ₆ in the structural formula (52) are in the structural formula (51). Q _{1 to} Q ₃ and L _{35B to} L _37B in the structural formula (52) have the same meanings as L _{32B to} L _34B in the structural formula (51), respectively.

In the group (1), R _22C represents a hydrogen atom, an aliphatic group, or an aromatic group. Z _12C represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be condensed with an aromatic ring or a heterocycle, the nitrogen-containing heterocycle, and the The aromatic ring and heterocyclic ring condensed to the nitrogen-containing heterocyclic ring may have a substituent.
In the group (1), X ⁻ represents a group capable of forming an anion. Examples of the anion that can be formed by X ⁻ include halogen ion (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonic acid ion, ethyl sulfate ion, 1,5-disulfonaphthalenedione, PF ₆ ^-, BF ₄ ^-, and ClO ₄ ^-, and the like. X ⁻ may be a substituent substituting any substitutable position of the cation moiety.

Examples of the nitrogen-containing heterocycle include an oxazole ring, a thiazole ring, a selenazole ring, a pyrrole ring, a pyrroline ring, an imidazole ring, and a pyridine ring. A 5-membered ring is preferred over a 6-membered ring.
The nitrogen-containing heterocycle may be condensed with an aromatic ring (benzene ring, naphthalene ring) or a heterocycle (pyridine, pyrazine, etc.), and the nitrogen-containing heterocycle and the condensed ring are further substituted. You may have.

Examples of the compound having an acidic nucleus include, for example, compounds in which an aromatic ring (for example, phenyl group, naphthyl group, etc.) substituted with an amino group or an alkoxy group and an acidic nucleus are connected by a methine chain. It is done. The number of methine chains is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. The acidic nucleus is preferably a 5-membered to 6-membered ring.
Other examples of the compound having an acidic nucleus include compounds represented by the following (A) and (B).

  The compound having an acidic nucleus not only improves the sensitivity of the photosensitive layer, but also has a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation.

(5) Fluorescent whitening agent The fluorescent whitening agent as a sensitizer is used for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to a photosensitive layer, which will be described later, or when the photosensitive layer is exposed and developed. It is added from the viewpoint of improving the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer before and after the development. By using the fluorescent brightening agent in combination, for example, the sensitivity of the photosensitive layer can be adjusted very easily to 0.1 to 100 mJ / cm ² .

  The fluorescent whitening agent, also known as a “fluorescent whitening agent”, can absorb light having a wavelength in the vicinity of 300 to 450 nm, which is ultraviolet to short wave visible, and has a wavelength in the vicinity of 400 to 500 nm. It is a colorless or weakly colored compound capable of emitting fluorescence having the following. A description of the physical principles and chemistry of optical brighteners is given in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Electronic Release, Wiley-VCH 1998. Basically, suitable optical brighteners contain a π-electron system comprising a carbocyclic or heterocyclic nucleus.

The fluorescent whitening agent as the sensitizer is not particularly limited and can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.).
As the fluorescent brightening agent, a compound having a nonionic nucleus is preferable. The nonionic nucleus is preferably at least one selected from, for example, a stilbene nucleus, a distyrylbenzene nucleus, a distyrylbiphenyl nucleus, and a divinylstilbene nucleus.

  The compound having a nonionic nucleus is not particularly limited and may be appropriately selected depending on the intended purpose. For example, pyrazolines, triazines, stilbenes, distyrylbenzenes, distyrylbiphenyls, divinyl Stilbenes, triazinylaminostilbenes, stilbenyltriazoles, stilbenylnaphthotriazoles, bis-triazolestilbenes, benzoxazoles, bisphenylbenzoxazoles, stilbenylbenzoxazoles, bis -Benzoxazoles, furans, benzofurans, bis-benzimidazoles, diphenylpyrazolins, diphenyloxadiazoles, naphthalimides, xanthenes, carbostyrils, pyrenes and 1,3,5-triazinyl -Derivatives etc. That. Among these, those having at least one selected from a styryl group, a benzoxazolyl group, and a benzothiazolyl group are preferable, and further, a distyrylbenzene, a distyrylbiphenyl, or an ethenyl group, an aromatic ring group, and a heterocyclic group. Bisbenzoxazoles, bisbenzothiazoles, and the like linked by a divalent linking group consisting of are particularly preferable.

  The fluorescent brightening agent may have a substituent. Examples of the substituent include an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and a carbon number of 30 or less. Alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, having 30 or less carbon atoms Acylaminosulfonyl group, alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio group having 30 or less carbon atoms (for example, methylthio group, ethylthio group) , Methylthioethyl Oethyl group, etc.), aryloxy groups having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro groups, alkyl groups having 30 or less carbon atoms, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl Groups (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group and the like), sulfamoyl groups (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, Peridinosulfonyl group, etc.), 30 or more carbon atoms Aryl groups (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino groups (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino) Group, acylamino group, etc.), substituted ureido group, substituted phosphono group, and the like.

Examples of each of the above representative optical brighteners include, for example, those described in Okawara “Dye Handbook”, Kodansha, pages 84 to 145, pages 432 to 439.
The triazines are not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene bismelamine, propylene-1,3-bismelamine, N, N′-dicyclohexylethylenebismelamine, N, N′-dimethylethylenebismelamine, N, N′-bis [4,6-di- (dimethylamino) -1,3,5-triazinyl] ethylenediamine, N, N′-bis (4,6-dipiperidino-1 , 3,5-triazinyl) ethylenediamine, N, N′-bis [4,6-di- (dimethylamino) -1,3,5-triazinyl] -N, N′-dimethylethylenediamine, and the like. Examples of typical optical brighteners are listed in the following structural formulas (53) to (59).

  More specifically, in the present invention, a fluorescent whitening agent having any one of the following partial structures is suitable for use.

  In the above partial structure formula, X is one of the following groups, and * in the following formula represents the position of the bond in the above formula.

  Here, one or more nuclei in each of the above formulas may be substituted by the following groups. Examples of the substituent include an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and a carbon number of 30 or less. Alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, having 30 or less carbon atoms Acylaminosulfonyl group, alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio group having 30 or less carbon atoms (for example, methylthio group, ethylthio group) , Methylthioethyl Oethyl group, etc.), aryloxy groups having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro groups, alkyl groups having 30 or less carbon atoms, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl Groups (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group and the like), sulfamoyl groups (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, Peridinosulfonyl group, etc.), 30 or more carbon atoms Aryl groups (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino groups (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino) Group, acylamino group, etc.), substituted ureido group, substituted phosphono group, and the like.

  The fluorescent brightening agent is preferably a compound that can be dissolved in an organic solvent, water, or an alkaline aqueous solution. Moreover, the compound which can be disperse | distributed and emulsified in an organic solvent, water, and aqueous alkali solution may be sufficient. The optical brightener can be used as a single compound or as a mixture of several substances.

  Among the fluorescent brighteners, those having the following partial structures are particularly preferred, but the present invention is not limited to these.

In the above formula,
a) R ^1D is a methyl group, R ^2D , R ^3D , R ^4D and R ^5D are hydrogen atoms,
b) R ^2D , R ^3D and R ^4D are methoxy groups, R ^1D and R ^5D are hydrogen atoms,
c) R ^1D represents a cyano group, R ^2D , R ^3D , R ^4D and R ^5D represent a hydrogen atom, or d) R ^3D represents a cyano group, and R ^1D , R ^2D , R ^4D and R ^5D represent a hydrogen atom.

In the above formula, R ^1E , R ^2E , R ^3E and R ^4E represent a hydrogen atom, and R ^5E represents a methoxy group.

In the above formula,
a) R ^1F , R ^2F , R ^3F , R ^4F , R ^5F , R ^6F , R ^7F , R ^8F , R ^9F and R ^10F are hydrogen atoms,
b) R ^1F , R ^2F , R ^4F , R ^5F , R ^6F , R ^7F , R ^8F , R ^9F and R ^10F are hydrogen atoms, R ^3F is a methoxy group, or c) R ^1F , R ^2F , R ^4F , R ^5F , R ^6F , R ^7F , R ^9F , R ^10F are hydrogen atoms, R ^3F and R ^8F are methoxy groups,
Represents.

In the above formula,
a) R ^1G and R ^3G represent a hydrogen atom, R ^2G represents a SO ₃ Ph, or b) R ^1G represents a hydrogen atom, R ^2G represents a cyano group, and R ^3G represents a chlorine atom.

In the above formula,
a) R ^1H is a t-butyl group, R ^2H is a hydrogen atom, R ^3H is a phenyl group,
b) R ^1H is a methyl group, R ^2H is a hydrogen atom, R ^3H is a methoxycarbonyl group (COOMe), or c) R ^1H is a hydrogen atom, R ^2H is a hydrogen atom, and R ^3H is 2- (4-methyl-oxa -3,3-diazole)
Represents.

In the above formula,
a) X ^I is 4,4′-stilbendiyl, R ^1I and R ^2I are hydrogen atoms,
b) X ^I is 2,5-thiophenediyl, R ^1I and R ^2I are t-butyl groups,
c) X ^I represents 1,4-naphthalenediyl, R ^1I and R ^2I represent a hydrogen atom, or d) X ^I represents 1,1-ethenediyl, R ^1I and R ^2I represent a methyl group.

In the above formula, R ^1J and R ^2J represent a diethylamino group.

In the above formula,
a) R ^1K and R ^2K are hydrogen atoms, R ^3K is SO ₂ NH ₂ ,
b) R ^1K and R ^2K are hydrogen atoms, R ^3K is SO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ NMe ₂ ,
c) R ^1K and R ^2K are hydrogen atoms, R ^3K is SO ₂ CH ₂ CH ₂ OCH (CH ₃ ) CH ₂ NMe ₂ ,
d) R ^1K and R ^2K are hydrogen atoms, R ^3K is SO ₂ CH ₃ , or e) R ^1K and R ^2K are hydrogen atoms, R ^3K is SO ₂ CH ₂ CH ₂ OH
Represents.

In the above formula,
a) R ^1L , R ^2L , R ^3L , R ^4L , R ^5L , R ^6L , R ^7L , R ^8L , R ^9L , R ^10L are hydrogen atoms, R ^11L is

b) R ^1L , R ^2L , R ^3L , R ^4L , R ^5L , R ^6L , R ^7L , R ^8L , R ^9L , R ^10L are hydrogen atoms, R ^11L is

^{c) R 1L, R 2L,} R 4L, R 5L, R 6L, R 7L, R 8L, R 9L, R 10L is hydrogen ^{atom, R 3L} is t- ^{butyl, R 11L} is

d) R ^1L , R ^2L , R ^4L , R ^5L , R ^6L , R ^7L , R ^8L , R ^9L , R ^10L are hydrogen atoms, R ^3L is a t-butyl group, R ^11L is

^{e) R 1L, R 2L,} R 4L, R 5L, R 6L, R 7L, R 8L, R 9L, R 10L is hydrogen ^{atom, R 3L} is a methoxy ^{group, R 11L} is

f) R ^1L , R ^5L , R ^6L , R ^7L , R ^8L , R ^9L , R ^10L are hydrogen atoms, R ^2L and R ^4L are methoxy groups, R ^3L is a t-butyl group, R ^11L is

g) R ^1L , R ^2L , R ^4L , R ^5L , R ^6L , R ^7L , R ^9L , R ^10L are hydrogen atoms, R ^3L is a t-butyl group, R ^8L is a methoxy group, R ^11L is

In the above formula,
a) R ^1M , R ^2M , R ^3M , R ^4M , R ^5M , R ^6M , R ^7M , R ^8M , R ^9M , R ^10M are hydrogen atoms, R ^11M is

b) R ^1M , R ^2M , R ^3M , R ^4M , R ^5M , R ^6M , R ^7M , R ^8M , R ^9M , R ^10M are hydrogen atoms, R ^11M is

c) R ^1M , R ^2M , R ^4M , R ^5M , R ^6M , R ^7M , R ^8M , R ^9M , R ^10M are hydrogen atoms, R ^3M is a t-butyl group, R ^11M is

d) R ^1M , R ^2M , R ^4M , R ^5M , R ^6M , R ^7M , R ^8M , R ^9M , R ^10M are hydrogen atoms, R ^3M is a t-butyl group, R ^11M is

e) R ^1M , R ^2M , R ^4M , R ^5M , R ^6M , R ^7M , R ^8M , R ^9M , R ^10M are hydrogen atoms, R ^3M is a methoxy group, R ^11M is

f) R ^1M , R ^5M , R ^6M , R ^7M , R ^8M , R ^9M , R ^10M are hydrogen atoms, R ^2M and R ^4M are methoxy groups, R ^3M is a t-butyl group, R ^11M is

g) R ^1M , R ^2M , R ^4M , R ^5M , R ^6M , R ^7M , R ^9M , R ^10M are hydrogen atoms, R ^3M is a t-butyl group, R ^8M is a methoxy group, R ^11M is

In the above formula,
a) R ^1N represents a hydrogen atom, R ^2N represents a methoxy group, R ^3N represents a methyl group, or b) R ^1N and R ^2N represent an ethoxy group, and R ^3N represents a methyl group.

In the above formula,
a) R ^1P and R ^2P are methyl groups, R ^3P is a hydrogen atom, or b) R ^1P and R ^2P are methyl groups, and R ^3P is OCOMe
Represents.

In the above formula,
a) X ^Q represents 1,2-ethenediyl, R ^1Q represents a methyl group, or b) X ^Q represents 4,4′-stilbenediyl, and R ^1Q represents a methyl group.

In the above formula, R ^1R represents a phenyl group, R ^2R represents a diethylamino group (NEt ₂ ), and R ^3R represents an ethyl group.

In the above formula, R ^1S and R ^2S represent a methoxy group.

