WO2010113478A1 - Curable resin composition and printed wiring board - Google Patents

Curable resin composition and printed wiring board Download PDF

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Publication number
WO2010113478A1
WO2010113478A1 PCT/JP2010/002305 JP2010002305W WO2010113478A1 WO 2010113478 A1 WO2010113478 A1 WO 2010113478A1 JP 2010002305 W JP2010002305 W JP 2010002305W WO 2010113478 A1 WO2010113478 A1 WO 2010113478A1
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WO
WIPO (PCT)
Prior art keywords
resin
parts
group
manufactured
compound
Prior art date
Application number
PCT/JP2010/002305
Other languages
French (fr)
Japanese (ja)
Inventor
伊藤信人
有馬聖夫
Original Assignee
太陽インキ製造株式会社
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Filing date
Publication date
Priority claimed from JP2009087372A external-priority patent/JP5385663B2/en
Priority claimed from JP2009118731A external-priority patent/JP5385680B2/en
Application filed by 太陽インキ製造株式会社 filed Critical 太陽インキ製造株式会社
Priority to KR1020117022729A priority Critical patent/KR101690811B1/en
Priority to CN201080014677.0A priority patent/CN102369482B/en
Publication of WO2010113478A1 publication Critical patent/WO2010113478A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Definitions

  • the present invention relates to a curable resin composition used as a solder resist for printed wiring boards.
  • a carboxyl group-containing photosensitive resin generally an epoxy acrylate modified resin derived by modification of an epoxy resin
  • a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound is disclosed (patent) Reference 1).
  • (meth) acrylic acid is added to the epoxy resin obtained by reacting the reaction product of salicylaldehyde and monohydric phenol with epichlorohydrin, and polybasic carboxylic acid or its anhydride is further reacted.
  • a solder resist composition composed of a photosensitive resin, a photopolymerization initiator, an organic solvent, and the like is disclosed (see Patent Document 2).
  • an epoxy skeleton is generally introduced by reacting epichlorohydrin containing chlorine or the like.
  • chlorine ion impurities that cause a decrease in insulation reliability are by-produced, and it is very difficult to remove them. Therefore, the epoxy resin used as a raw material contains a large amount of chlorine ion impurities. Is almost. Also, it is very difficult to remove this chloride ion impurity after the epoxy acrylate modification.
  • solder resists are also required to have high performance such as excellent developability and high workability in response to the recent increase in the density of printed wiring boards as electronic devices become lighter and thinner.
  • high performance such as excellent developability and high workability in response to the recent increase in the density of printed wiring boards as electronic devices become lighter and thinner.
  • PCT pressure cooker test
  • the solder resist is also required to have reactivity with ultraviolet rays used for patterning, that is, high exposure sensitivity.
  • the conventional liquid development type solder resist has only a few hours to a few dozen hours in the PCT resistance test and does not have sufficient wet heat resistance. Also, when the package is mounted, moisture absorbed by the solder resist boils the moisture absorbed inside the package during reflow, causing cracks in the solder resist film inside the package and its surroundings, and sufficient crack resistance cannot be obtained. is there.
  • the present invention has been made to solve the above-mentioned problems, has good workability, high sensitivity and excellent developability, and the cured product thereof is used, for example, in a printed wiring board or a semiconductor package.
  • Another object of the present invention is to provide a curable resin composition capable of obtaining excellent PCT resistance and high insulation reliability.
  • the curable resin composition of the present invention reacts a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide or a cyclocarbonate. Containing a carboxyl group-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid with the reaction product obtained and reacting the resulting reaction product with a polybasic acid anhydride, and a photopolymerization initiator.
  • a curable resin composition is provided.
  • R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.
  • the cured product has high reliability such as excellent PCT resistance and high insulation reliability when used for, for example, a printed wiring board or a semiconductor package. It becomes possible. Also, in the carboxyl group-containing photosensitive resin, the unsaturated group and the carboxyl group do not exist on the same chain and are located at the end of the side chain, respectively, so that the reactivity is high (high sensitivity) and the alkali development is excellent. Can be realized.
  • the acid value of the carboxyl group-containing photosensitive resin is preferably 30 to 150 mgKOH / g. By setting the acid value within this range, alkali development is possible and sufficient development resistance can be obtained.
  • the alkylene oxide is preferably ethylene oxide and propylene oxide or ethylene oxide or propylene oxide
  • the cyclocarbonate compound is preferably ethylene carbonate and propylene carbonate or ethylene carbonate or propylene carbonate.
  • the unsaturated group-containing monocarboxylic acid is preferably acrylic acid and methacrylic acid or acrylic acid or methacrylic acid. With such a configuration, it can be used as a highly sensitive photocurable resin composition. Moreover, in the curable resin composition of this invention, it is preferable that carboxyl group-containing photosensitive resin does not contain a hydroxyl group. With such a configuration, the moisture absorption resistance is excellent, and excellent PCT resistance can be obtained in the cured product.
  • the curable resin composition of the present invention preferably contains a thermosetting component. With such a configuration, it can be used as a thermosetting resin composition capable of main curing by heat, and heat resistance is further imparted to the curable resin composition.
  • the curable resin composition of the present invention preferably contains a colorant.
  • a colorant when used as a solder resist for a printed wiring board, it is possible to obtain a concealing property such as a circuit.
  • such a curable resin composition can be applied to a substrate and cured by irradiation with active energy rays and heating or irradiation with active energy rays or heating to obtain a cured product.
  • a cured product for example, when used for a printed wiring board or a semiconductor package, it is possible to obtain high reliability such as excellent PCT resistance and high insulation reliability.
  • such a curable resin composition can be applied to a film and dried to be used as a curable dry film.
  • a resist layer can be easily formed without coating.
  • this dry film can be affixed to a substrate and cured by active energy ray irradiation and heating or active energy ray irradiation or heating to obtain a cured product.
  • a cured product for example, when used for a printed wiring board or a semiconductor package, it is possible to obtain high reliability such as excellent PCT resistance and high insulation reliability.
  • the curable resin composition has good workability, high sensitivity and excellent developability, and in the cured product, for example, when used for a printed wiring board or a semiconductor package, Excellent PCT resistance and high insulation reliability can be obtained.
  • the present inventors have started a phenol resin having at least one skeleton of the general formulas (I) to (VI) as an essential component of the composition.
  • the inventors have found that the above object can be achieved by using a carboxyl group-containing photosensitive resin as a raw material, and have completed the present invention.
  • This carboxyl group-containing photosensitive resin is excellent in flexibility by chain extension by addition reaction between a phenol resin having at least one skeleton of general formulas (I) to (VI) and alkylene oxide or cyclocarbonate, Elongation can be obtained.
  • unsaturated group-containing monocarboxylic acid and polybasic acid anhydride are added to the terminal hydroxyl group generated by the addition reaction of alkylene oxide or cyclocarbonate, and the unsaturated group or carboxyl group is on the same side chain. Since it does not exist and is located at the end of each side chain, it has excellent reactivity. Furthermore, it has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain.
