JP5550136B2 - Photosensitive composition for blue-violet semiconductor laser - Google Patents

Description

  The present invention relates to a sensitizer containing a squarylium compound and a photosensitive composition for a blue-violet semiconductor laser using the sensitizer.

  In recent years, researches on lithography and printing using laser light as an exposure light source have been actively conducted.

  Various light sources from ultraviolet to infrared are known as laser light. Laser light that can be used for image exposure includes visible to infrared regions such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser. The one that emits this light is regarded as promising, and recently, blue-violet semiconductor lasers have attracted attention.

  However, although a semiconductor laser that can oscillate stably in the blue-violet region can be used, the sensitivity of the photosensitive composition is not necessarily sufficient because its output is lower than other visible regions. It cannot be said that there is a problem that has not reached a level that can be put into practical use not only in the direct drawing method but also in the lithography method.

Examples of the sensitizer used for the photosensitive composition in the wavelength region (350 nm to 450 nm) of the blue-violet semiconductor laser include benzophenone compounds, coumarin compounds, and squarylium compounds (Patent Documents 1 and 2).
However, these compounds have a drawback that sufficient sensitivity cannot be obtained.

JP 2004-086122 A JP 2009-024991 A

  The objective of this invention is providing the sensitizer excellent in the sensitivity with respect to a blue-violet semiconductor laser, and the photosensitive composition for blue-violet semiconductor lasers using the same.

  As a result of intensive studies, the present inventors have found that a photosensitive composition for a blue-violet semiconductor laser using a squarylium compound as a sensitizer can solve the above problems, and have completed the present invention.

  That is, the present invention is as follows.

  1st invention is a sensitizer characterized by including the squarylium compound which consists of a squarylium compound ion represented by the following general formula (A)-(D), and a hydrogen ion or a transition metal ion.

（式（Ａ）中、Ｒ_１〜Ｒ_６は、同一又は異なってもよい水素、ハロゲン原子、置換基を有してもよいアルキル基、ハロゲン化アルキル基、シアノアルキル基、アルコキシ基、フェニルアルキル基、アルキルスルホン酸基を示し、Ｒ_２とＲ_３、Ｒ_３とＲ_４、Ｒ_５とＲ_６、Ｒ_６とＲ_１は連結して炭化水素環を形成してもよい。）

(In formula (A), R _{1 to} R ₆ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. And R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₆ and R ₁ may be linked to form a hydrocarbon ring.

（式（Ｂ）中、Ｒ_７は、水素又は置換基を有してもよいアルキル基であり、Ｒ_８〜Ｒ_１１は、同一又は異なってもよい水素、ハロゲン原子、置換基を有してもよいアルキル基、ハロゲン化アルキル基、シアノアルキル基、アルコキシ基、フェニルアルキル基、アルキルスルホン酸基を示し、Ｒ_８とＲ_９、Ｒ_１０とＲ_１１は連結して炭化水素環を形成してもよい。）

(In Formula (B), R ₇ is hydrogen or an alkyl group that may have a substituent, and R _{8 to} R ₁₁ have the same or different hydrogen, halogen atom, and substituent. Represents an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an alkoxy group, a phenylalkyl group, an alkylsulfonic acid group, and R ₈ and R ₉ , R ₁₀ and R ₁₁ are linked to form a hydrocarbon ring. May be.)

（式（Ｃ）中、Ｒ_１２〜Ｒ_１４は、同一又は異なってもよい水素、ハロゲン原子、置換基を有してもよいアルキル基、ハロゲン化アルキル基、シアノアルキル基、アルコキシ基、フェニルアルキル基、アルキルスルホン酸基を示す。）

(In the formula (C), R _{12 to} R ₁₄ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. Group represents an alkylsulfonic acid group.)