  As the fluorescent brightening agent used in the present invention, one containing at least one compound represented by the following structural formula (60) or structural formula (61) may be used. The fluorescent whitening agent is a spectral sensitizing dye and has a function of spectrally sensitizing a compound capable of generating radicals or cations (radical or cation generator). Therefore, when irradiated with visible to infrared light corresponding to the absorption of the spectral sensitizing dye, even if it contains a radical or cation generator that has no absorption in this region, the radical or cation from the generator Can be promoted.

In the structural formula (60) and the structural formula (61), R ^{1h to} R ^12h are each independently a hydrogen atom, a saturated or unsaturated alkyl group which may have a substituent, an aralkyl group, an aryl group, saturated or An unsaturated alkyloxy group, an aralkyloxy group, an aryloxy group, a saturated or unsaturated alkylthio group, an aralkylthio group, an arylthio group, an amino group, a dialkylamino group, a diarylamino group, and a halogen atom are represented. R ^{1h to} R ^{12h each} further represents an unsaturated nitrogen-containing heterocyclic group, and a nitrogen atom in the ring may be bonded to a benzene ring. The groups R ^{1h to} R ^12h may form a saturated or unsaturated ring together with the adjacent groups.
In the structural formula (60) and the structural formula (61), X ^h , Y ^h , and Z ^h each independently represent an oxygen atom, a sulfur atom, or a monosubstituted nitrogen atom.
P in the structural formula (60) and L ^{1h to} L ^3h in the structural formula (61) each independently represent a divalent linking group composed of an aromatic ring or a heteroaromatic ring which may have a substituent. .
Q represents a 1,3,5-benzenetriyl group or a nitrogen atom. n represents any integer of 1 or more.
In the structural formula (61), a, b and c each independently represent an integer of 0 or 1 or more, but when Q is a nitrogen atom, it represents any integer of 1 or more.

In the structural formula (60) and the structural formula (61), examples of the saturated alkyl group represented by R ^{1h to} R ^12h include linear, branched, and cyclic alkyl groups, and the number of carbon atoms is 1 to 30. Is preferable, and 1 to 20 is more preferable. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a 2-ethylhexyl group, a cyclohexyl group, and an octadecyl group.

When the alkyl group represented by R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61) has a substituent, examples of the substituent include a carboxyl group, a sulfo group, a cyano group, and a halogen atom (for example, Fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, Arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy) Group), carbon number of 30 or less Alkylthio group (for example, methylthio group, ethylthio group, methylthioethylthioethyl group, etc.), aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), Examples thereof include a nitro group, an alkyl group having 30 or less carbon atoms, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group.

  Acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), Acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, carbamoyl group, N , N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon An aryl group having a number of 30 or less (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group) , Diarylamino group, acylamino group, etc.), substituted urea De group, a substituted phosphono group, and a heterocyclic group. Here, the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in a salt state.

In the structural formula (60) and the structural formula (61), examples of the unsaturated alkyl group represented by R ^{1h to} R ^12h include linear, branched, and cyclic alkenyl groups. 2-30 are preferable and, as for the number of atoms, 2-20 are more preferable. The alkenyl group may be a substituted alkenyl group having a substituent or an unsubstituted alkenyl group. The preferred range of the number of carbon atoms in the alkenyl part of the substituted alkenyl group is the same as in the case of the alkenyl group. is there. Examples of the substituent for the substituted alkenyl group include the same substituents as those for the substituted alkyl group.

Furthermore, examples of the unsaturated alkyl group represented by R ^{1h to} R ^{12h in the} structural formula (60) and the structural formula (61) include linear, branched, and cyclic alkynyl groups, and the carbon of the alkynyl group. 2-30 are preferable and, as for the number of atoms, 2-20 are more preferable. The alkynyl group may be a substituted alkynyl group having a substituent or an unsubstituted alkynyl group, and the preferred range of the number of carbon atoms in the alkynyl part of the substituted alkynyl group is the same as in the case of the alkynyl group. is there. Examples of the substituent for the substituted alkynyl group include the same substituents as those for the substituted alkyl group.

Examples of the aralkyl group represented by R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61) include linear, branched, and cyclic aralkyl groups, and the number of carbon atoms is 7 to 30. 7-20 are more preferable. Specific examples include a benzyl group and a phenethyl group. The aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group.

As said aryl group which R ^{< 1h>} -R ^<12h> in the said Structural formula (60) and Structural formula (61) represents, C6-C30 is preferable and 6-20 are more preferable. Examples of such an aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like.

As said saturated alkyloxy group which R ^{< 1h>} -R ^<12h> in the said Structural formula (60) and Structural formula (61) represents, C1-C30 is preferable and 1-20 are more preferable. Examples of such an alkyloxy group include a methoxy group, an ethoxy group, a 2-ethylhexyloxy group, a phenoxyethoxy group, and the like. Examples of the unsaturated alkyloxy group include an alkenyloxy group and an alkynyloxy group, and the alkenyl group and alkynyl group have the same meanings as those of the aforementioned unsaturated alkyl group.

As said aralkyloxy group which R ^{< 1h>} -R ^<12h> in the said Structural formula (60) and Structural formula (61) represents, C7-C12 is preferable and 7-10 are more preferable. Examples of such aralkyloxy groups include benzyloxy group and phenethyloxy group.

As said aryloxy group which R ^{< 1h>} -R ^<12h> in the said Structural formula (60) and Structural formula (61) represents, C6-C30 is preferable and 6-20 are more preferable. Examples of such aryloxy groups include phenoxy group, 4-methylphenoxy group, α-naphthyloxy group and the like.

As said saturated alkylthio group which R ^{< 1h>} -R ^<12h> in the said Structural formula (60) and Structural formula (61) represents, C1-C30 is preferable and 1-20 are more preferable. Examples of such an alkylthio group include a methylthio group, an ethylthio group, an n-butylthio group, and a 2-ethylhexylthio group. Examples of the unsaturated alkylthio group include an alkenylthio group and an alkynylthio group, and the alkenyl group and alkynyl group have the same meanings as those of the aforementioned unsaturated alkyl group.

The aralkylthio group represented by R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61) preferably has 7 to 30 carbon atoms, and more preferably 7 to 20 carbon atoms. Examples of such an aralkylthio group include a benzylthio group and a phenethylthio group.

As said arylthio group which R ^{< 1h>} -R ^<12h> in the said Structural formula (60) and Structural formula (61) represents, C6-C30 is preferable and 6-20 are more preferable. Examples of such an arylthio group include a phenylthio group, a 4-methylphenylthio group, an α-naphthylthio group, and the like.

The dialkylamino group represented by R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61) is an amino group substituted by any two of the alkyl groups described above, and has 1 to 30 carbon atoms. preferable. Examples of such a dialkylamino group include a dimethylamino group, a diethylamino group, a dibutylamino group, a dioctylamino group, and a didecylamino group.

The diarylamino group represented by R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61) is an amino group substituted with any two of the aryl groups described above, and has 6 to 30 carbon atoms. preferable. Examples of such a diarylamino group include a diphenylamino group, a ditolylamino group, a dixylylamino group, a di-α-naphthylamino group, and a di-β-naphthylamino group.

Examples of the halogen atom represented by R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61) further represent an unsaturated nitrogen-containing heterocyclic group, and a nitrogen atom in the ring may be bonded to a benzene ring. The nitrogen-containing heterocyclic ring is a 5- to 7-membered unsaturated nitrogen-containing heterocyclic group which may have a substituent, and specific examples are shown below. The substitution position of the nitrogen-containing heterocycle is preferably any one of R ^2h , R ^3h , R ^6h , R ^7h , R ^10h and R ^{11h in} the structural formula (60) and the structural formula (61). Moreover, as a preferable substituent, an alkyl group, an aryl group, an alkoxy group, a dialkylamino group, and a diarylamino group are mentioned.

In addition, the groups of R ^{1h to} R ^{12h in} the structural formula (60) and the structural formula (61) may form a saturated or unsaturated ring together with adjacent groups. Examples of such saturated or unsaturated rings include a tetrahydroquinoline ring and a julolidine ring.

In the structural formula (60) and the structural formula (61), the monosubstituted nitrogen atom represented by X ^h , Y ^h , or Z ^h is a nitrogen atom substituted with an alkyl group or an aryl group, and an alkyl on the nitrogen atom A group and an aryl group are synonymous with the said alkyl group and aryl group represented by R ^{< 1h>} -R ^<12h> .

In the above structural formula (60) and structural formula (61), the divalent aromatic ring group which may have a substituent represented by P and L ^{1h to} L ^3h is a divalent aromatic ring group shown below. Can be mentioned.

  Among the above structural formulas, the divalent aromatic ring groups shown below are particularly preferable.

In the structural formula (60) and structural formula (61), the divalent heteroaromatic ring group which may have a substituent represented by P and L ^{1h to} L ^3h is a divalent heteroaromatic group shown below. A cyclic group is mentioned.

  Among the above structural formulas, the divalent heteroaromatic ring groups shown below are particularly preferable.

Here, R ^13h , R ^15h and R ^16h represent a lower alkyl group, and R ^14h has the same ^meaning as the group represented by R ^{1h to} R ^12h in the structural formula (60) and the structural formula (61). .

In Structural Formula (60) and Structural Formula (61), n represents any integer of 1 or more, and 1, 2, and 3 are particularly preferable. When n represents an integer of 2 or more, the P may be a combination of an aromatic ring and a heteroaromatic ring. In the structural formula (60) and the structural formula (61), when a, b and c represent an integer of 1 or more, the substituents represented by L ^{1h to} L ^3h may be different from each other.

  Specific examples (Exemplary Compound Nos. 1 to 57) of the compound represented by Structural Formula (60) or Structural Formula (61) are shown below, but the invention is not limited thereto.

  The fluorescent brightening agent not only improves the sensitivity of the photosensitive layer, but also has a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation.

<Other ingredients>
Examples of other components in the photosensitive composition as the resist for circuit formation include known surfactants, plasticizers, color formers, colorants and the like, and further adhesion promoters and other assistants to the substrate surface. Combined use of agents (for example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) May be. By appropriately containing these components, it is possible to adjust properties such as stability, photographic properties, print-out properties, and film physical properties of the intended photosensitive layer (the pattern forming material).

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

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

(2) Color former The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound which does not have oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane, but can be oxidized to a coloring compound; Id dyes; U.S. Pat. Nos. 3,042,515 and 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole), and among these, triarylmethane compounds such as leuco crystal violet are preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4- Chlorophenyl) ethane); halogenated alcohol compounds (eg, 2,2,2-trichloroethanol, Bromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) Di (2-bromoethyl) ether, 1,2- Chloroethyl ethyl ether, etc.); halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); a compound having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitro) Phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

  As content of the said color former, 0.01-20 mass% is preferable with respect to all the components of the said photosensitive composition, 0.05-10 mass% is more preferable, 0.1-5 mass% is especially preferable. preferable. Moreover, as content of the said halogen compound, 0.001-5 mass% is preferable with respect to all the components of the said photosensitive composition, and 0.005-1 mass% is more preferable.

(3) Colorant The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include red, green, blue, yellow, purple, magenta, cyan, and black. Examples of such pigments and dyes include Victoria Pure Blue BO (C.I. 42595), Auramin (C.I. 41000), Fat Black HB (C.I. 26150), Mono Light Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (C Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Le Bee FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1) and carbon black can be mentioned.

Examples of the colorant suitable for producing a color filter include C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 83, C.I. I. Pigment violet 23, and those described in JP-A-2002-162752 (0138) to (0141).
There is no restriction | limiting in particular as an average particle diameter of the said coloring agent, Although it can select suitably according to the objective, For example, 5 micrometers or less are preferable and 1 micrometer or less is more preferable. Moreover, when producing a color filter, as said average particle diameter, 0.5 micrometer or less is preferable.

  As content of the said coloring agent, 0.01-5 mass% is preferable with respect to all the components of the said photosensitive composition, 0.05-3 mass% is more preferable, 0.1-2 mass% is especially preferable. preferable.

(4) Dye A dye can be used in the photosensitive composition for the purpose of improving handleability or imparting storage stability.
Examples of the dye include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein. , Methyl violet 2B, quinaldine red, rose bengal, metanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzo Purpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuxin, oil blue # 603 (Orien Chemical Co., Ltd.), Rhodamine B, Rhodamine 6G, etc. Victoria Pure Blue BOH can be cited, among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, for example, a residue such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid ( Anion) and the like.

  As content of the said dye, 0.001-10 mass% is preferable with respect to all the components of the said photosensitive composition, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable. .

(5) Adhesion promoter In the photosensitive composition, the adhesion of the photosensitive layer formed using the photosensitive composition (adhesion with other layers when used as the pattern forming material, or with the substrate) In order to improve the (adhesion), a known so-called adhesion promoter can be used for each layer.

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

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

  The photosensitive composition is, for example, J.P. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Is mentioned.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

(6) Surfactant A known surfactant can be added to the photosensitive composition in order to improve surface unevenness that occurs when the photosensitive layer is formed.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

As content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the said photosensitive composition.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.

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

As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable.
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.

[Solder resist]
The photosensitive composition as the solder resist includes at least a binder, a polymerizable compound, a photopolymerization initiator, a carbon-based nanomaterial, and a thermal crosslinking agent, and other sensitizers and the like appropriately selected as necessary. Contains the ingredients.

<Carbon-based nanomaterials>
As the carbon-based nanomaterial used for the photosensitive composition as the solder resist, the same carbon-based nanomaterials as those exemplified as the carbon-based nanomaterial contained in the photosensitive composition as the circuit forming resist can be used.
The content of the carbon-based nanomaterial contained in the photosensitive composition as the solder resist is preferably 0.0001% by mass to 10% by mass, and 0.0005% by mass with respect to the entire photosensitive composition. More preferably, it is -5 mass%, and it is still more preferable that it is 0.001 mass%-1 mass%.
If the content is less than 0.0001% by mass, it tends to be affected by external environmental factors such as fluctuations in environmental temperature, and the variation in line width may increase. On the contrary, the scattering of light increases and the variation in line width may increase.