  • this carboxyl group-containing photosensitive resin is excellent in moisture absorption resistance because it has no or only a slightly reactive hydrophilic alcoholic hydroxyl group.
  • the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but significantly reduces moisture resistance.
  • the carboxyl group-containing photosensitive resin in the present invention can improve moisture resistance by substantially not containing a hydroxyl group. And the improvement of the moisture resistance makes it possible to improve the PCT resistance required for the IC package.
  • the phenol resin having at least one skeleton of the general formulas (I) to (VI) used in the present invention is characterized in that the hydroxyl equivalent is larger than that of normal phenol or cresol type novolac resin.
  • a cured product using a carboxyl group-containing resin derived from the phenols has better flexibility than general novolak resins.
  • a solder resist composition using a carboxylic acid-containing resin derived from a phenol resin having at least one skeleton of general formulas (I) to (VI) It is possible to improve the thermal shock resistance and PCT resistance of the resulting cured product.
  • the carboxyl group-containing photosensitive resin derived from the general formula (III) can obtain very excellent insulation reliability and PCT resistance.
  • the carboxyl group-containing photosensitive resin constituting the curable resin composition of the present invention can be easily obtained by the following method.
  • An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide, A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.
  • An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with a cyclocarbonate compound.
  • a carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.
  • the carboxyl group-containing photosensitive resin in the present invention is obtained using phenol resins having various skeletons as starting materials. Since the phenol resin containing almost no chloride ion impurities can be easily obtained, the chloride ion impurity concentration in the resulting carboxyl group-containing photosensitive resin can be greatly suppressed.
  • the chloride ion content of such a carboxyl group-containing photosensitive resin is preferably 100 ppm or less. More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less.
  • such a carboxyl group-containing photosensitive resin is also characterized in that it is a resin that does not substantially contain a hydroxyl group.
  • substantially free of hydroxyl groups means that a trace amount of hydroxyl groups is allowed.
  • carboxyl group-containing resin in the present invention can greatly reduce the number of ester bonds to the aromatic ring per repeating unit depending on the phenol resin raw material used.
  • a cured resist coating is formed on a copper-clad laminate with very fine pitch lines / spaces, and voltage is applied to judge the insulation reliability.
  • voltage is applied to judge the insulation reliability.
  • the absorbed water causes electrolysis between the electrodes. At this time, it becomes alkaline on the cathode side and acidic on the anode side.
  • a conventional phenol novolac type epoxy acrylate is obtained by adding acrylic acid to an epoxy resin synthesized from a phenol novolac resin and adding an acid anhydride to the hydroxyl group to be produced. Therefore, the number of ester bonds to the aromatic ring per repeating unit is 2.
  • the carboxyl group-containing resin according to the present invention derived from a phenol resin reacts with an acrylic acid or an acid anhydride after reacting an alkylene oxide or a cyclocarbonate compound with a phenol resin having various skeletons. Therefore, the number of ester bonds per aromatic ring per repeating unit is theoretically never greater than 1.0.
  • the number of ester bonds to the aromatic ring per repeating unit is 1, 0.5 in the general formula (IV), 0.66 in the general formula (VI), and the general formula In (III), it is possible to reduce to 0.33, and therefore it is possible to exhibit excellent insulation reliability.
  • the number of ester bonds to the aromatic ring per repeating unit of the carboxyl group-containing resin used in the present invention is 1 or less, preferably 0.75 or less, more preferably 0.5 or less.
  • a cured product obtained from a carboxyl group-containing resin derived from a phenol resin having various skeletons used in the present invention is compared with a cured product obtained from a carboxyl group-containing resin derived from a conventional phenol novolac resin. It is possible to develop excellent characteristics derived from the phenol resin raw material used. For example, various properties such as improvement of glass transition temperature (Tg), improvement of breaking strength of cured coating film and provision of toughness, improvement of thermal shock resistance, improvement of hydrolysis resistance, and further improvement of flame retardancy Can be granted.
  • Tg glass transition temperature
  • breaking strength of cured coating film and provision of toughness improvement of thermal shock resistance, improvement of hydrolysis resistance, and further improvement of flame retardancy
  • glycidyl (meth) acrylate 4-hydroxybutyl acrylate glycidyl ether, or 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of reactivity and supply.
  • (Meth) acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the addition amount of such a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is preferably 5% equivalent to 40% equivalent to the carboxyl group.
  • the added amount is less than 5% equivalent, sufficient sensitivity increase and improvement of the solder resist characteristics cannot be obtained, and when it exceeds 40% equivalent, the maximum development life is shortened and the dryness to the touch is deteriorated. More preferably, it is 10% equivalent to 30% equivalent.
  • the acid value of the carboxyl group-containing photosensitive resin is preferably in the range of 30 to 150 mgKOH / g. When it is lower than 30 mgKOH / g, the solubility in an aqueous alkali solution is lowered, and development of the formed coating film becomes difficult.
  • the concentration is higher than 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line fades more than necessary, or dissolution and peeling occurs with the developer without distinction between the exposed portion and the unexposed portion. It may be difficult to draw a resist pattern. And it causes the appearance defect and the deterioration of electrical characteristics. More preferably, it is in the range of 40 to 130 mgKOH / g.
  • the weight average molecular weight of such a carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally preferably in the range of 2,000 to 150,000.
  • the weight average molecular weight is less than 2,000, tack-free performance is deteriorated, the moisture resistance of the coated film after exposure is poor, film loss occurs during development, and resolution may be greatly deteriorated.
  • the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated and the storage stability may be inferior. More preferably, it is 5,000 to 100,000.
  • the blending amount of such a carboxyl group-containing photosensitive resin is preferably 20 to 60% by mass in the entire composition. When it is less than 20% by mass, the coating film strength is lowered. On the other hand, when it is more than 60% by mass, the viscosity becomes high, and the coating property and the like are lowered. More preferably, it is 30 to 50% by mass.
  • the carboxyl-containing resin used in the present invention is not particularly limited as long as it is derived from a phenol resin having a structure of general formulas (I) to (VI).
  • R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.
  • phenol resin used in the present invention examples include bisphenol A-formaldehyde type phenol resin, salicylaldehyde type phenol resin, phenyl aralkyl type phenol resin, biphenyl aralkyl type phenol resin, phenylene aralkyl type phenol resin, ⁇ -naphthol, ⁇ -naphthol and the like.
  • a naphthol aralkyl type phenol resin, a dicyclopentadiene skeleton-containing phenol resin, or the like can be used.
  • the resin having a skeleton of the general formula (I) for example, BPA-D manufactured by Meiwa Kasei Co., Ltd. can be used.
  • the resin having the skeleton of the general formula (II) for example, MEH-7500 manufactured by Meiwa Kasei Co., Ltd. can be used.