（式（Ｄ）中、Ｒ_１５〜Ｒ_１９は、同一又は異なってもよい水素、ハロゲン原子、置換基を有してもよいアルキル基、ハロゲン化アルキル基、シアノアルキル基、アルコキシ基、フェニルアルキル基、アルキルスルホン酸基を示し、ＸはＯ、Ｓ、Ｎ−Ｒ_２０、Ｃ−Ｒ_２１Ｒ_２２（Ｒ_２０〜Ｒ_２２は同一又は異なってもよい水素、ハロゲン原子、置換基を有してもよいアルキル基、ハロゲン化アルキル基、シアノアルキル基、アルコキシ基、フェニルアルキル基、アルキルスルホン酸基を示す。）を示す。）

(In the formula (D), R _{15 to} R ₁₉ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. Group, an alkylsulfonic acid group, X is O, S, N—R ₂₀ , C—R ₂₁ R ₂₂ (R _{20 to} R ₂₂ may be the same or different and each has a hydrogen atom, a halogen atom, or a substituent. An alkyl group, a halogenated alkyl group, a cyanoalkyl group, an alkoxy group, a phenylalkyl group, or an alkylsulfonic acid group.

  The second invention is the sensitizer according to the first invention, which has a maximum spectral sensitivity peak at 350 nm to 450 nm.

  The third invention is a photosensitive composition for a blue-violet semiconductor laser, characterized by containing the sensitizer described in the first or second invention.

  The fourth invention is the photosensitive composition for blue-violet semiconductor laser according to the third invention, which contains an ethylenically unsaturated compound.

  5th invention is a photosensitive composition for blue-violet semiconductor lasers as described in 3rd or 4th invention characterized by containing a photoinitiator.

  A sixth invention is an image forming material comprising a layer of the blue-violet semiconductor laser photosensitive composition according to any one of the third to fifth inventions formed on a temporary support film. .

  A seventh invention is an image forming material, wherein the image forming material according to the sixth invention is laminated on the substrate to be processed on the photosensitive composition layer side.

  According to the present invention, a photosensitive composition for a blue-violet semiconductor laser having excellent sensitivity to a blue-violet semiconductor laser is obtained by using the squarylium compounds represented by the general formulas (A) to (D) as sensitizers. Can be provided.

  The sensitizer of the present invention will be described.

  The sensitizer of the present invention is a squarylium compound comprising a squarylium compound represented by general formulas (A) to (D) and a hydrogen ion or a transition metal ion.

In general formula (A), R _{1 to} R ₆ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₁ may be linked to form a hydrocarbon ring.

In general formula (B), R ₇ is hydrogen or an alkyl group which may have a substituent, and R _{8 to} R ₁₁ have the same or different hydrogen, halogen atom and substituent. Represents an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an alkoxy group, a phenylalkyl group, an alkylsulfonic acid group, and R ₈ and R ₉ , R ₁₀ and R ₁₁ are linked to form a hydrocarbon ring. Also good.

In general formula (C), R _{12 to} R ₁₄ may be the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. Group, an alkylsulfonic acid group.

In the general formula (D), R _{15 to} R ₁₉ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. Group, an alkylsulfonic acid group, X is O, S, N—R ₂₀ , C—R ₂₁ R ₂₂ (R _{20 to} R ₂₂ may be the same or different and each has a hydrogen atom, a halogen atom, or a substituent. An alkyl group, a halogenated alkyl group, a cyanoalkyl group, an alkoxy group, a phenylalkyl group, or an alkylsulfonic acid group.

  Examples of transition metal ions include nickel ions, iron ions, copper ions, cobalt ions, zinc ions, magnesium ions and the like, with nickel ions being particularly preferred.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom is mentioned.

  Examples of the alkyl group which may have a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, n- Examples thereof include straight-chain or branched alkyl groups having 1 to 20 carbon atoms such as hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group and n-octadecyl group. Preferred are 10 linear or branched alkyl groups.

  The halogenated alkyl group is a linear or branched halogenated alkyl group having 1 to 12 carbon atoms. The halogen atom of the halogenated alkyl group is particularly preferably a fluorine atom, that is, a fluorinated alkyl group, from the viewpoint of excellent effects of improving the sensitivity of the squarylium compound and the compatibility with the resin.

  Examples of the fluorinated alkyl group include trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 5,5,5, 5-trifluoropentyl group, 6,6,6-trifluorohexyl group, 8,8,8-trifluorooctyl group, 2-methyl-3,3,3-trifluoropropyl group, perfluoroethyl group, perfluoropropyl Group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, 2-trifluoromethyl-perfluoropropyl group and the like.

  The cyanoalkyl group is preferably a linear or branched cyanoalkyl group having 1 to 10 carbon atoms, and the number of substituted cyano groups is preferably 1 to 3. Particularly preferred are propionitrile group, butyronitrile group, pentylnitrile group, 1-methylpropionitrile group, 1-methylbutyronitrile group and the like.