<Binder>
The binder used in the photosensitive composition as the solder resist is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-51-131706, JP-A-52-94388, Epoxy acrylate compounds having an acidic group described in JP-A No. 64-62375, JP-A-2-97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296976, and the like, , Vinyl copolymers having (meth) acryloyl group and acidic group in the side chain, vinyl copolymers having epoxy acrylate compound and (meth) acryloyl group and acidic group in the side chain, maleic anhydride copolymer, etc. It is done.
Moreover, the thing similar to what was illustrated as a binder contained in the said photosensitive composition as said resist for circuit formation can be used.

  The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained by, for example, a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.

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

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

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

  Also, compounds obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 can be used as the epoxy acrylate of the present invention.

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

  An acrylic resin having at least one polymerizable group such as an acidic group or a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or (meth) acrylamide group, various polymerizations such as vinyl ester of carboxylic acid, vinyl ether, allyl ether Sex double bonds can be used. More specifically, acrylic resins containing carboxyl groups as acidic groups, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexene oxide in the same molecule (meth) Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an acryloyl group. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate.

  Furthermore, as the binder, a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain can be used. Specifically, for example, (1) a vinyl monomer having an acidic group, (2) (Co) heavy obtained by vinyl (co) polymerization of a vinyl monomer having a functional group that can be used in the polymer reaction described later, if necessary, and (3) other copolymerizable vinyl monomers as necessary And (4) a (meth) acryloyl group and a functional group having reactivity with at least one of an acidic group in the (co) polymer or a functional group available for polymer reaction. It is obtained by polymer-reacting with a compound having it.

There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has said (1) acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, These Among these, a carboxyl group is preferable. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and a monomer having a hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono ( And (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  In the vinyl monomer having a functional group usable for the polymer reaction of (2), the functional group usable for the polymer reaction is a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. Moreover, the carboxyl group and acid anhydride group of the above-mentioned (1) are also mentioned as usable functional groups.

  Examples of the vinyl monomer having a hydroxyl group include compounds represented by the structural formulas (4) to (12).

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

  Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (1) to (3).

  Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (62).

However, in the structural formula (62), R ^j represents a hydrogen atom or a methyl group.

Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
Moreover, each said monomer may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

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

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

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

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

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

Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (1) to (3), as in the above-described (2).
Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.
Examples of the monomer having a hydroxyl group include compounds represented by the structural formulas (4) to (12) as in the above-described (2).

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

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

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

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

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

Examples of commercially available binders include “Kaneka Resin AX; manufactured by Kaneka Chemical Co., Ltd.”, “CYCLOMER A-200; manufactured by Daicel Chemical Industries, Ltd.”, and “CYCLOMER M”. -200; manufactured by Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; manufactured by Showa Polymer Co., Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 Polyimide precursors described in Japanese Patent Laid-Open No. 11-282155, and the like can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), amide group-containing styrene / acid anhydride copolymer, or polyimide precursor is preferably 3,000 to 500,000, 5,000-100,000 are more preferable. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

As the binder, a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer can also be used. The copolymer is a maleamic acid copolymer having at least a maleamic acid unit B having a maleic acid half amide structure and a unit A not having the maleic acid half amide structure, represented by the following structural formula (63). It is preferably a coalescence.
The unit A may be one type or two or more types. For example, assuming that the unit B is one type, when the unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit A is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
The unit A is an aryl group which may have a substituent and a vinyl monomer described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with the vinyl monomer (c) is preferred.

However, in said structural formula (63), R ^<3i> and R ^<4i> represent either a hydrogen atom or a lower alkyl group. x and y represent the mole fraction of the repeating unit. For example, when the unit A is one, x is 85 to 50 mol%, and y is 15 to 50 mol%.

In the structural formula (63), as R ¹ⁱ , for example, (—COOR ¹⁰ⁱ ), (—CONR ¹¹ⁱ R ¹²ⁱ ), an aryl group which may have a substituent, (—OCOR ¹³ⁱ ), (—OR ¹⁴ⁱ ), a substituent such as ( ^-COR15i ). Here, each of R ^{10i to} R ¹⁵ⁱ independently represents any of a hydrogen atom (—H), an optionally substituted alkyl group, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{10i to} R ¹⁵ⁱ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, and cyclohexyl. 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.
Specific examples of R ^{1i in} the structural formula (63) include benzene such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, and 2,4-dimethylphenyl. Derivatives: n-propyloxycarbonyl, n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

^Examples of R ²ⁱ in Structural Formula (63) include an alkyl group, an aryl group, and an aralkyl group that may have a substituent. These may have a cyclic structure or a branched structure. Specific examples of R ² include, for example, benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, and α-methyl. Benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) Ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) Til, 4-fluoro-α, α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl, Ethyl, propyl, i-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3 -Methoxypropyl, 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropylamine and the like.

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

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

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

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

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

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

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), a compound obtained by reacting an anhydride group of the maleic anhydride copolymer with a primary amine compound, or a binder such as a polyimide precursor, 3,000 to 500,000 are preferable, and 5,000 to 100,000 are more preferable. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

  5-80 mass% is preferable and, as for solid content content in the said photosensitive composition of the said binder, 10-70 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 50% by mass, the exposure sensitivity is increased. May decrease.

<Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, the polymerizable compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. The compound is preferable, and the same compounds as those exemplified as the polymerizable compound contained in the photosensitive composition as the circuit forming resist can be used. For example, the compound is selected from monomers having a (meth) acryl group. Suitable examples include at least one of the above.

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

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

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected depending on the purpose. For example, the photosensitive composition as the circuit forming resist The thing similar to what was illustrated as a photoinitiator contained in a thing can be used.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferred examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which can handle laser light having a wavelength of 405 nm in the later-described exposure. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

  As solid content in the said pattern formation material of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose.For example, in order to improve the film strength after curing of the photosensitive layer, it does not adversely affect developability, for example, An epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
Examples of the epoxy compound having at least two oxirane rings in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, odor Phenol novolac type epoxy resin), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (phthalic acid diglycidyl ester) Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4 Poxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.” HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin A reaction product of 4-vinylcyclohexene-1-oxide obtained by epoxidation with peracetic acid, an epoxy resin having a linear phosphorus-containing structure, an epoxy resin having a cyclic phosphorus-containing structure, α-methylstilbene Type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP- 5 0S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

In the structural formula (i), R ^k represents one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 20.
In the structural formula (ii), R ^k represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^m represents any one of a hydrogen atom and CH ₃ , and n represents any of 0 to 20 Represents an integer.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

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

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

  Solid content in the said photosensitive composition of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

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

Further, for the purpose of improving the storage stability of the pattern forming material having a photosensitive layer formed using the photosensitive composition of the present invention, a blocking agent is reacted with the isocyanate group of the polyisocyanate and its derivative. You may use the compound obtained by this.
Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert.-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert.-butylphenol, p -Sec.-butylphenol, p-sec.-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, Dialkyl malonate, methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetooxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

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

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

<Other ingredients>
Examples of other components in the photosensitive composition as the solder resist include extender pigments, colorants (color pigments or dyes), and further adhesion promoters to the substrate surface and other auxiliary agents ( For example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination.
These components may be the same as those contained in the photosensitive composition as the circuit forming resist. By appropriately containing these components, the stability, photographic properties, and film physical properties of the intended photosensitive layer are included. Etc. can be adjusted.

-Extender pigment-
The extender pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include inorganic pigments and organic fine particles.
In the photosensitive composition as the solder resist, if necessary, it is possible to improve the surface hardness of the permanent pattern or keep the coefficient of linear expansion low, or keep the dielectric constant or dielectric loss tangent of the cured film itself low. For the purpose, the inorganic pigment and organic fine particles can be added.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.

The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

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

(Pattern forming material)
The pattern forming material has at least a support and a photosensitive layer made of the photosensitive composition of the present invention on the support, and is laminated with other appropriately selected layers such as a cushion layer according to the purpose. Do it.
The photosensitive composition includes a photosensitive composition of any one of the circuit forming resist and the solder resist.

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

The material of the support is preferably made of a synthetic resin and transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester , Poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, Various plastic films such as polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

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

<Photosensitive layer>
The photosensitive layer is formed from the photosensitive composition. There is no restriction | limiting in particular as a location provided in the said pattern formation material of the said photosensitive layer, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body.
The photosensitive layer may be a single layer or a plurality of layers.

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

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

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

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

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

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

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

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

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesion of the pattern forming material is not particularly limited and can be appropriately selected depending on the purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. By setting such an interlayer adhesive strength, the support and the cushion layer are peeled from the laminate, and the photosensitive layer is exposed, and then the photosensitive layer can be developed using an alkaline developer. Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer can be peeled from the laminate, and the photosensitive layer can be developed using an alkaline developer.

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

There is no restriction | limiting in particular as an ethylene copolymerization ratio in the copolymer which uses the said ethylene as an essential copolymerization component, Although it can select suitably according to the objective, For example, 60-90 mass% is preferable, 60- 80 mass% is more preferable, and 65-80 mass% is especially preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are very easily peeled off, including the cushion layer. It may be difficult to manufacture the pattern forming material.

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

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

-Protective film-
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said pattern formation material of the said protective film, According to the objective, it can select suitably, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

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

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

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

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

  Next, the photosensitive resin composition solution is applied onto the substrate or the support and dried to form a photosensitive layer, whereby a pattern forming material can be produced.

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

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least a photosensitive layer made of the photosensitive composition of the present invention on the substrate and other layers appropriately selected according to the purpose.
As the photosensitive layer in the photosensitive laminate, any of a resist layer for circuit formation made of the photosensitive composition as the resist for circuit formation and a solder resist layer made of the photosensitive composition as the solder resist. These are preferably photosensitive layers formed of the pattern forming material.

<Substrate>
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 pattern forming material of the present invention is transferred, and is not particularly limited, and is appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a substrate for producing a known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, and a metal plate.

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

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

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

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

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

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, a laminator (For example, Taisei Laminator company make, VP-II) etc. are mentioned suitably.

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

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

[Exposure process]
The said exposure process is a process of exposing with respect to the said photosensitive layer in the photosensitive laminated body of this invention. Examples of the photosensitive layer in the photosensitive laminate of the present invention include a photosensitive layer formed from the photosensitive composition of the present invention and a photosensitive layer transferred from the pattern forming material.
The exposure step is a step of forming a two-dimensional pattern on the exposed surface by exposing the exposure head and the exposed surface of the photosensitive layer by relative scanning while modulating light according to pattern information. Yes, the exposure is maskless exposure. The exposure head includes at least light irradiation means and light modulation means. The relative scanning is performed by moving at least one of the exposure head and the photosensitive layer.
Light irradiation may be performed before or after the substrate transfer, but exposure after the transfer is preferable from the viewpoint of preventing misalignment.

  The maskless exposure (also referred to as “maskless pattern exposure”) refers to the exposure head and the photosensitive layer covered while modulating the light from the light irradiation means based on pattern information (also referred to as “image data”). In this exposure method, a two-dimensional pattern (also referred to as “image”) is formed on the exposed surface of the photosensitive layer by performing relative scanning with the exposed surface. On the other hand, in the conventional exposure method using a mask, a mask formed with a pattern using a material that does not transmit exposure light or a material that transmits exposure light by weakening the exposure light is used as an optical path on the exposed surface of the photosensitive layer. It is the method of arrange | positioning and performing exposure.

  The light source of light emitted from the light irradiation means is not particularly limited and can be appropriately selected according to the purpose. For example, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a copying machine, etc. Fluorescent tubes, LEDs, and laser beams (semiconductor lasers, solid state lasers, liquid lasers, gas lasers), etc., among these, ultra-high pressure mercury lamps and laser beams are preferable, and light on / off control can be performed in a short time, From the viewpoint of easy light interference control, laser light is more preferable.

  There is no restriction | limiting in particular as a wavelength of the said light source, Although it can select suitably according to the objective, For example, as an ultra-high pressure mercury lamp, i line | wire (365 nm) is preferable, As a solid laser, YAG-SHG solid is preferable. A laser (532 nm) and a semiconductor excitation solid-state laser (532 nm, 355 nm, 266 nm) are preferable. As a gas laser, a KrF laser (249 nm) and an ArF laser (193 nm) are preferable. The semiconductor laser is preferably 300 to 500 nm, more preferably 340 to 450 nm, and particularly preferably 405 nm or 410 nm from the viewpoints of shortening the exposure time of the photosensitive composition and easy availability. .

The beam diameter of the laser beam is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of resolution in the photosensitive layer, a 1 / e ² value of a Gaussian beam is preferably 5 to 30 μn, 7-20 micrometers is more preferable.
The amount of light energy of the laser light is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 100 mJ / cm ² from the viewpoint of shortening the exposure time and resolution. 20 mJ / cm ² is more preferable.

The light source is preferably a bundle-shaped fiber light source in which a plurality of optical fibers that enter light from one end and emit the incident light from the other end are bundled, and the optical fiber receives two or more light from the light source. More preferably, the combined laser beam can be emitted.
There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of combining and irradiating a combined laser beam with a lens system that collects light and couples it to the multi-mode optical fiber is exemplified.

  In the exposure step, the light modulating means for modulating the light from the light irradiating means is a two-dimensional shape of n (where n is a natural number of 2 or more) that receives and emits the light from the light irradiating means. There is no particular limitation as long as it has arranged picture element parts and the picture element parts can be controlled based on pattern information, and can be appropriately selected according to the purpose. For example, a spatial modulation element And an optical polygon mirror (polygon mirror).