  • the resin having the skeleton of the general formula (III) for example, MEH-851 manufactured by Meiwa Kasei Co., Ltd. can be used.
  • the resin having a skeleton of the general formula (IV) for example, MEH-7800 manufactured by Meiwa Kasei Co., Ltd. can be used.
  • the resin having a skeleton of the general formula (V) for example, DPP-6115H manufactured by Shin Nippon Oil Co., Ltd. can be used.
  • the resin having a skeleton of the general formula (VI) for example, Kayahard CBN manufactured by Nippon Kayaku Co., Ltd. can be used.
  • alkylene oxide examples include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and the like, and ethylene oxide and propylene oxide are preferable from the viewpoint of price and supply system.
  • cyclocarbonate compound known carbonate compounds can be used, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate. Among these, 5-membered ethylene carbonate and propylene carbonate are preferable from the viewpoint of reactivity and supply system.
  • These alkylene oxides and cyclocarbonate compounds can be used alone or in admixture of two or more.
  • An alkylene oxide or a cyclocarbonate compound is obtained by adding an alcoholic hydroxyl group from a phenolic hydroxyl group by an addition reaction using a basic catalyst to the phenolic hydroxyl group of a phenol resin having a structure of general formulas (I) to (VI). It can be modified to have a resin.
  • the addition amount at this time is preferably in the range of 0.3 to 10 mol per equivalent of phenolic hydroxyl group. When the addition amount is less than 0.3 mol, a reaction with an unsaturated group-containing monocarboxylic acid or polybasic acid anhydride described later hardly occurs, and the photosensitivity and solubility in a dilute alkaline aqueous solution are lowered.
  • the addition amount exceeds 10 moles, water resistance decreases due to the ether bond to be generated, and electrical insulation, PCT resistance and the like decrease.
  • the range is more preferably 0.8 to 5 mol, and still more preferably 1.0 to 3 mol.
  • unsaturated group-containing monocarboxylic acids examples include acrylic acid, methacrylic acid, or even hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adducts. More preferred are acrylic acid and / or soot or methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.
  • Polybasic acid anhydrides include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydroanhydride Alicyclic dibasic acid anhydrides such as phthalic acid and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, etc.
  • Aliphatic or aromatic dibasic acid anhydride or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, Benzophenone Tet Aliphatic or aromatic tetrabasic acid dianhydride such as dianhydrides may be mentioned, it is possible to use one or more of them.
  • the photopolymerization initiator constituting the curable resin composition of the present invention includes an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.
  • One or more photopolymerization initiators selected from the group consisting of initiators can be used.
  • Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, N-1919 manufactured by Adeka, and Adeka Arcles NCI-831.
  • numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
  • X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms),
  • Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1), and substitute
  • Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents an alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene , Furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-di
  • n is represented by an integer of 0 or 1.
  • X and Y are each a methyl group or an ethyl group
  • Z is methyl or phenyl
  • n is 0, and Ar is preferably phenylene, naphthylene, thiophene or thienylene.
  • the blending amount of such oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount of such oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated.
  • it exceeds 5 parts by mass light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.
  • ⁇ -aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like.
  • Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.
  • acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
  • Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.
  • the blending amount of these ⁇ -aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.
  • examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. Compounds, tertiary amine compounds, and xanthone compounds.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
  • anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
  • thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
  • Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
  • Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
  • the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc.
  • 4,4′-dimethylaminobenzophenone Non-dimethylaminobenzophenone
  • Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (die
  • Dialkylamino group-containing coumarin compounds ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure® DMB manufactured by International Bio-Synthetics), 4-dimethyl Minobenzoic acid (n-butoxy) ethyl (Quantacure® BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol® 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.
  • Kayacure EPA manufactured by
  • composition of the present embodiment preferably contains a thioxanthone compound from the viewpoint of deep curability, and in particular, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl.
  • Thioxanthone compounds such as thioxanthone are preferred.
  • the compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis
  • a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
  • dialkylaminobenzophenone compound 4,4′-diethylaminobenzophenone is preferable because of its low toxicity.
  • the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to provide a solder resist film.
  • 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
  • the blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained.
  • the amount exceeds 20 parts by mass light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
  • These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
  • the total amount of the photopolymerization initiator, the photoinitiator assistant, and the sensitizer as described above is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
  • these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and they may work as ultraviolet absorbers. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to enhance the photoreactivity of the surface, and changes the resist line shape and opening to vertical, tapered, and inversely tapered, and processing accuracy of line width and opening diameter Can be improved.
  • curable resin composition of the present invention optional components described below can be blended.
  • thermosetting component in order to provide heat resistance, a thermosetting component can be mix
  • the thermosetting component used in the present invention include known and commonly used blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like.
  • a thermosetting resin can be used.
  • Such thermosetting components can be used alone or in combination of two or more.
  • thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in one molecule.
  • cyclic (thio) ether groups There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
  • thermosetting component having a plurality of cyclic (thio) ether groups in the molecule contains either one of the three-, four- or five-membered cyclic ether groups or cyclic thioether groups or two types of groups in the molecule.
  • a compound having a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and a plurality of thioether groups in the molecule.
  • Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011 manufactured by Tohto Kasei Co., Ltd. YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd.
  • E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd.
  • Hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd.
  • Type A epoxy resin jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd.
  • Glycidylamine type epoxy resin Glycidylamine type epoxy resin; Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd.
  • E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names); YL-6056, YX-4000 and YL-6121 manufactured by Japan Epoxy Resin Co., Ltd.
  • Bixylenol type or biphenol type epoxy resins such as trade name) or mixtures thereof; bisphenols such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC (trade name) S-type epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Japan (all trade names) Tetraphenylolethane type epoxy resin; Chiba Japan Heterocyclic epoxy resin such as Araldide PT810 manufactured by Nihon Kagaku Kogyo Co., Ltd.
  • Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP-7200 manufactured by DIC Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN Modified epoxy resin (for example, YR-102 City Chemical Co., YR-450, etc.) and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more.
  • polyfunctional oxetane compound examples 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)
  • polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene
  • Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • the amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing photosensitive resin. More preferably, it is in the range of 0.8 to 2 equivalents.
  • the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable.
  • the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
  • thermosetting component having a plurality of cyclic (thio) ether groups in the molecule
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
  • Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
  • Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like.
  • thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
  • thermosetting catalysts is sufficient in the usual quantitative ratio, for example, with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin or thermosetting component having a plurality of cyclic (thio) ether groups in the molecule.
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass.
  • amino resins such as a melamine derivative and a benzoguanamine derivative
  • examples of the amino resin include a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound.
  • the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound, and alkoxymethylated urea compound are each methylol melamine compound, methylol benzoguanamine compound, methylol glycoluril compound, methylol group of methylol urea compound.
  • the type of the alkoxymethyl group is not particularly limited, and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
  • a melamine derivative having a formalin concentration friendly to the human body and the environment of 0.2% or less is preferable.
  • Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mx-100 Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.).
  • the photosensitive resin composition of the present invention contains a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule in order to improve the curability of the composition and the toughness of the resulting cured film. can do.
  • a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule.
  • the compound which has, ie, a blocked isocyanate compound, etc. are mentioned.
  • polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
  • aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer.
  • aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
  • alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
  • adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.
  • the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
  • a blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
  • the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
  • aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
  • isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxi
  • the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117.
  • the compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
  • the compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 2 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. A proportion of 70 parts by weight is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, since the storage stability of a composition falls, it is unpreferable.
  • a urethanization catalyst can be blended in order to promote the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group.
  • this urethanization catalyst it is preferable to use one or more urethanization catalysts selected from tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. .
  • the tin catalyst examples include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
  • the metal chloride is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.
  • the metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Is mentioned.
  • the metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.
  • the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).
  • Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′.
  • N ′′, N ′′ -pentamethyldiethylenetriamine N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N′- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxy Chill) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N, N, N′-trimethyl
  • the compounding amount of the urethanization catalyst is sufficient in an ordinary quantitative ratio.
  • it is preferably 0.1 to 20 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. 5 to 10 parts by mass.
  • a bismaleimide compound can be mix
  • the bismaleimide compound include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide.
  • the polyfunctional aliphatic / alicyclic maleimide include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate, and aliphatic / alicyclic maleimide carboxylic acid.
  • Isocyanurate skeletal polymide compounds such as isocyanurate skeleton maleimide urethane compounds obtained by urethanization of tris (carbamate hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol
  • Maleimides isophorone bisurethane bis (N-ethylmaleimide), triethylene glycol bis (maleimidoethyl carbonate), aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyols dehydrated or esterified
  • Family / alicyclic Aliphatic / alicyclic polymaleimide ester compounds obtained by transesterification of maleimide carboxylic acid ester with various aliphatic / alicyclic polyols; aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic Aliphatic / alicyclic polymaleimide ester compounds obtained
  • aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols
  • maleimide Of aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides maleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates
  • aromatic polyfunctional maleimides aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols
  • maleimide Of aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides
  • aromatic polymaleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates
  • polyfunctional aromatic maleimide examples include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2, 6-tolylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene Bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4′- [3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylme
  • Examples of these commercially available products include BMI-1000, BMI-1000H, BMI-1000S, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI- 5100, BMI-7000, BMI-7000H, BMI-TMH (manufactured by Daiwa Kasei Kogyo Co., Ltd.), MIA-200 (manufactured by DIC), and the like.
  • These bismaleimide compounds may be synthesized by a conventional method, or commercially available products may be used. Particularly, among the bismaleimide compounds, those that do not contain a halogen atom in the molecule are preferable from the viewpoint of not placing a burden on the environment. These can be used individually by 1 type or in combination of 2 or more types.
  • a benzoxazine compound, an oxazoline compound, and a carbodiimide compound can be mix
  • the benzoxazine compound include bisphenol A type benzoxazine, bisphenol F type benzoxazine, and bisphenol S type benzoxazine.
  • examples of commercially available products include “Fa” (manufactured by Shikoku Kasei Co., Ltd.).
  • the oxazoline compound is not particularly limited as long as it contains an oxazoline group.
  • the cyclocarbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond.
  • the alkylene carbonate compound which has a polyfunctional structure is mentioned.
  • the carbodiimide compound include dicyclohexylcarbodiimide and diisopropylcarbodiimide.
  • the curable resin composition of the present invention may contain known N phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like as chain transfer agents.
  • chain transfer agents include chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethan
  • Polyfunctional mercaptan compounds can be used and are not particularly limited.
  • Aliphatic thiols such as xylylene dimercaptan, 4,4'-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) s of polyhydric alcohols such as tetrakis (mercaptoacetate) and dipenta
  • heterocyclic compound having a mercapto group that functions as a chain transfer agent examples include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2- Mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4 -Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy ) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5 Valerolactone, 2-mercapto-5-valerol
  • heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4- Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred.
  • chain transfer agents can be used alone or in combination of two or more.
  • the blending amount of such a mercapto compound is suitably 0.01 parts by weight or more and 10 parts by weight or less, more preferably 0.05 parts by weight or more, with respect to 100 parts by weight of the carboxyl group-containing photosensitive resin. 5 parts by mass or less. If it is less than 0.01 parts by mass, the effect of adding a mercapto compound is not confirmed. On the other hand, if it exceeds 10 parts by mass, it may cause development failure of the photosensitive resin composition, a decrease in the dry management width, etc., which is not preferable. .
  • a reactive diluent is blended in order to incur or insolubilize the carboxyl group-containing photosensitive resin in an alkaline aqueous solution by photocuring by irradiation with active energy rays. be able to.
  • reactive diluents include compounds having a plurality of ethylenically unsaturated groups in the molecule, and commonly known polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates. , Carbonate (meth) acrylate, epoxy (meth) acrylate, and the like.
  • hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol Diacrylates of glycols such as propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate; Multivalent acrylates such as these ethylene oxide adducts, propylene oxide adducts, or ⁇ -caprolactone adducts; phenoxy
  • an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
  • a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
  • a hydroxy acrylate such as pentaerythritol triacrylate
  • a diisocyanate such as isophorone diisocyanate
  • the compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is desirably 5 to 100 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin.
  • the ratio is 70 parts by mass.
  • the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable.
  • the amount exceeds 100 parts by mass the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
  • the photosensitive resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing photosensitive resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. Can do.
  • organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether a
  • the photosensitive resin composition of this invention can mix
  • colorant conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
  • Red colorant examples include monoazo, disazo, monoazo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. Specifically, those having the following color index numbers (CI; issued by The Society of Dyers and Colorists) can be used.
  • Monoazo series includes Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. are used.
  • Monoazo lakes include Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2. , 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68 etc. are used.
  • Examples of benzimidazolone-based compounds include Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, and Pigment Red 208.
  • perylene systems include Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, and the like.
  • Examples of the diketopyrrolopyrrole include Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, and Pigment Red 272.
  • Examples of condensed azo compounds include Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, and Pigment Red 242.
  • Examples of anthraquinone include Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207, and the like.
  • Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 and the like are used.
  • Blue colorant examples include phthalocyanine and anthraquinone.
  • compounds classified as Pigment specifically, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, etc. are used.
  • Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 67 70 etc. are used.
  • metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • Green colorant examples include phthalocyanine series, anthraquinone series, and perylene series. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • Yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.
  • Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202, and the like are used.
  • isoindolinone compounds include Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, and Pigment Yellow 185.
  • Examples of condensed azo compounds include Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, and Pigment Yellow 180.
  • benzimidazolone series Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 and the like are used.
  • monoazo series Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 116, 167, 168, 169, 182, 183, etc. are used.
  • disazo group Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and the like are used.