  As the alkoxy group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methoxyethoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, methoxymethyl group, methoxyethyl group , Methoxypropyl group, methoxybutyl group, methoxyhexyl group, methoxyoctyl group, ethoxyethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, ethoxyhexyl group, ethoxyoctyl group, propoxymethyl group, propoxypropyl group, propoxy C1-C18 linear or branched alkoxy groups, such as a hexyl group and a butoxyethyl group, are mentioned.

  As said phenylalkyl group, the C1-C8 thing of an alkyl group is preferable, and a phenyl group may have a substituent, an alkyl group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, You may have an at least 1 sort (s) of substituent from the group which consists of an amino group, an alkoxy group, a halogenated alkyl group, and a halogen. Examples of the phenylalkyl group include benzyl group, phenethyl group, phenylpropyl group, phenyl-α-methylpropyl group, phenyl-β-methylpropyl group, phenylbutyl group, and phenylpentyl group.

  As said alkylsulfonic acid group, a C1-C6 alkylsulfonic acid group is preferable. Specific examples include a methyl sulfonic acid group, an ethyl sulfonic acid group, and a propyl sulfonic acid group.

  Specific examples of the squarylium compound ions (chemical formulas (1) to (24)) are shown below.

  The squarylium compound of the present invention has a good solubility in an organic solvent and is excellent in photosensitivity to a blue-violet semiconductor laser.

  Next, the photosensitive composition for blue-violet semiconductor laser of the present invention will be described.

  The photosensitive composition for blue-violet semiconductor laser of the present invention comprises a sensitizer containing a squarylium compound comprising a squarylium compound ion represented by general formulas (A) to (D) and a hydrogen ion or a transition metal ion. It is a photosensitive composition for a blue-violet semiconductor laser having at least the characteristics to be contained and obtained by mixing and polymerizing a photopolymerization initiator and an ethylenically unsaturated compound.

  A binder, an additive (a polymerization accelerator, a thermal polymerization inhibitor, a plasticizer, etc.) can be used as necessary.

  The photopolymerization initiator, when irradiated with light in the presence of a sensitizer containing a squarylium compound, receives photoexcitation energy of the sensitizer and generates active radicals, leading to polymerization of the ethylenically unsaturated compound. Radical generators, for example, hexaarylbiimidazole compounds, titanocene compounds, halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, diaryliodonium salts, organoborates, An organic peroxide etc. are mentioned. From the aspects of sensitivity as a blue-violet laser photosensitive composition, adhesion to a substrate and storage stability, hexaarylbiimidazole compounds and titanocene compounds are preferable, and hexaarylbiimidazole compounds are particularly preferable.

  The ethylenically unsaturated compound is addition-polymerized by the action of a photopolymerization initiation system containing a photopolymerization initiator when the photosensitive composition for a blue-violet semiconductor laser is irradiated with actinic rays, and optionally cross-linked. It is a compound having at least one radical polymerizable ethylenically unsaturated bond in the molecule that cures.

  Examples of the ethylenically unsaturated compound include compounds having one ethylenically unsaturated bond in the molecule, for example, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, etc. Or its alkyl ester, (meth) acrylonitrile, (meth) acrylamide, styrene, etc., and ethylenically unsaturated bond from the point of being able to expand the difference in polymer solubility and developer solubility between exposed and unexposed areas. Is preferably a compound having two or more in the molecule, and particularly preferably an acrylate compound whose unsaturated bond is derived from a (meth) acryloyloxy group.

  Examples of the binder include polymethacrylic acid ester, polyacrylic acid ester, polyvinyl acetate, copolymer of vinyl acetate and ethylene, polystyrene, polyvinyl formal, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, and chlorine. Polypropylene, phenol novolac resin, polyvinyl phenol, copolymer of vinyl phenol and methacrylic acid ester, polyethylene oxide, polymethyl isopropenyl ketone, copolymer of methacrylic acid ester and phenyl isopropenyl ketone, polyurethane, polyamide, polycarbonate , Polyethylene terephthalate, polybutylene terephthalate, acetylcellulose, acetylbutylcellulose, nitrocellulose, polyvinylcarbazo , Copolymers of vinyl carbazole and styrene, a copolymer of vinylcarbazole and methacrylic acid esters, copolymers of vinyl carbazole and acrylic acid esters.