The spatial light modulation element is not particularly limited and may be appropriately selected depending on the intended purpose. However, a digital micromirror device (DMD) or a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM) may be used. Preferred examples include a special light modulator, a mirror gradation type spatial modulation element, an optical element that modulates transmitted light by an electro-optic effect (PLZT element), and a liquid crystal light shutter (FLC).
Note that MEMS is a general term for a micro system that integrates micro-sized sensors, actuators, and control circuits based on a micro-machining technology using an IC manufacturing process as a substrate. It means a spatial light modulator driven by electromechanical operation using Further, a plurality of Grading Light Valves (GLVs) arranged in two dimensions can be used. In the configuration using these reflective spatial light modulators (GLV) and transmissive spatial light modulators (LCD), a lamp or the like can be used as the light source in addition to the laser.
Among these spatial light modulation elements, DMD and mirror gradation type spatial modulation elements are more preferable, and DMD is particularly preferable.

  The optical polygon mirror (polygon mirror) is a rotating member having a plurality of (for example, six) plane reflecting surfaces, and is not particularly limited as long as light can be scanned by rotation. Can be selected as appropriate. In the exposure using the optical polyhedron (polygon mirror), the exposed surface of the photosensitive layer is moved at a right angle to the scanning direction of the optical polyhedron (polygon mirror), so that the front surface of the exposed surface is moved. Can be exposed.

In the exposure step, the method for exposing the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include digital exposure and analog exposure, but digital exposure is preferred. .
The digital exposure method is not particularly limited and may be appropriately selected depending on the purpose. For example, the digital exposure method is performed using laser light modulated according to a control signal generated based on predetermined pattern information. Is preferred.
Furthermore, in the exposure step, the method for exposing the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of enabling high-speed exposure in a short time, It is preferably carried out while relatively moving the photosensitive layer, and particularly preferably used in combination with the digital micromirror device (DMD).

The exposure step is preferably performed in an inert gas atmosphere. The method for exposing the photosensitive layer formed in the photosensitive layer forming step is not particularly limited and can be appropriately selected according to the purpose. For example, a method of directly spraying an inert gas on the surface of the photosensitive layer, A sample on which a photosensitive layer to be exposed is placed in an exposure space in a sample table in which one side of the frame-shaped frame is opened and an inert gas introduction hole is formed on at least one remaining side. Examples thereof include a method of performing exposure while introducing an inert gas from an active gas introduction hole and covering the surface of the photosensitive layer with an inert gas.
In addition, it is possible to introduce an inert gas into the sealed space under reduced pressure using the exposure space as a sealed space.
The inert gas is not particularly limited as long as it can prevent the polymerization reaction of the photosensitive layer from being inhibited by the influence of oxygen, and can be appropriately selected according to the purpose. For example, nitrogen, helium, argon, etc. Is mentioned.

Hereinafter, an embodiment of a method for producing a color filter of the present invention and an exposure apparatus suitably used for the method for producing the color filter will be described with reference to the drawings.
As the exposure apparatus, in addition to a so-called flat bed type exposure apparatus, an outer drum type exposure apparatus in which a photosensitive material is wound around the outer peripheral surface of the drum, and an inner drum type in which the photosensitive material is mounted on the inner peripheral surface of the cylinder The exposure apparatus may be used. Hereinafter, a flat bed type exposure apparatus will be described as an example.

<Exposure device>
As shown in FIG. 1, the exposure apparatus adsorbs to the surface a laminate 12 (hereinafter referred to as “photosensitive layer 12” or “photosensitive material 12”) formed by laminating the photosensitive layer on the substrate. A flat moving stage 14 is provided. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The exposure apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

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

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

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

  When the sub scanning of the photosensitive layer 12 by the scanner 24 is completed and the rear end of the photosensitive layer 12 is detected by the sensor 26 (or the camera 26), the stage 14 is moved along the guide 20 by the stage driving device 304. It returns to the origin on the most upstream side of the gate and is moved again along the guide 20 from the upstream side to the downstream side of the gate 22 at a constant speed.

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

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

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

  In the position below each slit 28 in the stage 14, when performing N double exposure, a pixel unit is used in a later-described used pixel part specifying process for selecting a pixel part in order to realize an ideal N double exposure. A single cell type photodetector (not shown) as a light spot position detecting means for detecting a light spot may be incorporated. Further, the photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in a used pixel part specifying process described later.

  The operation mode of the exposure apparatus at the time of exposure may be a mode in which exposure is continuously performed while the exposure head is constantly moved, or at each movement destination position while the exposure head is moved stepwise. The exposure head may be stationary and the exposure operation may be performed.

  The exposure method is preferably performed while relatively moving the exposure light and the photosensitive layer, and in this case, it is preferable to use the high-speed modulation together. Thereby, high-speed exposure can be performed in a short time.

<< Exposure head >>
An example of a schematic configuration of the exposure head 30 is shown in FIGS. 4, 5A, and 5B. 4, 5 </ b> A, and 5 </ b> B, each component is shown along an optical path of light propagating through the exposure head 30.
In this example, a DMD 36 (manufactured by Texas Instruments Inc., USA) is provided as light modulation means (spatial light modulation element that modulates each pixel part) according to image data in accordance with image data. As a light irradiation means, a fiber array light source 38 is provided.

As shown in FIG. 4, on the light incident side of the DMD 36, there is provided a laser emitting portion in which the emission end portion (light emitting point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32. The fiber array light source 38, the condensing lens system 40 that corrects the laser light emitted from the fiber array light source 38 and condenses the light on the DMD, and reflects the laser light transmitted through the condensing lens system 40 toward the DMD 36. The mirrors 42 are arranged in this order. In FIG. 4, the condensing lens system 40 is schematically shown.
Further, an imaging lens system 50 that images the laser light reflected by the DMD 36 on the exposure surface of the photosensitive layer 12 is disposed on the light reflection side of the DMD 36. In FIG. 4, the imaging lens system 50 is schematically shown.

For example, as shown in FIGS. 5A and 5B, the condensing lens system 40 includes a pair of combination lenses 44 for collimating the laser light emitted from the fiber array light source 38, and the collimated laser light. It is composed of a pair of combination lenses 46 for correcting the light quantity distribution to be uniform, and a condensing lens 48 for condensing the laser light whose light quantity distribution is corrected on the DMD 36, and further includes other members and the like which will be described later. .
The imaging lens system 50 includes, for example, two lenses 52 and 54 arranged so that the DMD 36 and the exposure surface of the photosensitive layer 12 have a conjugate relationship, and further includes a microlens array and an aperture array. And other lens groups described later.

-Light modulation means-
As shown in FIG. 6, the DMD 36 as the light modulating means has a large number of micromirrors 58 arranged in a lattice form on the SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). This is a mirror device. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (integrated).

When an image signal representing the density of each point constituting a desired two-dimensional pattern in binary is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the column is centered on the diagonal line. As shown in FIG. 2, the angle is inclined to ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed. FIG. 7A shows a state in which the micromirror 58 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 58 is tilted to −α degrees in the off state. Thus, by controlling the tilt of the micromirror 58 in each pixel of the DMD 36 according to the image signal, the laser light B incident on the DMD 36 is reflected in the tilt direction of each micromirror 58.
The on / off control of each micromirror 58 is performed by the controller 302 of FIG. 8 connected to the DMD 36. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

  Further, it is preferable that the DMD 36 is disposed with a slight inclination so that the short side forms a predetermined angle θ (for example, 0.1 ° to 5 °) with the sub-scanning direction. 9A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 36 is not tilted, and FIG. 9B shows the scanning trajectory of the exposure beam 53 when the DMD 36 is tilted.

In the DMD 36, a number of micromirror arrays in which a number of micromirrors are arranged in the longitudinal direction (for example, 1024) are arranged in a short direction (for example, 756 pairs). , by inclining the DMD 36, the pitch P ₂ of the scanning locus of the exposure beams 53 from each micromirror (scan line), becomes narrower than the pitch P ₁ of the scanning line in the case of not tilting the DMD 36, greatly improve the resolution be able to. On the other hand, since the inclination angle of the DMD 36 is minute, the scanning width _{W 2} in the case of tilting the DMD 36, is substantially equal to the scanning width _{W 1} when not inclined DMD 36.

By exposing the same scanning line on different micromirror rows in an overlapping manner, it is possible to control a minute amount of the exposure position with respect to the alignment mark, realizing high-definition exposure, and arranging in the main scanning direction It is possible to connect the joints between the plurality of exposure heads (joint areas between the heads) without any step by a very small amount of control.
The same effect can be obtained even if each micromirror array is shifted by a predetermined interval in the direction orthogonal to the sub-scanning direction and arranged in a zigzag pattern as shown in FIG. 10 instead of inclining the DMD.

  As shown in FIG. 10, the entire surface of the photosensitive layer 12 may be exposed by one scanning in the X direction by the scanner 24. As shown in FIGS. 11A and 11B, the photosensitive layer 12 is removed by the scanner 24. After scanning in the X direction, the scanner 24 is moved one step in the Y direction, and scanning in the X direction is repeated, so that the entire surface of the photosensitive layer 12 is exposed by a plurality of scans. May be.

-Light irradiation means-
As a suitable example of the light irradiating means, a means capable of irradiating a combined laser, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated from each of the plurality of lasers to collect the multimode. A means (fiber array light source) having a lens system coupled to an optical fiber will be described.

  As shown in FIG. 12, the fiber array light source 38 includes a plurality of (for example, 14) laser modules 60, and one end of a multimode optical fiber 62 is coupled to each laser module 60. An optical fiber 64 having a cladding diameter smaller than that of the multimode optical fiber 62 is coupled to the other end of the multimode optical fiber 62. As shown in detail in FIG. 13, seven ends of the optical fiber 64 opposite to the multimode optical fiber 62 are arranged along the direction orthogonal to the scanning direction, and these are arranged in two rows to form the laser emitting unit 66. Is configured.

  As shown in FIG. 13, the laser emitting portion 66 constituted by the end portion of the optical fiber 64 is sandwiched and fixed between two support plates 68 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the optical fiber 64 for protection. The light exit end face of the optical fiber 64 has a high light density and is likely to collect dust and easily deteriorate. However, by arranging the protective plate as described above, it is possible to prevent the dust from adhering to the end face and to delay the deterioration. Can do.

  For example, as shown in FIG. 14, an optical fiber 64 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip of the multimode optical fiber 62 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 64 is fused and joined to the outgoing end face of the multimode optical fiber 62 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 64 a of the optical fiber 64 is the same as the diameter of the core 62 a of the multimode optical fiber 62.

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

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

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

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

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

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

  As shown in FIGS. 16 and 17, the combined laser light source is housed in a box-shaped package 400 having an upper opening together with other optical elements. The package 400 includes a package lid 410 manufactured so as to close the opening. After the degassing process, a sealing gas is introduced, and the package 400 and the package lid are closed by closing the opening of the package 400 with the package lid 410. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the reference numeral 410.

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

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

  16 and 17, in order to avoid complication of the drawings, only the GaN semiconductor laser LD7 among the plurality of GaN semiconductor lasers is numbered, and only the collimator lens L7 among the plurality of collimator lenses. It is numbered.

  FIG. 18 shows a front shape of a mounting portion of the collimator lenses L1 to L7. Each of the collimator lenses L <b> 1 to L <b> 7 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses L1 to L7 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 18).

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

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

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

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

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

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

  Further, as the light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 19, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on the heat block 110. An array can be used. Further, a chip-shaped multicavity laser 111 in which a plurality of (for example, five) light emitting points 111a shown in FIG. 20A are arranged in a predetermined direction is known. Since the multicavity laser 111 can arrange the light emitting points with higher positional accuracy than the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multi-cavity laser 111 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 111a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 20B, a plurality of multi-cavity lasers 111 are arranged on the heat block 110 in the same direction as the arrangement direction of the light emitting points 111a of each chip. A multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 21, a combined laser light source including a chip-shaped multicavity laser 111 having a plurality of (for example, three) light emitting points 111a can be used. The combined laser light source includes a multi-cavity laser 111, a single multi-mode optical fiber 62, and a condenser lens 200. The multicavity laser 111 can be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

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

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

  Further, as shown in FIG. 22, a multi-cavity laser 111 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 111 are equally spaced on the heat block 110. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 111 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 111a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 111, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 62, and a condenser lens 200 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

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

  Still another example of the combined laser light source will be described. As shown in FIGS. 23A and 23B, this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180, and is stored between two heat blocks. A space is formed. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 111 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 111a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

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

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

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

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

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

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

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

-Brightness-
In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array A combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained for each of the fibers 64. Therefore, the output at the laser emitting section in which the six optical fibers 64 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emission part of the fiber array light source, high-luminance light emitting points are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has a low output, so that a desired output cannot be obtained unless multiple rows are arranged. Since the laser light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. In addition, since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion is 1.6 × 10 ⁶ (W / m ² ), which is per optical fiber. The luminance of is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, when the light irradiating means is a means capable of irradiating a combined laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion is Since it is 0.0081 mm ² (0.325 mm × 0.025 mm), the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), and the luminance is increased by about 80 times compared to the conventional case. Can do. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared to the conventional one.