  • colorants such as purple, orange, brown and black may be added for the purpose of adjusting the color tone.
  • colorants include Pigment® Violet® 19, 23, 29, 32, 36, 38, 42, Solvent® Violet® 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, and CI Pigment Orange.
  • the blending ratio of the colorant as described above is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. Is enough.
  • a filler can be blended as necessary in order to increase the physical strength of the coating film.
  • known and commonly used inorganic or organic fillers can be used.
  • barium sulfate, spherical silica and talc are preferably used.
  • metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers.
  • the amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. .
  • the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.
  • a binder polymer can be used for the purpose of improving the touch drying property and the handling property.
  • polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used.
  • These binder polymers can be used alone or as a mixture of two or more.
  • the photosensitive resin composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving brittleness of the cured product.
  • an elastomer for the purpose of imparting flexibility and improving brittleness of the cured product.
  • a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or the like can be used.
  • an elastomer in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
  • epoxy-containing polybutadiene elastomers acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. These elastomers can be used alone or as a mixture of two or more.
  • the photosensitive resin composition of the present invention prevents oxidation.
  • An antioxidant can be added.
  • PCT resistance is improved, and peeling and discoloration during HAST are reduced, which is effective.
  • the radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, TINUVIN 5100 Japan) Product name).
  • antioxidant acting as a peroxide decomposer examples include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.
  • the peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilizer TPS (Sumitomo Chemical) Company name, product name).
  • Said antioxidant can be used individually by 1 type or in combination of 2 or more types.
  • the photosensitive resin composition of the present invention includes, in addition to the above antioxidant, in order to take a countermeasure against stabilization against ultraviolet rays. UV absorbers can be used.
  • ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
  • benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Is mentioned.
  • benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
  • benzotriazole derivative examples include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like.
  • the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
  • Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Japan, trade name) and the like.
  • Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, the molding obtained from the photosensitive resin composition of this invention can be stabilized. I can plan.
  • the photosensitive resin composition of the present invention can be used.
  • adhesion promoters include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical Industry Co., Ltd.) Axel M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzo Examples include triazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.
  • the photosensitive resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary.
  • a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc.
  • Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics.
  • thermal polymerization inhibitors silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, and bisphenols
  • Known and conventional additives such as copper damage prevention agents such as those based on triazine and triazine thiols can be blended.
  • the thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
  • 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, ⁇ -naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
  • the curable resin composition of the present invention configured as described above is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method It is applied by a method such as screen printing or curtain coating.
  • a tack-free coating film is formed by volatilizing and drying (preliminary drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C.
  • the volatile drying is supported by a hot air circulation drying furnace, IR furnace, hot plate, convection oven or the like (a method equipped with an air heating type heat source by steam and contacting the hot air in the dryer countercurrently and the nozzle. Can be performed using a method of spraying on the body).
  • the curable resin composition of the present invention is applied on a carrier film, dried and wound up as a film to form a dry film, and this is laminated on a substrate to form a resin insulation layer May be.
  • paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy All grades (FR-4, etc.) of copper clad laminates such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate esters, etc., other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer board, etc. can be mentioned.
  • pattern exposure irradiation of active energy rays
  • a contact method or non-contact method
  • pattern exposure irradiation of active energy rays
  • an active energy ray through a photomask on which a pattern is formed, or by exposure or a laser direct exposure machine.
  • a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
  • a direct drawing apparatus for example, devices manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device that oscillates laser light having a maximum wavelength of 350 to 410 nm may be used.
  • either a gas laser or a solid-state laser may be used as long as it has a maximum wavelength in the range of 350 to 410 nm.
  • the exposure amount varies depending on the film thickness and the like, but can generally be in the range of 5 to 1000 mJ / cm 2 , preferably 10 to 500 mJ / cm 2 , more preferably 20 to 400 mJ / cm 2 .
  • the exposed portion (the portion irradiated by the active energy ray) is cured, and then the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution).
  • a dilute alkaline aqueous solution for example, 0.3 to 3% sodium carbonate aqueous solution.
  • the developing method can be a dipping method, a shower method, a spray method, a brush method, etc.
  • the developer is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicic acid.
  • Alkaline aqueous solutions such as sodium, ammonia and amines can be used.
  • thermosetting component when added, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing photosensitive resin and a plurality of cyclic ether groups in the molecule and A thermosetting component having a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
  • the curable resin composition of the present invention by containing a carboxyl group-containing photosensitive resin, a photopolymerization initiator, and, if necessary, a diluent, a thermosetting component, a colorant, etc., it is excellent. Alkali developability, and excellent workability and mass productivity can be obtained. Furthermore, the coating film obtained by applying this is selectively exposed, developed, and finish-cured as necessary, so that adhesion, chemical resistance, electroless gold plating resistance, thermal shock resistance, PCT A cured product excellent in resistance, electrical insulation and the like can be obtained, and high reliability can be provided by using the cured product for a printed wiring board.
  • resin solution A-1 While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%. . This is designated as resin solution A-1.
  • a propylene carbonate reaction product of bisphenol A-formaldehyde type phenol resin was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
  • After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ⁇ 10 ° C. for 7 hours with stirring. 11.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene.
  • reaction synthesis example 5 A reaction vessel was charged with 205 parts of a phenol resin of the general formula (III) (Maywa Kasei Co., Ltd., trade name “MEH-7851”, OH equivalent: 205), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, and stirred. The reaction was started by heating to 150 to 160 ° C., and then the reaction was continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 269 g / eq.
  • a propylene carbonate reaction product of a phenol resin of the general formula (III) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
  • After the above reactants were dissolved in 150 parts of toluene, 36.0 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone were charged therein, and air was blown at a rate of 10 ml / min. The mixture was reacted at 100 ⁇ 10 ° C. for 7 hours with stirring. 9.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene.
  • resin solution R-1 a resin solution having a solid content of 65% was obtained. This is designated as resin solution R-1.
  • resin solution R-2 786 g (7.86 mol) of succinic anhydride and 423 g of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, and a resin having a solid content acid value of 100 mgKOH / g and a solid content of 65%. A solution was obtained. This is designated as resin solution R-2.
  • Examples 1 to 27 and Comparative Examples 1 to 4 thus obtained were evaluated as follows. These evaluation results are shown in Tables 3 and 4.
  • (Performance evaluation) ⁇ Optimal exposure>
  • the obtained curable resin compositions of Examples and Comparative Examples were subjected to circuit printing with a copper thickness of 35 ⁇ m after buffing, washed with water, dried and then applied to the entire surface by a screen printing method. It was dried for 60 minutes in a drying furnace. After drying, the step tablet remaining after exposure through a step tablet (Kodak No. 2) using an exposure device equipped with a high-pressure mercury lamp and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) in 90 seconds. The optimal exposure amount was obtained when the pattern was 7 steps.