  Examples of the polymerization accelerator include 2-mercaptobenzothiazole. Examples of the thermal polymerization inhibitor include p-tert-butylcatechol, hydroquinone, chloranil and the like. Examples of the plasticizer include diethyl hexyl phthalate, diisobutyl phthalate, tricresyl phosphate, diethyl hexyl sebacate, diethyl hexyl adipate, and the like. Examples of the thermosetting compound include a methacrylate monomer or acrylate monomer having at least one epoxy group, a styrene monomer having at least one epoxy group, and a polyglycidyl compound having no other reactive group. Further, polymers having two or more epoxy groups, such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, urethane modified epoxy resins, epoxy group-containing copolymers, etc., respectively Can be mentioned.

  As a solvent used when manufacturing the photosensitive composition for blue-violet semiconductor laser of the present invention, it is desirable that the solvent has good solubility or good dispersibility with respect to each component. Cellosolve, ethyl cellosolve, butyl solosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl acetate, butyl acetate, methanol, ethanol, 2-propanol, N, N-dimethylformamide, dimethyl Examples include acetamide, N-methylpyrrolidone, cyclohexane, and toluene.

  0.001-5 mass parts is preferable with respect to 100 mass parts of all compositions, and, as for the usage-amount of the sensitizer in the photosensitive composition for blue-violet semiconductor lasers of this invention, 0.01-2 mass parts is more. Preferably mentioned. 0.1-100 mass parts is preferable with respect to 1 mass part of sensitizers, and 1-50 mass parts is mentioned more preferably with a photoinitiator. 2-1000 mass parts is preferable with respect to 1 mass part of sensitizers, and, as for an ethylenically unsaturated compound, 20-200 mass parts is mentioned more preferably.

350-450 nm is preferable, as for the maximum peak of the preferable spectral sensitivity of the photosensitive composition for blue-violet semiconductor lasers of this invention, 355-440 nm is more preferable, 360-430 nm is mentioned especially preferable.
If it is less than 350 nm or more than 450 nm, there is a drawback that sensitivity to a blue-violet semiconductor laser is lowered.

  The maximum spectral sensitivity peak in the present invention refers to a photocurable image-forming material sample having a photocurable composition layer formed on a substrate surface, which is obtained by transversely dividing light obtained by spectrally measuring from a light source of a xenon lamp using a spectral sensitivity measuring device. After exposure in the axial direction, an image corresponding to the sensitivity of each exposure wavelength is obtained by developing, and the exposure energy that allows image formation is calculated from the height of the image. The maximum peak in the spectral sensitivity curve obtained by plotting the reciprocal of the exposure energy.

  Moreover, solubility can be improved by using the squarylium compound of a transition metal salt. When dissolved and used, it is preferable to use a squarylium compound of a transition metal salt.

  Next, the image forming material will be described.

  The image forming material is usually applied onto a temporary support film as a coating solution in which the above-described components are dissolved in an appropriate solvent and dried. If necessary, the surface of the prepared photosensitive composition layer is covered with a coating film. Is formed. Examples of such an image forming material include a dry film resist material.

The image forming material can be used to form the image forming material of the present invention.
When the photosensitive composition layer side of the image forming material is covered with a coating film, the coating film is peeled off and laminated on the substrate to be processed. There is a way.
(1) A coating solution is prepared by dissolving each component of the blue-violet laser-sensitive composition in an appropriate solvent. (2) Apply directly on the substrate to be processed and dry. (3) A layer of the negative blue-violet laser photosensitive composition of the present invention is formed on the substrate to be processed.
Furthermore, the image forming material is suitably used in the following image forming method. That is, the photosensitive composition layer of the image forming material is scanned and exposed with a laser beam having a wavelength of 340 to 430 nm, for example, and developed to reveal an image.

  As the temporary support film when used as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. At that time, when those films have the solvent resistance, heat resistance, etc. necessary for the production of the dry film resist material, the photosensitive composition coating solution is directly applied on the temporary support film. It can be applied and dried to produce a dry film resist material, and even if those films have low solvent resistance, heat resistance, etc., for example, polytetrafluoroethylene film, release film, etc. First, a photosensitive composition layer is formed on a film having releasability, and then a temporary support film having low solvent resistance and heat resistance is laminated on the layer, and then the film having releasability is peeled off. By doing so, a dry film resist material can also be produced.