-Depth of focus-
Here, with reference to FIG. 24A and FIG. 24B, the difference in the depth of focus between the conventional exposure head and the exposure head of the present embodiment will be described. The diameter of the light emission region of the bundled fiber light source of the conventional exposure head in the sub-scanning direction is 0.675 mm, and the diameter of the light emission region of the fiber array light source of the exposure head in the sub-scanning direction is 0.025 mm. As shown in FIG. 24A, in the conventional exposure head, since the light emitting area of the light irradiation means (bundle-shaped fiber light source) 38a is large, the angle of the light beam incident on the DMD 36 becomes large, and as a result, the scanning surface (photosensitive layer 12). The angle of the light beam incident on becomes larger. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 24B, in the exposure head of the exposure apparatus of the present invention, the diameter of the light emitting area of the fiber array light source 38b is small in the sub-scanning direction. As a result, the angle of the light beam incident on the scanning surface (photosensitive layer 12) is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. The DMD is a reflective spatial light modulator, but FIGS. 24A and 24B are developed views for explaining the optical relationship.

[Light intensity distribution correction method]
In a digital exposure apparatus provided with the light modulation means, it is important that the light quantity of each drawing unit in the exposure head is uniform in order to form a fine pattern with high accuracy in each drawing unit. However, in practice, the light beam emitted from the exposure head has a problem that the light intensity in the peripheral portion is lower than the central portion of the optical axis due to the lens system.
Therefore, a method for correcting the light amount distribution of the light emitted from the light irradiation unit to the light modulation unit and correcting the light amount distribution of the exposure light on the exposed surface will be described below.

  The light amount distribution correcting method is to provide a distribution of light amount in an irradiation region of light irradiated from the light irradiation unit to the light modulation unit by a condensing lens system, and to cover the photosensitive layer of the light modulated by the light modulation unit. This is a method for correcting the light amount distribution on the exposure surface to be uniform, and the first and second embodiments described below are preferable.

-First embodiment-
A projection optical system is provided on the light reflection side of the DMD, and this projection optical system projects a light source image on the photosensitive layer on the exposure surface on the light reflection side of the DMD, so that in order from the DMD side to the photosensitive layer. , An optical member for each exposure of a lens system, a microlens array, and an objective lens system is arranged.
The lens system and the objective lens system are configured as a magnifying optical system in which a plurality of lenses (such as a convex lens and a concave lens) are combined, and magnify the cross-sectional area of the laser beam (light beam) reflected by the DMD. Thus, the area of the exposure area on the photosensitive layer by the laser beam reflected by the DMD is enlarged to a predetermined size. The photosensitive layer is disposed at the back focal position of the objective lens system.

  Normally, the light amount (light intensity) distribution of this light beam is lower in the peripheral portion than in the central portion of the optical axis due to factors of the lens system. However, the exposure head of this embodiment includes a fiber array light source. In order to make the light quantity distribution of the emitted laser light uniform and irradiate the DMD, a rod integrator is provided in a condensing lens system arranged on the optical path on the light incident side of the DMD. However, even with this rod integrator, in the system in which each drawing unit is condensed by the microlens array as in this embodiment, the light intensity in the peripheral portion with respect to the central portion of the optical axis is significantly reduced, and image exposure can be performed with higher accuracy. In this case, it is difficult to correct the light quantity distribution to the required accuracy. In order to improve the correction accuracy of this light quantity distribution, it is conceivable to lengthen the rod integrator, but in that case, the rod integrator is a very expensive optical component, so the device cost increases, There is an adverse effect that the exposure head becomes larger.

  On the other hand, in the exposure head of the present embodiment, as described above, the laser light incident from the fiber array light source 38 to the condensing lens system has a distribution in the angle of the principal ray and is a peripheral portion compared to the optical axis center. Therefore, the light intensity distribution in the laser light irradiation area of the DMD is higher than that at the center of the optical axis because the light is emitted from the condenser lens system and emitted to the DMD. It is done. Therefore, when the light beam modulated for each pixel by the DMD passes through the microlens array having the characteristic of reducing the amount of transmitted light from the center of the optical axis to the periphery, and is irradiated onto the exposure surface of the photosensitive layer. The light amount distribution of the light beam on the exposure surface is corrected to be uniform.

-Second Embodiment-
The second embodiment is similar to the first embodiment by providing a telecentric optical system having an aspheric lens in the condenser lens system in the exposure head of the exposure apparatus according to the first embodiment described above. This is a technique for uniformizing the light quantity distribution of the light beam on the exposure surface.

  In the exposure head according to the second embodiment, for example, a concentrating lens system is provided with a telecentric optical system constituted by a pair of plano-convex lenses in a condensing lens system. It is arranged between the optical lenses.

  The plano-convex lens is an aspheric lens having a convex surface formed in an aspheric shape. The plano-convex lens arranged on the laser beam incident side (fiber array light source side) has an aspherical surface in which the surface shape of the incident surface increases as the radius of curvature increases from the optical axis (center of the optical axis). The aspheric surface becomes smaller as the distance from the optical axis X increases, and the exit surface is planar. In addition, the plano-convex lens disposed on the laser beam emission side (DMD side) has an aspherical surface in which the incident surface is flat and the surface shape of the emission surface decreases as the radius of curvature increases from the optical axis X. For example, the aspherical surface has a curvature that increases as the distance from the optical axis X increases.

[Focus position accuracy correction method]
The curvature of field, astigmatism, distortion and the like of the projection lens constituting the imaging lens system have a problem that the telecentricity is lowered and the focus position accuracy of the exposure light is deteriorated. If multiple exposure is performed in order to eliminate this influence, there is a problem that the exposure speed is lowered, the image quality is lowered, and the like.
Therefore, a method for correcting the focus position accuracy of the exposure light on the exposed surface in the imaging lens system will be described below.

  As the method of correcting the focal position accuracy, for example, a method using a focus adjusting unit that adjusts the focus of the exposure light imaged on the exposed surface of the photosensitive layer by changing the optical path length of the light modulated by the light modulating unit. And a method of forming an image of light modulated by the light modulation means only in a substantially rectangular region including the central portion of the imaging lens system. Further, a method of moving the relative movement direction of the photosensitive layer (photosensitive material) toward the waviness direction of the photosensitive material is also preferable.

[Exposure pattern image distortion correction method]
The distortion of the surface of each picture element portion of the spatial light modulator has the problem of causing distortion to the light beam at the condensing position, particularly when the DMD is used as a spatial light modulator, There is a problem that a high-definition exposure pattern is not formed.
Accordingly, a method of correcting distortion of an image formed on the exposed surface of the photosensitive layer by correcting distortion of the exit surface of the DMD in a microlens array that converges light from the DMD will be described below. explain.

  The exposure pattern image distortion correction method includes, for example, that each microlens of the microlens array has a characteristic of correcting aberration due to distortion of the surface of the image element portion, such as Specific examples of the microlens include a microlens having an aspherical surface, a microlens having a refractive index distribution, and a microlens having a lens opening shape that does not allow light from a peripheral portion to enter.

  In the embodiment described above, the end surface on the light exit side of the microlens is an aspheric surface (toric surface). However, the microlens has one of two light passage end surfaces as a spherical surface and the other as a cylindrical surface. A microlens array can be configured to obtain the same effect as in the above embodiment.

  Furthermore, in the embodiment described above, the microlens of the microlens array has an aspheric shape that corrects aberration due to distortion of the reflection surface of the micromirror, but instead of adopting such an aspheric shape. The same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution for correcting aberration due to distortion of the reflection surface of the micromirror.

  In addition, in the microlens whose surface shape is aspherical like the microlens described above, the above-described refractive index distribution is also given, and the reflection surface of the micromirror is determined by both the surface shape and the refractive index distribution. You may make it correct | amend the aberration by distortion of this.

Next, a microlens array composed of microlenses having a lens aperture shape that does not allow light from the peripheral portion of the picture element portion to enter will be described.
As described above, there is distortion on the reflection surface of the DMD micromirror, but the amount of change in the distortion tends to increase gradually from the center of the micromirror to the periphery. The amount of change in the peripheral portion distortion in one diagonal direction (y direction) of the micromirror is larger than the amount of change in the peripheral portion distortion in another diagonal direction (x direction), and the above-described tendency is more remarkable. In order to cope with this problem, it is preferable that the microlenses arranged in an array have a circular lens opening.
Therefore, as described above, the laser light reflected at the periphery of the reflective surface of the micromirror having a large distortion, particularly at the four corners, is not condensed by the microlens, and the shape of the condensed laser light at the condensing position is distorted. Can be prevented. Therefore, a higher-definition image without distortion can be exposed on the photosensitive layer.

[Correction by multiple exposure]
As described above, the influence of the distortion of the exposure light caused by the various lens systems constituting the exposure head can be equalized by the effect of offset by selecting the micromirror to be used. Further, resolution variations and density unevenness due to deviations in the mounting position and mounting angle of the exposure head can be equalized by the effect of offset by selecting a micromirror to be used.

  Specifically, an exposure head in which the column direction of the picture element portions forms a predetermined set inclination angle θ with respect to the scanning direction can be used by the use picture element specifying means for the exposure head. Among the picture element parts, the picture element part to be used for N double exposure (where N is a natural number of 2 or more) is designated, and the used picture element part is controlled by the use pixel part control means for the exposure head. A method in which exposure is performed by moving the exposure head relative to the photosensitive layer in the scanning direction by controlling the drawing unit so that only the drawing unit designated by the designation unit is involved in exposure. Are preferable.

The N double exposure is an exposure in which a straight line parallel to the scanning direction of the exposure head intersects N light lines irradiated on the exposed surface in almost all regions of the exposed surface on the photosensitive layer. Say.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

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

(1) Method for designating used pixel portion in single exposure head In the present embodiment (1), the exposure apparatus 10 performs double exposure on the photosensitive layer 12, and each exposure head 30 A description will be given of a method for designating a used pixel part for reducing resolution variation and density unevenness caused by an attachment angle error and realizing ideal double exposure.

As the set inclination angle θ in the column direction of the pixel portion (micromirror 58) with respect to the scanning direction of the exposure head 30, as long as there is no mounting angle error or the like of the exposure head 30, usable 1024 columns × It is assumed that an angle slightly larger than the angle θ _ideal which is exactly double exposure using 256 lines of pixel parts is adopted.
This angle θ _ideal corresponds to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p in the column direction of the usable micromirrors 58, and the microscopic state when the exposure head 30 is tilted. For the pitch δ of the scanning line formed by the mirror,
spsin θ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcos θ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 degrees according to the equation 3. Therefore, as the set inclination angle θ, for example, an angle of about 0.50 degrees may be employed. It is assumed that the exposure apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

  FIG. 25 is an explanatory diagram showing an example of unevenness in the pattern on the exposure surface due to the influence of the mounting angle error of one exposure head 30 and pattern distortion in the exposure apparatus 10 initially adjusted as described above. is there. In the following drawings and description, the light spot in the m-th row is represented by r (m) with respect to the light spot generated by each pixel part (micromirror) and constituting the exposure area on the exposed surface. ), The light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

The upper part of FIG. 25 shows a pattern of light spots from the usable micromirror 58 projected onto the exposed surface of the photosensitive layer 12 with the stage 14 being stationary, and the lower part is the upper part. 2 shows the state of the exposure pattern formed on the surface to be exposed when the stage 14 is moved and continuous exposure is performed in a state where the light spot group pattern as shown in FIG.
In FIG. 25, for convenience of explanation, the exposure pattern by the odd-numbered columns and the exposure pattern by the even-numbered columns of the micromirrors 58 that can be used are separately shown. Two exposure patterns are superimposed.

In the example of FIG. 25, as a result of adopting the set inclination angle θ slightly larger than the angle theta _ideal and fine adjustment of the mounting angle of the exposure head 30 is difficult, the actual mounting angle and the above As a result of the error in the set inclination angle θ, density unevenness occurs in any region on the exposed surface. Specifically, in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, it is ideal in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows. Overexposure occurs with respect to double exposure, resulting in a redundant drawing area and uneven density.

Furthermore, the example of FIG. 25 is an example of pattern distortion appearing on the exposure surface, and “angular distortion” occurs in which the inclination angle of each pixel column projected on the exposure surface is not uniform. The causes of such angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposure surface, distortion of the DMD 36 itself, micromirror placement errors, and the like.
The angle distortion appearing in the example of FIG. 25 is a distortion in which the tilt angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

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

−Specification of actual inclination angle θ′−
FIG. 26 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
In the example of the present embodiment (1), the angle formed by the 512th light spot row positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle θ ′. . Specifically, the micromirror 58 in the first row and the 512th column and the micromirror 58 in the 256th row and the 512th column on the DMD 36 are turned on, and the light spots on the exposure surface corresponding to each of the micromirrors 58 are turned on. The positions of P (1, 512) and P (256, 512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual inclination angle θ ′.

FIG. 27 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
First, in a state where the micromirror 58 in the 256th row and the 512th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is changed. The slit 28 is positioned at an arbitrary position so as to be between the upstream slit 28a and the downstream slit 28b. The coordinates of the intersection of the slit 28a and the slit 28b at this time are (X0, Y0). The values of the coordinates (X0, Y0) are determined and recorded from the movement distance of the stage 14 to the above position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 27 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 27, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 27 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 27, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

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

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

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

FIG. 28 shows how the unevenness on the exposure surface shown in FIG. 25 is improved in the exposure performed using only the light spot generated by the micromirror selected as the micromirror actually used as described above. It is explanatory drawing which showed.
In this example, it is assumed that T = 253 is derived as the natural number T and the micromirrors in the first row to the 253rd row are selected. For the micromirrors in the 254th to 256th lines that have not been selected, a signal for setting the angle of the always-off state is sent by the used pixel part control means, and these micromirrors are substantially Is not involved in exposure. As shown in FIG. 28, in the exposure region near the 512th column, overexposure and underexposure are almost completely eliminated, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 28 (near c (1) in the figure), the inclination angle of the light spot sequence on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is smaller than the inclination angle of the light beam row in the region. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, the ideal double pattern is used for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. An area that is underexposed with respect to the exposure is slightly generated.
However, in the actual exposure pattern formed by overlaying the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the regions where the exposure amount is insufficient are complemented with each other, and the exposure unevenness due to the angular distortion is double-exposed. The effect of offsetting can be minimized.