  • the characteristics of the obtained printed circuit board were evaluated as follows. ⁇ Acid resistance> The evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and the penetration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed. Examples 15 to 27 and Comparative Examples 3 and 4 were evaluated in the same manner except that a 10% by mass HCl aqueous solution was used.
  • Electroless gold plating resistance Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5 ⁇ m and gold 0.05 ⁇ m, and tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows. A: No soaking or peeling is observed. ⁇ : Slight penetration is confirmed after plating, but does not peel off after tape peeling. ⁇ : Slight penetration after plating and peeling after tape peel. X: There is peeling after plating.
  • ⁇ PCT resistance> The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation, 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film was determined. evaluated. Judgment criteria are as follows. ⁇ : No swelling, peeling, discoloration, or elution ⁇ : Some swelling, peeling, discoloration, or elution ⁇ : Many swelling, peeling, discoloration, or elution ⁇ Resistance to thermal shock>
  • the evaluation board substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced.
  • the obtained evaluation substrate was subjected to a 1000 cycle resistance test with a thermal shock tester (manufactured by ETAC Co., Ltd.) at a cycle of ⁇ 55 ° C./30 minutes to 150 ° C./30 minutes. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.
  • ⁇ Crack generation rate of less than 30%
  • ⁇ Crack generation rate of 30-50%
  • ⁇ Crack occurrence rate of 50% or more Note that Examples 15 to 27 and Comparative Examples 3 and 4 were judged according to the following criteria.
  • the curable resin composition of the present embodiment is excellent in PCT resistance, thermal shock resistance, electrical characteristics, and solder required for use as a solder resist for IC packages. It was found that it has sufficient characteristics in heat resistance and electroless gold plating resistance. On the other hand, Comparative Examples 1 and 2 had good characteristics such as acid resistance and alkali resistance, but sufficient characteristics such as PCT resistance, thermal shock resistance, and electrical characteristics could not be obtained.
  • the cover film was peeled off, the film was heat-laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the evaluation of the coating film properties of the above-mentioned composition.
  • the carrier film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was developed for 90 seconds under the condition of a spray pressure of 0.2 MPa / cm 2 to obtain a resist pattern.
  • This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes to prepare a test substrate.
  • the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Tables 5 and 6.
  • resist cured products using carboxyl group-containing photosensitive resins derived from various phenol skeletons are required to have PCT resistance when used for electronic components such as semiconductor packages, It can be seen that it has excellent thermal characteristics as well as excellent thermal shock resistance.
  • This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes.
  • the obtained evaluation substrate was evaluated for flame retardancy by a method and apparatus conforming to the flame retardant test standard UL94 of a polymer material of United States Underwriters Laboratories Inc. (abbreviated as UL).
  • UL United States Underwriters Laboratories Inc.
  • the curable resin composition of the present invention also has excellent flame retardancy.

Abstract

Disclosed is a curable resin composition which has good workability and high sensitivity, and is capable of providing a cured product thereof with high reliability when the cured product is used, for example, in a printed wiring board or a semiconductor package. Also disclosed is a cured product of the curable resin composition. The curable resin composition contains a photopolymerization initiator and a carboxyl group-containing photosensitive resin which is obtained by reacting a polybasic acid anhydride with a reaction product that is obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product that is obtained by reacting a phenol resin having a specific skeleton with an alkylene oxide or a cyclocarbonate compound.

Description

硬化性樹脂組成物およびプリント配線板Curable resin composition and printed wiring board
　本発明は、プリント配線基板のソルダーレジスト等として用いられる硬化性樹脂組成物に関する。 The present invention relates to a curable resin composition used as a solder resist for printed wiring boards.
　現在、一部の民生用プリント配線板並びにほとんどの産業用プリント配線板のソルダーレジストには、高精度、高密度の観点から、紫外線照射後、現像することにより画像形成し、熱及び／又は光照射で仕上げ硬化（本硬化）する液状現像型ソルダーレジストが使用され、環境問題への配慮から、現像液としてアルカリ水溶液を用いるアルカリ現像型のフォトソルダーレジストが主流となり、広く用いられている（例えば、特許文献１など参照）。 At present, some consumer printed wiring boards and most industrial printed wiring board solder resists are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density, and heat and / or light. A liquid development type solder resist that undergoes final curing (main curing) by irradiation is used, and in consideration of environmental problems, an alkali development type photo solder resist using an alkaline aqueous solution as a developing solution has become the mainstream and widely used (for example, , See Patent Document 1).
　このような液状現像型ソルダーレジストにおいて、カルボキシル基含有感光性樹脂、一般に、エポキシ樹脂の変性により誘導されたエポキシアクリレート変性樹脂が用いられている。
　例えば、ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂、光重合開始剤、希釈剤及びエポキシ化合物からなるソルダーレジスト組成物が開示されている（特許文献１参照）。また、サリチルアルデヒドと一価フェノールとの反応生成物にエピクロロヒドリンを反応させて得られたエポキシ樹脂に（メタ）アクリル酸を付加し、さらに多塩基性カルボン酸又はその無水物を反応させて得られる感光性樹脂、光重合開始剤、有機溶剤等からなるソルダーレジスト組成物が開示されている（特許文献２参照）。 In such a liquid development type solder resist, a carboxyl group-containing photosensitive resin, generally an epoxy acrylate modified resin derived by modification of an epoxy resin is used.
For example, a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound is disclosed (patent) Reference 1). In addition, (meth) acrylic acid is added to the epoxy resin obtained by reacting the reaction product of salicylaldehyde and monohydric phenol with epichlorohydrin, and polybasic carboxylic acid or its anhydride is further reacted. A solder resist composition composed of a photosensitive resin, a photopolymerization initiator, an organic solvent, and the like is disclosed (see Patent Document 2).
　このように、エポキシアクリレート変性樹脂に用いられるエポキシ樹脂において、一般に、塩素を含有するエピクロロヒドリンなどを反応させることによりエポキシ骨格が導入される。この際、絶縁信頼性の低下を招く塩素イオン不純物が副生され、これを除去することが非常に困難であるため、原料に用いられるエポキシ樹脂中には塩素イオン不純物が多く含まれているものがほとんどである。また、この塩素イオン不純物は、エポキシアクリレート変性後に除去することも非常に困難である。 Thus, in an epoxy resin used for an epoxy acrylate-modified resin, an epoxy skeleton is generally introduced by reacting epichlorohydrin containing chlorine or the like. At this time, chlorine ion impurities that cause a decrease in insulation reliability are by-produced, and it is very difficult to remove them. Therefore, the epoxy resin used as a raw material contains a large amount of chlorine ion impurities. Is almost. Also, it is very difficult to remove this chloride ion impurity after the epoxy acrylate modification.