  The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility with respect to the components used and gives good film formability. For example, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether and other propylene glycol solvents, Butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate Ester solvents such as ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as methanol, isopropanol, heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketones such as cyclohexanone, methyl ethyl ketone, etc. Examples of the solvent include aromatic solvents such as toluene, high-polarity solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and those obtained by adding an aromatic hydrocarbon thereto. Among these, single or mixed solvents such as methyl ethyl ketone, methanol, isopropanol, and toluene are preferable from the viewpoint of solubility and viscosity. The use ratio of the solvent is in the range of about 0.5 to 2 times by mass ratio with respect to the total amount of the photosensitive composition.

  Examples of the coating method include a die coating method, a knife coating method, a roll coating method, a spray coating method, and a spin coating method. In this case, the coating amount is usually 5 μm or more as a dry film thickness, and preferably 10 μm or more as a dry film resist material, from the viewpoints of image formability and subsequent processability such as etching and plating. More preferably, it is 15 μm or more, and in terms of sensitivity and the like, it is preferably 200 μm or less, and more preferably 100 μm or less.

  When used as a dry film resist material or the like, it is preferable to cover the surface of the formed photosensitive composition layer with a coating film until it is laminated on a substrate to be processed. Conventionally known films such as a film, a polypropylene film and a polytetrafluoroethylene film are used.

  When the photosensitive composition layer side of the dry film resist material is covered with a coating film, the coating film is peeled off and laminated by heating, pressing, or the like, or the photosensitive composition The substrate to be processed in producing a resist image-forming material by directly applying and drying an object coating solution appears by exposing the photosensitive composition layer formed thereon to a laser beam and developing it. A pattern such as a circuit or an electrode is formed on the surface by etching or plating using the resulting image as a resist. Copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel It may be a metal plate itself such as epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol, etc. Thermosetting resin such as fat, melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, resin such as thermoplastic resin, paper , Glass and inorganic materials such as alumina, silica, barium sulfate, calcium carbonate, or composite materials such as glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin, etc. The metal or metal foil such as indium oxide, tin oxide, indium oxide doped tin oxide or the like is heated and pressure-bonded laminated on the surface of the insulating support having a thickness of about 0.02 to 10 mm. Or the thickness of the metal is 1-1 by sputtering, vapor deposition, plating, etc. Metal-clad laminate formed with 0μm approximately conductive layer is preferably used.

  In the case where an image forming material is produced by directly applying and drying the photosensitive composition coating solution, the polymerization inhibiting action by oxygen of the photosensitive composition layer formed on the substrate to be processed is prevented. For example, a protective layer formed by applying and drying a solution of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, or the like may be provided on the photosensitive composition layer. .

  Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited at all by this Example. “%” In the examples represents “% by mass”.

<Synthesis of squarylium compound>
The squarylium compounds (compounds (a) to (j)) used in the examples are summarized in Table 1.

(Production of squarylium compound (a))
In a three-necked flask equipped with a condenser tube, 5.0 parts of 3,4-dichloro-3-cyclobutene-1,2-dione and 4.6 parts of N, N-dibutylaniline are placed, and 80 parts of dehydrated toluene are added thereto. And stirred at room temperature for 24 hours. After completion of the reaction, the mixture was washed with an aqueous NaHCO ₃ solution, extracted with toluene, and the solvent was distilled off under reduced pressure. The obtained solid was collected by filtration under reduced pressure, washed with hexane, and dried under reduced pressure to give 3-chloro-4- [4- (N, N-dibutylamino) phenyl] 3-cyclobutene-1,2-dione 5 .5 parts were obtained.

  In a three-necked flask equipped with a condenser, 5.5 parts of 3-chloro-4- [4- (N, N-dibutylamino) phenyl] 3-cyclobutene-1,2-dione and acetic acid: water = 4: 50 parts of 1 mixed solution was added and stirred with heating at 100 ° C. for 5 hours. After the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration under reduced pressure. After washing with water and drying under reduced pressure, 4.1 parts of squarylium compound (a) was obtained.

(Production of squarylium compound (b))
The squarylium compound (b) was prepared in the same manner as the squarylium compound (a) except that N, N-dibutylaniline was replaced with N, N-dimethyl-1-naphthylamine in the method of producing the squarylium compound (a). Obtained.