In the right region of FIG. 28 (near c (1024) in the figure), the inclination angle of the light beam on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is larger than the inclination angle of the light beam row in the region. Therefore, in the exposure by the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, as shown in the figure, there is an overexposed region with respect to the ideal double exposure. It will occur slightly.
However, in the actual exposure pattern formed by superimposing the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the overexposed regions are complemented with each other, and the density unevenness due to the angular distortion is caused by the double exposure. The effect of offsetting can be minimized.

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

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

  As described above, according to the specification method of the used pixel portion of the present embodiment (1) using the exposure apparatus 10, resolution variation and density unevenness due to the influence of the mounting angle error of each exposure head and pattern distortion are reduced. In addition, ideal N double exposure can be realized.

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

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

FIG. 29 shows the influence of the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state in the exposure apparatus 10 initially adjusted as described above. FIG. 6 is an explanatory diagram showing an example of density unevenness generated in a pattern on the exposed surface. The displacement of the relative position of each exposure head in the X-axis direction can occur because it is difficult to finely adjust the relative position between the exposure heads.

The upper portion of FIG. 29 is a light spot group from the usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive layer 12 with the stage 14 being stationary. It is the figure which showed these patterns. The lower part of FIG. 29 shows an exposure pattern formed on the exposed surface when the stage 14 is moved and continuous exposure is performed in a state where the light spot group pattern as shown in the upper part appears. The state is shown for exposure areas 32 ₁₂ and 32 ₂₁ .
In FIG. 29, for convenience of explanation, every other exposure pattern of the micromirror 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

In the example of FIG. 29, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction from the ideal state, the exposure pattern by the pixel column group A and the pixel column group B In both of the above exposure patterns, a portion where the exposure amount is larger than the ideal double exposure state occurs in the connection area between the heads in the exposure areas 32 ₁₂ and 32 ₂₁ .

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

-Detection of position (coordinates)-
FIG. 30 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to FIG. 29 and the corresponding slits 28. The size of the slit 28 is large enough to cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ , that is, the slit 28 is formed on the exposed surface by the exposure heads 30 ₁₂ and 30 _21. The size is sufficient to cover the connection area between the heads.

Figure 31 is a top view for explaining a detection method of detecting the position of a point P of the exposure area _{32 21} as an example (256, 1024).
First, in a state where the micromirror in the 256th row and the 1024th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream. The slit 28 is positioned at an arbitrary position so as to be between the slit 28a on the side and the slit 28b on the downstream side. The coordinates of the intersection of the slit 28a and the slit 28b at this time are (X0, Y0). The values of the coordinates (X0, Y0) are determined and recorded from the movement distance of the stage 14 to the above position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 31, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 31 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 31, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

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

-Identification of unused pixel parts-
In the example of FIG. 29, first, the position of the point P of the exposure area _{32 12} (256,1) is detected by a set of slits 28 and a photodetector as the light spot position detecting unit. Subsequently, the position of each light spot on the 256 line of light spots row r of the exposure area _{32 21 (256), P (} 256,1024), to detect the P (256,1023) ··· and order periodically, where the exposure area _{32 21} of point P indicating the exposure area _{32 12} point P (256,1) larger X coordinate than the (256, n) is detected, and terminates the detecting operation. Then, the micro mirrors corresponding to light spots constituting the c (1024) from the light spot column c of the exposure area 32 ₂₁ (n + 1), specifies as a micro-mirror is not used during the exposure (unused pixel parts).
For example, in FIG. 29, the exposure area _{32 21} point P (256,1020) is shows a larger X coordinate than the point P of the exposure area _{32 12} (256,1) of the exposure area _{32 21} spot If P (256,1020) is that the detection operation at the detected ended, the light spots constituting the first 1024 lines from the 1021 line of exposure area _{32 21,} corresponding to the portion 70 covered with hatched in FIG. 32 The corresponding micromirror is identified as a micromirror that is not used during the main exposure.

Next, the number N of the N multiple exposure, the position of the point P of the exposure area _{32 12} (256, N) is detected. In the present embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.
Then, among the light spot columns of the exposure area 32 _21, except those identified as light spots string corresponding to the micromirrors is not used during the exposure in the above, the position of the light spot constituting the rightmost 1020 column a, P (1,1020) in order from P (1,1020), P (2,1020 ) ··· and continue to detection, greater than the point P of the exposure area _{32 12} (256,2) X When the light spot P (m, 1020) indicating the coordinates is detected, the detection operation is terminated.
Thereafter, the connected operational devices to said light detector, and X-coordinate of the exposure area _{32 12} of the light spot P (256, two), point P of the exposure area _{32 21} (m, 1020) and P (m- and X-coordinate of 1,1020) are compared, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m, 1020) is closer to the X coordinate of the point P in the exposure area _{32 12} (256, 2) a micro mirror corresponding to P (m-1,1020) from point P of the exposure area _322i (1,1020) is identified as a micro-mirror is not used during the exposure.
Also, if the direction of the X coordinate of the point P in the exposure area _{32 21} (m-1,1020) it is near to the X coordinates of the point P in the exposure regions _{32 12} (256, 2), the light exposure area _{32 21} Micromirrors corresponding to points P (1, 1020) to P (m-2, 1020) are identified as micromirrors that are not used for the main exposure.
Furthermore, the position of the point P of the exposure area _{32 12 (256, N-1} ) That point P (256,1), the position of each point constituting the first 1019 column is the next row of the exposure area _{32 21} The same detection process and identification of micromirrors that are not used are also performed.

  As a result, for example, micromirrors corresponding to the light spots constituting the shaded area 72 in FIG. 32 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set the micromirror angle to the off-state angle, and these micromirrors are substantially not used for exposure.

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

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

  As described above, according to the method for designating the used pixel portion of the present embodiment (2) using the exposure apparatus 10, the resolution variation and the density due to the relative position shift in the X-axis direction of the plurality of exposure heads. Unevenness can be reduced and ideal N-fold exposure can be realized.

(3) Specification method of used pixel parts between a plurality of exposure heads <2>
In this embodiment (3), the exposure apparatus 10 performs double exposure on the photosensitive layer 12, and is a head-to-head overlapping area on the exposed surface formed by a plurality of exposure heads 30. In the joint region, the relative position of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) from the ideal state in the X-axis direction, the mounting angle error of each exposure head, and the distance between the two exposure heads A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness due to the relative mounting angle error of the lens and realizing ideal double exposure.

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

FIG. 33 shows the mounting angle errors of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the exposure apparatus 10 in which the mounting angles of the exposure heads 30, that is, the DMDs 36 are initially adjusted as described above. FIG. 10 is an explanatory view showing an example of unevenness that occurs in a pattern on an exposure surface due to the influence of the relative mounting angle error between the exposure heads 30 ₁₂ and 30 ₂₁ and the relative position shift.

In the example of Figure 33, similar to the example of FIG. 29, as a result of the displacement of the relative position of the exposure head 30 ₁₂ X-axis direction 30 _21, exposure with every other row of light spots (pixel column groups A and B) In both exposure patterns 32 ₁₂ and 32 ₂₁ , the exposure amount overlaps on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface of the exposure areas 32 ₁₂ and 32 ₂₁ , which is more than the ideal double exposure state. A region 74 is generated, which causes uneven density.
Further, in the example of FIG. 33, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head to be slightly larger than the angle θ _ideal satisfying the formula (1) and the mounting angle of each exposure head. Therefore, as a result of the actual mounting angle deviating from the set inclination angle θ, even in regions other than the exposure region overlapping on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface, In the connection region between the pixel part columns, which is an overlapped exposure region on the exposed surface, formed by a plurality of pixel part columns, both in the exposure pattern by every other light spot group (pixel column group A and B). A region 76 that is overexposed than the ideal double exposure state is generated, and this causes further density unevenness.

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

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

-Identification of unused pixel parts-
The arithmetic device connected to the photodetector using the actual inclination angle θ ′ thus specified is similar to the following equation 4 similar to the arithmetic device in the embodiment (1) described above.
t tan θ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirrors in the (T + 1) th to 256th rows on the DMD 36 are not used for the main exposure. Processing to identify as a micromirror is performed.
For example, T = 254 for the exposure head _{30 12,} when T = 255 was derived for the exposure head _3O21, micro mirrors corresponding to light spots constituting the parts 78 and 80 covered with hatched in FIG. 34 These are specified as micromirrors that are not used for the main exposure. As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure is minimized. be able to.

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

Thereafter, with respect to the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered by the oblique lines in FIG. 34, the same processing as that of the present embodiment (3) described with reference to FIGS. 29 to 17 is performed. In FIG. 34, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. Not involved.

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

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

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

  Furthermore, in the above embodiments (1) to (3), the actual inclination angle θ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle θ ′ is obtained. Although the micromirror to be used is selected based on the above, it is also possible to select a micromirror that can be used without deriving the actual inclination angle θ ′. Furthermore, for example, the reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by visually confirming the resolution and density unevenness of the reference exposure result. It is included in the scope of the invention.

In addition to the angular distortion described in the above example, there are various forms of pattern distortion that can occur on the exposed surface.
As an example, as shown in FIG. 35A, there is a form of magnification distortion in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.
As another example, as shown in FIG. 35B, there is a form of beam diameter distortion in which the light from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposure surface with a different beam diameter. These magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposure surface.
As yet another example, there is a form of light amount distortion in which light beams from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposure surface with different light amounts. This light amount distortion is not only various aberrations and misalignment, but also the position dependency of the transmittance of the optical elements between the DMD 36 and the exposure surface (for example, the lenses 52 and 54 in FIGS. 5A and 5B, which are single lenses), and the DMD 36 itself. This is caused by unevenness in the amount of light. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposure surface.

  According to the above embodiments (1) to (3), the residual elements of pattern distortion in these forms after selecting the micromirrors actually used for the main exposure are the same as the residual elements of angular distortion described above. It can be leveled by the effect of offset by double exposure.

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

FIG. 36A and FIG. 36B are explanatory views showing an example of a form in which reference exposure is performed using only (N-1) rows of micromirrors using a single exposure head.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the odd-numbered light spot rows indicated by the solid lines in FIG. 36A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and density unevenness, or estimating an actual inclination angle.
For example, micromirrors other than the micromirror corresponding to the light spot array shown by hatching in FIG. 36B are designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. . For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and the micromirror used during the main exposure may be designated, or the same pattern as that for the odd-numbered light spot arrays may be applied. Good.
By specifying the micromirrors used in the main exposure as described above, in the main exposure using both the odd-numbered and even-numbered micromirrors, a state close to ideal double exposure can be realized.

FIG. 37 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference is made using only the micromirrors corresponding to the odd-numbered light spot rows of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction, which are indicated by solid lines in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the area 86 shown by hatching in FIG. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

FIG. 38A and FIG. 38B show an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total number of light spot rows. FIG.
In this example, it is assumed that double exposure is performed during main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows shown by the solid line in FIG. 38A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, a micromirror to be used in the main exposure can be designated.
For example, a micromirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 38B is designated as actually used in the main exposure among the micromirrors in the first to 128th rows. Can be done. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used in the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
By designating the micromirror to be used at the time of the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using the entire micromirror.

In FIG. 39, a plurality of exposure heads are used, and two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction are adjacent to each other corresponding to 1 / N rows of the total number of light spots. It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises a line.
In this example, it is assumed that double exposure is performed during main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows indicated by the solid line in FIG. 39, and the reference exposure results are output as samples. . Based on the reference exposure result outputted from the sample, it is possible to realize the main exposure in which the variation in resolution and the density unevenness in the region other than the joint region between the heads formed on the exposed surface by the two exposure heads are minimized. In addition, it is possible to designate a micromirror to be used during the main exposure.
For example, micromirrors other than the micromirrors corresponding to the light spot arrays in the region 90 shown shaded in FIG. 39 and the shaded region 92 are included in the micromirrors in the first row to the 128th row. Designated as actually used at the time of exposure. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used for the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
In this way, by specifying the micromirror to be used during the main exposure, a state close to ideal double exposure is realized in an area other than the inter-head connecting area formed on the exposed surface by two exposure heads. it can.

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

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

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a image development process, an etching process, a plating process, a hardening process process, etc. are mentioned. These may be used alone or in combination of two or more.
The developing step is a step of forming a pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing the uncured region by removing the uncured region.

-Development process-
The developing step can be preferably performed by, for example, developing means.
The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, means for spraying the developer, means for applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.
In addition, the developing unit may include a developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

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

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

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

-Etching process-
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor. Moreover, a well-known sandblasting method can be used.
A wiring pattern (circuit) can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.

-Plating process-
The plating step can be performed by an appropriately selected method selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.
A metal wiring pattern (circuit) is formed on the surface of the substrate by removing the pattern after plating by the plating process and further removing unnecessary portions by a resist stripping process or the like as necessary. Can do.

-Curing process-
The curing treatment step is a step of performing a curing treatment on the formed permanent pattern after the developing step is performed on the photosensitive layer made of the photosensitive composition as the solder resist.

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

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the photosensitive laminate on which the permanent pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, According to the objective, it can select suitably, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

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

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

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

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

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

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

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

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

  The photosensitive laminate may be formed by laminating the pattern forming material on the printed wiring board forming substrate, and forming the printed wiring board with a photosensitive composition solution for manufacturing the pattern forming material. The photosensitive layer and the support may be laminated on the printed wiring board forming substrate by applying directly to the surface of the printing substrate and drying.