　一方で、近年のエレクトロニクス機器の軽薄短小化に伴うプリント配線板の高密度化に対応して、ソルダーレジストにも優れた現像性や高い作業性といった高性能化が要求されている。また、最近では、電子機器の小型化、軽量化、高性能化に伴い、半導体パッケージの小型化、多ピン化が実用化され、量産化が進んでいる。例えば、ＢＧＡ（ボールグリッドアレイ）、ＣＳＰ（チップサイズパッケージ）等の半導体パッケージにおいて、高信頼性を得るために、特に耐湿熱性ともいうべきＰＣＴ（プレッシャークッカーテスト）耐性が要求されている。さらには、生産性の観点から、ソルダーレジストにおいても、パターニングの際に用いられる紫外線などに対する反応性、すなわち高い露光感度を有することが要求されている。 On the other hand, solder resists are also required to have high performance such as excellent developability and high workability in response to the recent increase in the density of printed wiring boards as electronic devices become lighter and thinner. Recently, along with the downsizing, lightening, and high performance of electronic devices, downsizing of semiconductor packages and increasing the number of pins have been put into practical use, and mass production is progressing. For example, in order to obtain high reliability in semiconductor packages such as BGA (ball grid array) and CSP (chip size package), PCT (pressure cooker test) resistance, which is also referred to as moisture heat resistance, is required. Furthermore, from the viewpoint of productivity, the solder resist is also required to have reactivity with ultraviolet rays used for patterning, that is, high exposure sensitivity.
　しかしながら、従来の液状現像型ソルダーレジストは、ＰＣＴ耐性試験にて数時間～十数時間程度しかもたず、十分な耐湿熱性が得られていないのが現状である。また、パッケージ実装時、ソルダーレジストの吸湿により、リフロー中にパッケージ内部で吸湿した水分が沸騰し、パッケージ内部のソルダーレジスト皮膜及びその周辺にクラックを生じ、十分なクラック耐性が得られないという問題がある。 However, the conventional liquid development type solder resist has only a few hours to a few dozen hours in the PCT resistance test and does not have sufficient wet heat resistance. Also, when the package is mounted, moisture absorbed by the solder resist boils the moisture absorbed inside the package during reflow, causing cracks in the solder resist film inside the package and its surroundings, and sufficient crack resistance cannot be obtained. is there.
特開昭６１－２４３８６９号公報Japanese Patent Laid-Open No. 61-243869 特開平３－２５００１２号公報Japanese Patent Laid-Open No. 3-250012
　本発明は、上記問題点を解決するためになされたものであり、作業性が良好で、高感度かつ現像性に優れ、しかも、その硬化物において、例えばプリント配線板や半導体パッケージに用いられる際に、優れたＰＣＴ耐性、高い絶縁信頼性を得ることが可能な硬化性樹脂組成物を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems, has good workability, high sensitivity and excellent developability, and the cured product thereof is used, for example, in a printed wiring board or a semiconductor package. Another object of the present invention is to provide a curable resin composition capable of obtaining excellent PCT resistance and high insulation reliability.
　このような目的を達成するために、本発明の硬化性樹脂組成物は、一般式（I）から（ＶＩ）のうちの少なくとも一つの骨格を有するフェノール樹脂とアルキレンオキサイド又はシクロカーボネートとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂と、光重合開始剤とを含有する硬化性樹脂組成物が提供される。
Figure JPOXMLDOC01-appb-C000001
 （一般式（III）、（IV）、（VI）のＲは水素、もしくはメチル基を表す。） In order to achieve such an object, the curable resin composition of the present invention reacts a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide or a cyclocarbonate. Containing a carboxyl group-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid with the reaction product obtained and reacting the resulting reaction product with a polybasic acid anhydride, and a photopolymerization initiator. A curable resin composition is provided.
Figure JPOXMLDOC01-appb-C000001
 (R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.)
　このような構成により、作業性、現像性に優れると共に、その硬化物においては、例えばプリント配線板や半導体パッケージに用いられる際に、優れたＰＣＴ耐性や高い絶縁信頼性などの高い信頼性を得ることが可能となる。また、カルボキシル基含有感光性樹脂において、不飽和基、カルボキシル基が同一鎖上に存在せず、かつ、それぞれ側鎖末端に位置するため、反応性に優れ（高感度）、また優れたアルカリ現像性を実現できる。 With such a configuration, workability and developability are excellent, and the cured product has high reliability such as excellent PCT resistance and high insulation reliability when used for, for example, a printed wiring board or a semiconductor package. It becomes possible. Also, in the carboxyl group-containing photosensitive resin, the unsaturated group and the carboxyl group do not exist on the same chain and are located at the end of the side chain, respectively, so that the reactivity is high (high sensitivity) and the alkali development is excellent. Can be realized.
　本発明の硬化性樹脂組成物において、カルボキシル基含有感光性樹脂の酸価が、３０～１５０ｍｇＫＯＨ／ｇであることが好ましい。酸価をこの範囲とすることにより、アルカリ現像が可能で且つ、充分な耐現像性を得ることができる。 In the curable resin composition of the present invention, the acid value of the carboxyl group-containing photosensitive resin is preferably 30 to 150 mgKOH / g. By setting the acid value within this range, alkali development is possible and sufficient development resistance can be obtained.
　本発明の硬化性樹脂組成物において、アルキレンオキシドは、エチレンオキサイド及びプロピレンオキサイドもしくはエチレンオキサイド又はプロピレンオキサイドであること、シクロカーボネート化合物は、エチレンカーボネート及びプロピレンカーボネートもしくはエチレンカーボネート又はプロピレンカーボネートであることが好ましい。
　このような構成により、カルボキシル基含有樹脂の鎖が延長され、可とう性が向上し、冷熱衝撃性を向上させることができる。 In the curable resin composition of the present invention, the alkylene oxide is preferably ethylene oxide and propylene oxide or ethylene oxide or propylene oxide, and the cyclocarbonate compound is preferably ethylene carbonate and propylene carbonate or ethylene carbonate or propylene carbonate. .
With such a configuration, the chain of the carboxyl group-containing resin is extended, the flexibility is improved, and the thermal shock resistance can be improved.
　本発明の硬化性樹脂組成物において、不飽和基含有モノカルボン酸は、アクリル酸及びメタクリル酸もしくはアクリル酸又はメタクリル酸であることが好ましい。
　このような構成により、高感度な光硬化性樹脂組成物として用いることが可能となる。
　また、本発明の硬化性樹脂組成物において、カルボキシル基含有感光性樹脂は、水酸基を含有しないことが好ましい。
　このような構成により、耐吸湿性に優れ、その硬化物において、優れたＰＣＴ耐性を得ることができる。 In the curable resin composition of the present invention, the unsaturated group-containing monocarboxylic acid is preferably acrylic acid and methacrylic acid or acrylic acid or methacrylic acid.
With such a configuration, it can be used as a highly sensitive photocurable resin composition.
Moreover, in the curable resin composition of this invention, it is preferable that carboxyl group-containing photosensitive resin does not contain a hydroxyl group.