(Production of squarylium compound (c))
In a three-necked flask equipped with a condenser tube, 12.3 parts of 3,4-dichloro-3-cyclobutene-1,2-dione and 10.9 parts of anhydrous aluminum chloride are placed, and 100 ml of anhydrous chloroform is placed therein, and nitrogen is added. Stir at room temperature under atmosphere. Thereto, 10.0 parts of anisole dissolved in 20 ml of anhydrous chloroform was added dropwise at room temperature. After completion of dropping, the mixture was stirred with heating for 10 hours. After completion of the reaction, 100 ml of water was added in a state cooled to 10 ° C. or lower, the organic layer was washed with water, and the solvent was distilled off under reduced pressure. The resulting solid was collected by filtration under reduced pressure, washed with toluene, and dried under reduced pressure to give 11.6 parts of 3-chloro-4- (p-methoxy-phenyl) -cyclobut-3-ene-1,2-dione. Got.
In a three-necked flask equipped with a condenser, 11.6 parts of 3-chloro-4- (p-methoxy-phenyl) -cyclobut-3-ene-1,2-dione and acetic acid: water = 1: 1 mixed solution 200 parts were added and stirred with heating at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the precipitated solid was collected by filtration under reduced pressure. After washing with water and drying under reduced pressure, 8.6 parts of squarylium compound (c) was obtained.

(Production of squarylium compound (d))
In a three-necked flask, 6.2 parts of 3,4-dimethoxy-3-cyclobutene-1,2-dione and 7.6 parts of 3-methyl-1- (3-propyl) -5-pyrazolone (manufactured by Lancaster) Then, 500 ml of methanol was added thereto and stirred at room temperature. Thereto, 5.9 parts of anhydrous potassium carbonate was added and stirred at room temperature for 5 hours. After completion of the reaction, the solid was filtered and washed with methanol. To the obtained solid, 200 ml of water and 2.7 parts of potassium carbonate were added, and the mixture was heated and stirred at 50 ° C. for 2 hours. After completion of the reaction, the solution was poured into 500 ml of 1M hydrochloric acid and the precipitated solid was filtered. After washing with water, it was dried under reduced pressure to obtain 4.3 parts of squarylium compound (d).

(Production of squarylium compound (e))
The squarylium compound (e) was obtained in the same manner as the squarylium compound (d) except that the method for producing the squarylium compound (d) was replaced with N-ethyl-2-methylthiazolium iodide.

(Production of squarylium compound (f))
Place 4.1 parts of squarylium compound (a) and 4.0 parts of nickel acid tetrahydrate in a three-necked flask equipped with a condenser, add 100 parts of THF, and heat and stir at 60 ° C. for 4 hours. did. After the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration under reduced pressure. After washing with water and drying under reduced pressure, 3-hydroxy-4- [4- (N-methyl-N-butylamino) phenyl] 3-cyclobutene-1,2-dione-nickel complex (squarylium compound (f)) 8 .3 parts were obtained.

(Production of squarylium compound (g))
A squarylium compound (g) was obtained by the same method as the squarylium compound (f) except that the squarylium compound (a) was replaced with (b).

(Production of squarylium compound (h))
The squarylium compound (h) was obtained by the same method as the squarylium compound (f) except that the squarylium compound (a) was replaced with (c).

(Production of squarylium compound (i))
The squarylium compound (i) was obtained by the same method as the squarylium compound (f) except that the squarylium compound (a) was replaced by (d).

(Production of squarylium compound (j))
A squarylium compound (j) was obtained by the same method as the squarylium compound (f) except that the squarylium compound (a) was replaced by (e).

  A benzophenone compound, a coumarin compound, and a squarylium compound were used as sensitizers for comparative examples. The compounds used in the comparative examples are shown in Table 2.

Example 1
<Production of photosensitive composition for blue-violet semiconductor laser and image forming material>
100 parts of pentaerythritol acrylate, 100 parts of polyvinylpyrrolidone, 10 parts of 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, squarylium compound (a ) 0.1 part was dissolved in 900 parts of methyl cellosolve to obtain a photosensitive composition for blue-violet laser. The obtained photosensitive composition for blue-violet laser was applied to a polyester film using a spin coater and dried to prepare an image forming material (film thickness: 2 μm).