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

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

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

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

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

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

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

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

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

[Use]
Since the photosensitive composition of the present invention, the pattern forming material having the photosensitive layer formed by the photosensitive composition, and the photosensitive laminate have a small sensitivity variation with respect to temperature and can form a high-definition pattern. It can be suitably used for formation of various patterns, production of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, and proofs.
Since the pattern forming apparatus and the pattern forming method according to the present invention include the photosensitive laminate according to the present invention, various patterns are formed, and liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, and partition walls are manufactured. It can be suitably used for the production of holograms, micromachines, and proofs.

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

Example 1
-Production of pattern forming material-
A photosensitive composition solution having the following composition was prepared on a polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) having a thickness of 16 μm as the support, and an ultrasonic disperser (SMT Co., Ltd., UH-600). After dispersion, it is applied and dried to form a photosensitive layer (resist layer for circuit formation) having a thickness of 15 μm, and then a polypropylene film (E200, Oji Paper (E200) as a protective film is formed on the photosensitive layer. The pattern forming material was manufactured by laminating with a laminate.

[Composition of photosensitive composition solution]
Carbon nanotube (Wako Chemical Co., Ltd., trade name: carbon nanotube (multi-layer), distributor: Wako Pure Chemical Industries, Ltd.) 0.01 part by mass t-butylcatechol 0.0049 part by mass Methacrylic acid / methyl methacrylate / Styrene copolymer (copolymer composition (mass ratio): 29/19/52, mass average molecular weight: 60,000,
Acid value 189, 30% by mass product, methyl ethyl ketone / propylene glycol monomethyl ether solvent) 84.4 parts by mass / polymerizable monomer represented by the following structural formula (64) 8.2 parts by mass / decamethylene diisocyanate and tetraethylene oxide Monomethacrylate 1/2 molar ratio adduct 8.2 parts by weight Dodecapropylene glycol diacrylate 4.3 parts by weight 2,2-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl Biimidazole 3.4 parts by mass-Sensitizer represented by the following structural formula (65) 0.20 parts by mass-Malachite green oxalic acid 0.03 parts by mass-Leuco Crystal Violet 0.2 parts by mass-Methyl ethyl ketone 30 parts by mass・ Propylene glycol monomethyl ether 40 parts by mass ・ Fluorosurfactant (Dainippon Ink, F780F, 30% by mass, methyl ethyl ketone / propylene glycol monomethyl ether solvent) 0.14 parts by mass
The binder (methacrylic acid / methyl methacrylate / styrene copolymer) had a glass transition temperature (Tg) of 131 ° C.

  However, in Structural Formula (64), EO represents an ethylene oxide group, PO represents a propylene oxide group, PO may be any of the following structural formulas (iii) and (iv), and an average of m + n The value is 10 and the average value of p + q is 4.

As the substrate, the photosensitive layer of the pattern forming material is peeled off from the surface of a copper-clad laminate (no through-hole, copper thickness 12 μm) polished, washed with water and dried. Crimping is performed using a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) so as to contact the copper-clad laminate, and the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support). A photosensitive laminate was prepared in which and were laminated in this order.
The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.
Using the photosensitive laminate, a photosensitive layer made of the photosensitive composition was exposed, and the sensitivity, resolution, sensitivity variation with respect to temperature, and edge roughness of the photosensitive layer were measured by the following methods. The exposure apparatus used is of the type that performs maskless exposure using a pattern forming apparatus having a 405 nm laser light source. The pattern forming apparatus has a light modulation unit made of the DMD.
The results are shown in Table 1.

<Measurement of sensitivity>
With respect to the photosensitive layer of the pattern forming material in the photosensitive laminate, from the polyethylene terephthalate film (support) side, using a pattern forming apparatus having a 405 nm laser light source as the light irradiation means, 1 mJ / cm ² And exposed to light having different light energy amounts up to 100 mJ / cm ^{2 at} intervals of 2 ^1/6, thereby curing a part of the photosensitive layer.
After standing at room temperature for 15 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) is applied to the entire surface of the photosensitive layer on the copper clad laminate. Spraying was performed at a spray pressure of 0.15 MPa for twice the shortest development time determined by the following method, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured.
Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was 15 μm, which was the same as the unexposed thickness, was determined as the amount of light energy necessary for curing the photosensitive layer.
As a result, the amount of light energy necessary for curing the photosensitive layer was 3 mJ / cm ² . The pattern forming apparatus includes a light modulating unit made of the DMD and includes the pattern forming material.

<Measurement of the shortest development time>
The polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. The shorter the shortest development time, the better the developability.
As a result, the shortest development time was 10 seconds.

<Measurement of resolution>
The said photosensitive laminated body was produced by the method similar to the above, and it left still for 10 minutes at room temperature (23 degreeC, 55% RH). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, exposure of each line width is performed in increments of 1 μm from 5 μm to 20 μm with a line / space = 1/1 by using the pattern forming apparatus. Each line width was exposed in increments of 5 μm from a line width of 20 μm to 50 μm. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material obtained by sensitivity measurement.
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. Spray the entire surface of the photosensitive layer on the copper-clad laminate with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa for twice the shortest development time determined by the above method. Then, the uncured region was dissolved and removed. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. did. The smaller the numerical value, the better the resolution.

<Measurement of sensitivity variation with temperature>
In the same manner as the above resolution measurement, except that the photosensitive laminate was left at room temperature (22 ° C., 55% RH), changed to 27 ° C., 55% RH, and line / space = 1/1. An exposure with a line width of 20 μm was performed. The exposure amount at this time was 5 mJ / cm ² .
The obtained pattern was observed with an optical microscope, the line width of the cured resin pattern was measured, and the exposure amount when the line width was 20 μm was determined. Room temperature (22 ℃, RH 55%) the exposure amount when left in the _{D 0,} 27 ℃, as _{D 1} the exposure amount when left in _{55% RH, | (D 1} -D 0) | values Was calculated. The smaller the fluctuation of the exposure amount with respect to the temperature change, the better.

<Measurement of edge roughness>
A pattern was formed in the same manner as the resolution measurement except that the pattern forming apparatus was used to perform exposure so that a horizontal line pattern perpendicular to the scanning direction of the exposure head was formed. Among the obtained patterns, any five points of a line having a line width of 30 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and among the edge positions in the field of view Then, the difference between the most swollen portion (mountain peak portion) and the most constricted portion (valley bottom portion) was obtained as an absolute value, and an average value of five observed positions was calculated, and this was defined as edge roughness. The edge roughness is preferably as the value is small because it exhibits good performance.

(Example 2)
The amount of the carbon nanotube of Example 1 is 0.01 parts by weight (corresponding to 0.02% by mass per total solid content of the photosensitive layer) to 0.001 parts by mass (corresponding to 0.002% by mass per total solid content of the photosensitive layer). A photosensitive laminate was prepared in the same manner as in Example 1 except that it was changed to, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

(Example 3)
The amount of the carbon nanotube of Example 1 is 0.01 part by weight (corresponding to 0.02% by mass per total solid content of the photosensitive layer) to 0.0001 part by mass (corresponding to 0.0002% by mass per total solid content of the photosensitive layer). A photosensitive laminate was prepared in the same manner as in Example 1 except that it was changed to, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Example 4
The amount of the carbon nanotube of Example 1 is 0.01 part by weight (corresponding to 0.02% by mass per total solid content of the photosensitive layer) to 0.1 part by mass (corresponding to 0.2% by mass per total solid content of the photosensitive layer). A photosensitive laminate was prepared in the same manner as in Example 1 except that it was changed to, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

(Example 5)
In Example 1, carbon nanotubes (manufactured by Wako Chemical Co., Ltd., trade name: carbon nanotubes (multi-layer), distributor: Wako Pure Chemical Industries, Ltd.) in the photosensitive composition were obtained from Strem Chemicals, Inc. Instead of carbon nanotubes (single wall) manufactured by the company (distributor: Wako Pure Chemical Industries, Ltd.), the addition amount is 0.01 mass parts (corresponding to 0.02 mass% per total solid content of the photosensitive layer) to 1 mass A photosensitive laminate was prepared in the same manner as in Example 1 except that the amount was changed to 1 part (corresponding to 2% by mass per total solid content of the photosensitive layer), and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

(Example 6)
In Example 1, carbon nanotubes (manufactured by Wako Chemical Co., Ltd., trade name: carbon nanotubes (multi-layer) (distributor: Wako Pure Chemical Industries, Ltd.)) in the photosensitive composition were obtained from Ulvic Inc. A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the product name was changed to a product name, Fullerene C60 / C70 (distributor: Wako Pure Chemical Industries, Ltd.).
The obtained photosensitive laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)
Example 1 and Example 1 except that the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with the sensitizer represented by the following structural formula (66). Similarly, a pattern forming material and a photosensitive laminate were produced.
The obtained photosensitive laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 8)
Example 1 and Example 1 except that the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with the sensitizer represented by the following structural formula (67). Similarly, a pattern forming material and a photosensitive laminate were produced.
The obtained photosensitive laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 9
Example 1 except that the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with 2-chloro-10-butylacridone (sensitizer) in Example 1. In the same manner, a pattern forming material and a photosensitive laminate were produced.
Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 10)
In Example 1, except that the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with a thioxanthone compound (trade name Speedcure CPTX, manufactured by Lambson Group Ltd.) (sensitizer). In the same manner as in Example 1, a pattern forming material and a photosensitive laminate were produced.
Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 11)
A pattern was obtained in the same manner as in Example 1 except that the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with 9-phenylacridine (sensitizer). A forming material and a photosensitive laminate were produced.
Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 12)
In Example 1, the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with a compound having a basic nucleus represented by the following structural formula (68) (sensitizer). Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1.

  Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 13)
In Example 1, the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with a compound (sensitizer) having an acidic nucleus represented by the following structural formula (69). Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1.

  Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 14)
In Example 1, except that the sensitizer represented by the structural formula (65) in the photosensitive composition was replaced with a fluorescent brightener (sensitizer) represented by the following structural formula (70). Produced a pattern forming material and a photosensitive laminate in the same manner as in Example 1.

  Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 15)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the pattern forming apparatus was subjected to double exposure instead of the one described below. The results are shown in Table 1.

<< Pattern Forming Apparatus >>
The combined laser light source shown in FIGS. 12 to 18 as the light irradiating means, and a micromirror array in which 1024 micromirrors 58 are arranged in the main scanning direction schematically shown in FIG. An exposure head 30 having a DMD 36 controlled to drive only 1024 × 256 rows out of 768 sets arranged in the scanning direction, and an optical system for imaging the light shown in FIG. 5 on the pattern forming material. The provided pattern forming apparatus 10 was used.

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

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 33, the light spot group from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the pattern forming material 12 with the stage 14 being stationary. Showed the pattern. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 33, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 33, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

The use of a set of slits 28 and a photodetector as a light spot position detection means, the position of the point P of the exposure head _{30 12} For the exposure area _{32 12} (1,1) and P (256,1), the exposure head For 30 ₂₁ , the positions of the light spots P (1,1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected, and the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head is determined. It was measured.

Using the actual inclination angle θ ′, the following equation 4
t tan θ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 34 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 34 were similarly covered with the region 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

(Comparative Example 1)
A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the photosensitive composition was prepared without adding the carbon nanotube.
Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 16)
-Production of pattern forming material-
A photosensitive composition solution having the following composition is applied to a 16 μm thick polyethylene terephthalate film as the support and dried to form a 35 μm thick photosensitive layer (solder resist layer). In addition, a 20 μm thick polypropylene film was laminated as a protective film to produce the pattern forming material.

[Composition of photosensitive composition solution]
・ Carbon nanotube (Wako Chemical Co., Ltd., trade name: carbon nanotube (multi-layer), distributor: Wako Pure Chemical Industries, Ltd.) 0.01 part by mass ・ N-phenylglycine 0.2 part by mass Industrial Co., Ltd., B30) Dispersion 63 parts by mass / epoxy acrylate compound: Binder (PR-300, concentration 67%, Showa Polymer Co., Ltd.) 24.5 parts by mass / (meth) acryloyl group and carboxyl in side chain Vinyl copolymer having a group: binder (SPC-2X, concentration 60%, manufactured by Showa Polymer Co., Ltd.) 13.8 parts by mass: epoxy compound represented by the following structural formula (71): thermal crosslinking agent 16. 7 parts by mass, dipentaerythritol hexaacrylate: polymerizable compound 5.5 parts by mass, sensitizer represented by the following structural formula (72) 0.23 parts by mass, Irgacure 69 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass, phenoxazine 0.055 parts by mass, dicyandiamide 0.4 parts by mass, 2MA-OK (manufactured by Shikoku Chemicals Co., Ltd.) 0.3 parts by mass Phthalocyanine green 0.42 parts by mass F780F (Dainippon Ink Co., Ltd. 30% concentration methyl ethyl ketone solution)
0.066 parts by mass ・ Methyl ethyl ketone 60.0 parts by mass

  The barium sulfate dispersion was prepared in advance by adding 22 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30), 12 parts by mass of a 67% by mass solution of PR-300 diethylene glycol monomethyl ether acetate, and 29 parts by mass of methyl ethyl ketone. After mixing, a motor mill M-200 (manufactured by Eiger) was used by dispersing for 3.5 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm.

-Formation of permanent pattern-
-Preparation of laminate-
Next, as the base material, a surface of a copper-clad laminate (no through hole, copper thickness 12 μm) on which wiring was formed was prepared by chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was peeled off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.
Using the photosensitive laminate, a photosensitive layer made of the photosensitive composition was exposed, and the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.
The shortest development time was 20 seconds.

(Comparative Example 2)
In Example 16, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 16 except that the carbon nanotubes in the photosensitive composition were added without preparation.
Using the obtained photosensitive laminate, the sensitivity, resolution, and edge roughness of the photosensitive layer were measured in the same manner as in Example 1. The results are shown in Table 1.