<Maximum peak of spectral sensitivity>
A sample obtained by cutting the image-forming material into a size of 50 × 60 mm, using a diffraction spectroscopic irradiator, and using a xenon lamp as a light source, the light split in the wavelength region of 350 to 650 nm, the exposure wavelength is linear in the horizontal axis direction, The exposure intensity is set to logarithmically change in the vertical axis direction, and exposure is performed by irradiating for 10 seconds. Then, a 0.7 mass% sodium carbonate aqueous solution at 25 ° C. is sprayed as a developing solution to 0.15 MPa, By performing spray development in 1.5 times the minimum development time, an image corresponding to the sensitivity of each exposure wavelength is obtained, and the exposure energy capable of image formation is calculated from the image height, the wavelength on the horizontal axis, The maximum peak in the spectral sensitivity curve obtained by plotting the reciprocal of the exposure energy on the vertical axis was read.

<Measurement of exposure sensitivity>
Using the blue-violet semiconductor laser having a center wavelength of 405 nm and a laser output of 5 mW, the obtained photosensitive composition layer was operated and exposed while changing the beam scanning interval and the scanning speed at an image plane illuminance of 2 mW and a beam spot diameter of 2 μm. Subsequently, a 0.7 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed as a developing solution to a pressure of 0.15 MPa, and a negative image was made to appear by spray development in a time twice as long as the minimum developing time. With respect to the obtained image, an exposure amount required for reproducing a line width of 20 μm was obtained and used as exposure sensitivity.

(Examples 2 to 10, Comparative Examples 1 to 3)
In Examples 2 to 10 and Comparative Examples 1 to 3, an image forming material was prepared in the same manner as in Example 1 using the sensitizers shown in Table 3, and the maximum spectral sensitivity peak and exposure sensitivity were measured.

  Table 3 shows the measurement results of the maximum peak of spectral sensitivity and the exposure sensitivity.

  From Table 3, it can be seen that Examples 1 to 10 have better sensitivity to the blue-violet semiconductor laser than Comparative Examples 1 to 3.

  Sensitizer of the present invention and photosensitive composition for blue-violet semiconductor laser using the same are used for liquid crystal display element, plasma display, large scale integrated circuit, thin transistor, semiconductor package, color filter, organic electroluminescence, hologram recording material Applicable to etc.

Claims (7)

A sensitizer comprising a squarylium compound comprising a squarylium compound ion represented by the following general formulas (A) to (D) and a hydrogen ion or a transition metal ion.

(In formula (A), R _{1 to} R ₆ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. And R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₆ and R ₁ may be linked to form a hydrocarbon ring.

(In Formula (B), R ₇ is hydrogen or an alkyl group that may have a substituent, and R _{8 to} R ₁₁ have the same or different hydrogen, halogen atom, and substituent. Represents an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an alkoxy group, a phenylalkyl group, an alkylsulfonic acid group, and R ₈ and R ₉ , R ₁₀ and R ₁₁ are linked to form a hydrocarbon ring. May be.)

(In the formula (C), R _{12 to} R ₁₄ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. Group represents an alkylsulfonic acid group.)

(In the formula (D), R _{15 to} R ₁₉ are the same or different hydrogen, halogen atom, optionally substituted alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxy group, phenylalkyl. Group, an alkylsulfonic acid group, X is O, S, N—R ₂₀ , C—R ₂₁ R ₂₂ (R _{20 to} R ₂₂ may be the same or different and each has a hydrogen atom, a halogen atom, or a substituent. An alkyl group, a halogenated alkyl group, a cyanoalkyl group, an alkoxy group, a phenylalkyl group, or an alkylsulfonic acid group.   The sensitizer according to claim 1, which has a maximum spectral sensitivity peak at 350 nm to 450 nm.   A photosensitive composition for a blue-violet semiconductor laser, comprising the sensitizer according to claim 1.   4. The photosensitive composition for blue-violet semiconductor laser according to claim 3, comprising an ethylenically unsaturated compound.   5. The photosensitive composition for blue-violet semiconductor laser according to claim 3, comprising a photopolymerization initiator.   An image forming material comprising a layer of the photosensitive composition for a blue-violet semiconductor laser according to any one of claims 3 to 5 formed on a temporary support film.   An image forming material, wherein the image forming material according to claim 6 is laminated on the substrate to be processed on the photosensitive composition layer side.