FIG. 1 is a perspective view showing an appearance of an example of an exposure apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the exposure apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the exposure apparatus of FIG. FIG. 7A is a diagram illustrating a state in which the micromirror is tilted to + α degrees in the on state. FIG. 7B is a diagram illustrating a state in which the micromirror is in an off state and tilted to −α degrees. FIG. 8 is an example of a controller that controls DMD based on pattern information. FIG. 9A is a diagram showing a scanning trajectory of a reflected light image (exposure beam) by each micromirror when the DMD is not tilted. FIG. 9B is a diagram showing the scanning trajectory of the exposure beam when the DMD is tilted. FIG. 10 is an example of a plan view for explaining an exposure method in which the photosensitive layer is exposed by one scanning by the scanner. FIG. 11A is a diagram for explaining an exposure method in which a photosensitive layer is exposed by scanning a plurality of times by the scanner, and after the photosensitive layer is scanned in the X direction by the scanner, the scanner is moved by one step in the Y direction. FIG. FIG. 11B is a diagram for explaining an exposure method for exposing the photosensitive layer by a plurality of scans by the scanner, and shows a state in which scanning is performed in the X direction after FIG. 11A. FIG. 12 is a perspective view showing an example of the configuration of the fiber array light source. FIG. 13 is a front view showing an example of the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 14 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 15 is an example of a plan view showing the configuration of the combined laser light source. FIG. 16 is an example of a plan view showing the configuration of the laser module. FIG. 17 is an example of a side view showing the configuration of the laser module shown in FIG. 18 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 19 is an example of a perspective view illustrating a configuration of a laser array. FIG. 20A is a perspective view showing an example of the configuration of a multi-cavity laser. 20B is a perspective view showing an example of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 20A are arranged in an array. FIG. 21 is an example of a plan view showing another configuration of the combined laser light source. FIG. 22 is an example of a plan view showing another configuration of the combined laser light source. FIG. 23A is a plan view showing an example of another configuration of the combined laser light source. FIG. 23B is a cross-sectional view showing an example of a configuration along the optical axis of FIG. 23A. FIG. 24A is an example of a cross-sectional view along the optical axis in a conventional exposure apparatus. FIG. 24B is an example of a cross-sectional view along the optical axis in the pattern forming method (exposure apparatus) of the present invention. FIG. 25 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposure surface when there is a mounting angle error and pattern distortion of the exposure head. FIG. 26 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 27 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 28 is an explanatory diagram showing a state in which unevenness occurring in the pattern on the exposure surface is improved as a result of using only the selected micromirrors for exposure. FIG. 29 is an explanatory diagram showing an example of unevenness that occurs in a pattern on an exposure surface when there is a relative position shift between adjacent exposure heads. FIG. 30 is a top view showing the positional relationship between the exposure areas by two adjacent exposure heads and the corresponding slits. FIG. 31 is a top view for explaining a method of measuring the position of the light spot on the exposure surface using a slit. FIG. 32 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 29 are actually moved and the unevenness in the pattern on the exposure surface is improved. FIG. 33 is an explanatory diagram showing an example of unevenness in the pattern on the exposure surface when there is a relative position shift and an attachment angle error between adjacent exposure heads. FIG. 34 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 35A is an explanatory diagram illustrating an example of magnification distortion. FIG. 35B is an explanatory diagram showing an example of beam diameter distortion. FIG. 36A shows a first example of reference exposure using a single exposure head, in which reference exposure is performed using only micromirrors corresponding to odd-numbered light spot rows indicated by solid lines, and the reference exposure result is obtained. It is a figure explaining the state which outputs a sample. FIG. 36B shows a first example of reference exposure using a single exposure head, in which micromirrors other than the micromirrors corresponding to the light spot rows covered with diagonal lines constitute odd-numbered light spot rows. It is a figure which shows the state designated as what is actually used in this exposure in a mirror. FIG. 37 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 38A shows a second example of reference exposure using a single exposure head, and uses only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows indicated by solid lines. It is explanatory drawing which shows the state which performs reference exposure and outputs the sample of the reference exposure result. FIG. 38B shows a second example of reference exposure using a single exposure head, in which micromirrors other than the micromirror corresponding to the light spot group indicated by hatching are in the first to 128th rows. It is a figure which shows the state which can be designated as what is actually used in the time of this exposure in a micromirror. FIG. 39 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads.

Explanation of symbols

B1 to B7 Laser beam L1 to L7 Collimator lens LD1 to LD7 GaN-based semiconductor laser 10 Exposure device 12 Photosensitive layer 14 Moving stage 18 Installation table 20 Guide 22 Gate 24 Scanner 26 Sensor (Camera)
28 Slit 30 Exposure Head 36 Digital Micromirror Device (DMD)
38 Fiber array light source 40 Condensing lens system 50 Imaging lens system 58 Micromirror (image element)
Reference Signs List 60 laser module 62 multimode optical fiber 64 optical fiber 66 laser emitting unit 110 heat block 111 multicavity laser 113 rod lens 114 lens array 140 laser array 200 condenser lens

Claims (34)

It is contained in the photosensitive layer that forms a two-dimensional pattern on the exposed surface by exposing the exposure head and the exposed surface of the photosensitive layer by relative scanning while modulating light based on the pattern information. A photosensitive composition comprising:
A photosensitive composition comprising at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial. When the photosensitive layer is exposed and developed, the minimum energy amount of exposure that does not change the thickness of the exposed portion of the photosensitive layer after exposure and development is 0.1 mJ / cm ^{2 to} 100 mJ / cm ^2. A photosensitive composition contained in the layer,
A photosensitive composition comprising at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial. Based on the pattern information, the photosensitive head is used for exposure to form a two-dimensional pattern on the exposed surface by exposing the exposure head and the exposed surface of the photosensitive layer by relative scanning while modulating light. A photosensitive composition contained in the layer,
When the photosensitive layer is exposed and developed, the minimum energy amount of exposure that does not change the thickness of the exposed portion of the photosensitive layer after exposure and development is 0.1 mJ / cm ^{2 to} 100 mJ / cm ² ,
A photosensitive composition comprising at least a binder, a polymerizable compound, a photopolymerization initiator, and a carbon-based nanomaterial.   The photosensitivity according to any one of claims 1 to 3, wherein the carbon-based nanomaterial is at least one selected from the group consisting of carbon nanotubes, fullerenes, and carbon microcoils. Composition.   The photosensitive composition according to any one of claims 1 to 4, further comprising a sensitizer.   The sensitizer is at least one selected from the group consisting of a condensed ring compound, a compound having a disubstituted aminobenzene as a partial structure, a compound having a basic nucleus, a compound having an acidic nucleus, and a fluorescent brightener. The photosensitive composition according to claim 5, comprising:   The photosensitive composition according to claim 6, wherein the condensed ring compound includes at least one selected from the group consisting of an acridone compound, a thioxanthone compound, a coumarin compound, and an acridine compound. . The photosensitive compound according to claim 6 or 7, wherein the compound having the disubstituted aminobenzene as a partial structure is at least one compound represented by the following general formulas (I) to (VII). Sex composition.

[In General Formula (I), R ¹ , R ² , R ⁵ , and R ⁶ each independently represent either an aliphatic group or an aromatic group, and R ³ , R ⁴ , R ⁷ , R ⁸ and R ^{9 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent. R ¹ and R ² , R ⁵ and R ⁶ , R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , and R ⁶ and R ⁸ are independently bonded to each other to form a nitrogen-containing complex. A ring may be formed. ]

[In General Formula (II), R ²¹ and R ²² each independently represent either an aliphatic group or an aromatic group, and R ^{23 to} R ³⁰ each independently represent a hydrogen atom or a monovalent group. X represents one of an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, and an imino group substituted with an aliphatic group or an aromatic group. R ²¹ and R ²² , R ²¹ and R ²³ , and R ²² and R ²⁴ may be independently bonded to each other to form a nitrogen-containing heterocyclic ring, and the benzene ring condensed to the heterocyclic ring is substituted. It may have a group. ]

[In General Formula (III), R ³¹ and R ³² each independently represent either an aliphatic group or an aromatic group, and R ^{33 to} R ³⁷ each independently represent a hydrogen atom or a monovalent group. And R ³⁸ represents a monovalent substituent. R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³⁴ may be independently bonded to each other to form a nitrogen-containing heterocycle. ]

[In General Formula (IV), R ⁴¹ and R ⁴² each independently represent either an aliphatic group or an aromatic group, and R ^{43 to} R ⁴⁷ each independently represent a hydrogen atom or a monovalent group. Y represents either an oxygen atom or NR ⁴⁸ , and R ⁴⁸ represents either a hydrogen atom or a monovalent substituent. R ⁴¹ and R ⁴² , R ⁴¹ and R ⁴³ , and R ⁴² and R ⁴⁴ may be independently bonded to each other to form a nitrogen-containing heterocycle. ]

[In General Formulas (V) to (VII), Rings A to G each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and Ring A, Ring B, and Ring D and Ring E, and Ring F and Ring G may be independently bonded to each other to form a bonded ring containing N.
In the general formula (VI), the linking group L represents a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the linking groups L and N are the aromatic hydrocarbon ring and aromatic group. And n represents any integer of 2 or more.
In the general formula (VII), R represents an alkyl group which may have a substituent.
Rings A to G and linking group L may have a substituent, and these substituents may be bonded to each other to form a ring. ]   The compound having a basic nucleus is at least one selected from the group consisting of a cyanine dye, a hemicyanine dye, a styryl dye, and a streptocyanine dye. The photosensitive composition of any one of Claims.   The photosensitive composition according to any one of claims 6 to 9, wherein the compound having an acidic nucleus is at least one selected from the group consisting of a merocyanine compound and a rhodacyanine compound.   The photosensitive composition according to any one of claims 6 to 10, wherein the optical brightener is a compound having a nonionic nucleus.   The photopolymerization initiator is selected from the group consisting of halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metallocenes, and acylphosphine oxide compounds. The photosensitive composition according to claim 1, wherein the photosensitive composition is at least one radical generator.   The photosensitive composition according to any one of claims 1 to 12, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.   The photosensitive composition according to claim 1, wherein the polymerizable compound is a monomer having at least one of an ethylene oxide group and a propylene oxide group.   The photosensitive material according to claim 1, wherein the binder includes a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative. Sex composition.   The photosensitive composition according to any one of claims 1 to 15, wherein the binder has a glass transition temperature (Tg) of 80 ° C or higher. In addition, it contains a thermal crosslinking agent
The binder includes at least one of an epoxy acrylate compound and at least one of a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. The photosensitive composition according to any one of claims 16 to 16.   The thermal crosslinking agent is at least one selected from the group consisting of 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 claim 17.   A pattern forming material comprising at least a support and a photosensitive layer containing the photosensitive composition according to any one of claims 1 to 18 on the support.   The pattern forming material according to claim 19, wherein a cushion layer and the photosensitive layer are provided on a support in order from the side close to the support.   A photosensitive layered product comprising a photosensitive layer containing the photosensitive composition according to any one of claims 1 to 18 on a substrate.   The photosensitive laminate according to claim 21, wherein the photosensitive layer is formed of the pattern forming material according to claim 19 or 20.   The pattern formation method characterized by including at least the exposure process which exposes with respect to the photosensitive layer of the photosensitive laminated body of Claim 21 or Claim 22.   24. The pattern forming method according to claim 23, wherein in the exposure step, exposure is performed with a laser beam having a wavelength of 350 to 415 nm. In the exposure step, a light irradiating unit 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 irradiating unit and light from the light irradiating unit. An exposure head provided with a light modulation means capable of controlling the picture element portion according to pattern information, wherein the column direction of the picture element portion has a predetermined set inclination with respect to the scanning direction of the exposure head. Using an exposure head arranged to form an angle θ,
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
25. The pattern forming method according to claim 23, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction.   Exposure is performed by a plurality of exposure heads, and a used pixel part specifying unit is configured to detect a pixel part related to exposure of a joint area between heads that is an overlapped exposure area on an exposed surface formed by the plurality of exposure heads. 26. The pattern forming method according to claim 25, wherein the pixel portion to be used for realizing N double exposure in the inter-head connecting region is designated.   Picture element part in which exposure is performed by a plurality of exposure heads and the used picture element part specifying means is involved in exposure other than the inter-head joint area which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads 27. The pattern forming method according to claim 25 or 26, wherein the picture element portion to be used for realizing N double exposure in an area other than the inter-head connecting area is designated. The set inclination angle θ is N of N multiple exposure numbers, the number s of pixel portions in the column direction, the interval p in the column direction of the pixel portions, and the scanning direction of the exposure head when the exposure head is inclined. to the column direction of the pitch δ of pixel parts along a direction orthogonal, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, characterized in that it is set so as to satisfy the relation theta ≧ theta _ideal The pattern formation method of any one of Claims 25-27. Use pixel part designation means,
A light spot position detecting means for detecting a light spot position on a surface to be exposed as a pixel unit generated by a picture element unit and constituting an exposure area on the surface to be exposed;
29. A pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. 2. The pattern forming method according to claim 1.   30. The pattern information according to claim 25, wherein the pattern information is converted so that a dimension of a predetermined part of the pattern represented by the pattern information matches a dimension of a corresponding part that can be realized by the designated used pixel part. The pattern formation method of any one of Claims 1.   The pattern forming method according to any one of claims 23 to 30, further comprising a developing step of developing the photosensitive layer after the exposing step.   32. The pattern forming method according to claim 31, further comprising at least one of an etching process and a plating process after the developing process.   32. The pattern forming method according to claim 31, further comprising a curing process step of performing a curing process on the photosensitive layer after the developing step.   34. The pattern forming method according to claim 33, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed on the photosensitive laminate.