With such a configuration, the moisture absorption resistance is excellent, and excellent PCT resistance can be obtained in the cured product.
　また、本発明の硬化性樹脂組成物において、熱硬化性成分を含有することが好ましい。このような構成により、熱による本硬化が可能な熱硬化性樹脂組成物として用いることができ、硬化性樹脂組成物に耐熱性がさらに付与される。 Further, the curable resin composition of the present invention preferably contains a thermosetting component. With such a configuration, it can be used as a thermosetting resin composition capable of main curing by heat, and heat resistance is further imparted to the curable resin composition.
　本発明の硬化性樹脂組成物において、着色剤を含有することが好ましい。着色剤を含有することにより、プリント配線板用ソルダーレジストとして用いられる際に、回路等の隠蔽性を得ることができる。 The curable resin composition of the present invention preferably contains a colorant. By containing a colorant, when used as a solder resist for a printed wiring board, it is possible to obtain a concealing property such as a circuit.
　さらに、このような硬化性樹脂組成物を、基材に塗布し、活性エネルギー線照射及び加熱もしくは活性エネルギー線照射又は加熱により硬化させて硬化物とすることができる。このような硬化物において、例えばプリント配線板や半導体パッケージに用いられる際に、優れたＰＣＴ耐性や高い絶縁信頼性などの高い信頼性を得ることが可能となる。 Furthermore, such a curable resin composition can be applied to a substrate and cured by irradiation with active energy rays and heating or irradiation with active energy rays or heating to obtain a cured product. In such a cured product, for example, when used for a printed wiring board or a semiconductor package, it is possible to obtain high reliability such as excellent PCT resistance and high insulation reliability.
　また、このような硬化性樹脂組成物を、フィルム上に塗布・乾燥して硬化性ドライフィルムとして用いることができる。このようなドライフィルムとすることにより、塗布することなく簡易にレジスト層を形成することができる。さらに、このドライフィルムを基材に貼り付け、活性エネルギー線照射及び加熱もしくは活性エネルギー線照射又は加熱により硬化させて硬化物とすることができる。このような硬化物において、例えばプリント配線板や半導体パッケージに用いられる際に、優れたＰＣＴ耐性や高い絶縁信頼性などの高い信頼性を得ることが可能となる。 Further, such a curable resin composition can be applied to a film and dried to be used as a curable dry film. By using such a dry film, a resist layer can be easily formed without coating. Furthermore, this dry film can be affixed to a substrate and cured by active energy ray irradiation and heating or active energy ray irradiation or heating to obtain a cured product. In such a cured product, for example, when used for a printed wiring board or a semiconductor package, it is possible to obtain high reliability such as excellent PCT resistance and high insulation reliability.
　そして、これら硬化物をプリント配線板に用いることにより、優れたＰＣＴ耐性や高い絶縁信頼性などの高い信頼性を得ることが可能となる。 And by using these hardened | cured material for a printed wiring board, it becomes possible to obtain high reliability, such as the outstanding PCT tolerance and high insulation reliability.
　本発明によれば、硬化性樹脂組成物において、作業性が良好で、高感度かつ優れた現像性を有し、しかも、その硬化物において、例えばプリント配線板や半導体パッケージに用いられる際に、優れたＰＣＴ耐性、高い絶縁信頼性を得ることが可能となる。 According to the present invention, the curable resin composition has good workability, high sensitivity and excellent developability, and in the cured product, for example, when used for a printed wiring board or a semiconductor package, Excellent PCT resistance and high insulation reliability can be obtained.
　本発明者らは、このような課題を解決するため鋭意検討を重ねた結果、組成物の必須成分として、一般式（I）から（ＶＩ）のうちの少なくとも一つの骨格を有するフェノール樹脂を出発原料とするカルボキシル基含有感光性樹脂を用いることにより上記目的を達成し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve such problems, the present inventors have started a phenol resin having at least one skeleton of the general formulas (I) to (VI) as an essential component of the composition. The inventors have found that the above object can be achieved by using a carboxyl group-containing photosensitive resin as a raw material, and have completed the present invention.
　このカルボキシル基含有感光性樹脂は、一般式（I）から（ＶＩ）のうちの少なくとも一つの骨格を有するフェノール樹脂とアルキレンオキサイド又はシクロカーボネートとの付加反応による鎖延長によって、優れた可撓性、伸びを得ることができる。また、アルキレンオキサイド又はシクロカーボネートの付加反応によって生じた末端水酸基に、不飽和基含有モノカルボン酸の付加及び多塩基酸無水物の付加が行われ、不飽和基やカルボキシル基が同一側鎖上に存在せず、かつ、それぞれ側鎖の末端に位置するため、優れた反応性を有する。さらに、主鎖から離れた末端カルボキシル基の存在により、優れたアルカリ現像性を有する。 This carboxyl group-containing photosensitive resin is excellent in flexibility by chain extension by addition reaction between a phenol resin having at least one skeleton of general formulas (I) to (VI) and alkylene oxide or cyclocarbonate, Elongation can be obtained. In addition, unsaturated group-containing monocarboxylic acid and polybasic acid anhydride are added to the terminal hydroxyl group generated by the addition reaction of alkylene oxide or cyclocarbonate, and the unsaturated group or carboxyl group is on the same side chain. Since it does not exist and is located at the end of each side chain, it has excellent reactivity. Furthermore, it has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain.
　また、このカルボキシル基含有感光性樹脂は、反応性の低い親水性のアルコール性の水酸基を有しないか、あるいは僅かに有するだけであるため、耐吸湿性に優れている。水酸基の存在は、水素結合による密着性の向上など優れた特徴も有しているが、著しく耐湿性を低下させる。この点で、本発明におけるカルボキシル基含有感光性樹脂は、実質的に水酸基を含まないことにより、耐湿性を向上させることができる。そして、耐湿性の向上により、ＩＣパッケージに要求されるＰＣＴ耐性の向上が可能となる。 In addition, this carboxyl group-containing photosensitive resin is excellent in moisture absorption resistance because it has no or only a slightly reactive hydrophilic alcoholic hydroxyl group. The presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but significantly reduces moisture resistance. In this respect, the carboxyl group-containing photosensitive resin in the present invention can improve moisture resistance by substantially not containing a hydroxyl group. And the improvement of the moisture resistance makes it possible to improve the PCT resistance required for the IC package.
　また、本発明に用いられる一般式（I）から（ＶＩ）のうちの少なくとも一つの骨格を有するフェノール樹脂は、通常のフェノール、あるいはクレゾール型ノボラック樹脂と比較して水酸基当量が大きいことが特徴として挙げられる。即ち、前記フェノール類より誘導されるカルボキシル基含有樹脂を用いた硬化物は一般的なノボラック樹脂類と比較して良好な可とう性を有する。これに伴い、従来のノボラック樹脂類と比較して、一般式（I）から（ＶＩ）のうちの少なくとも一つの骨格を有するフェノール樹脂から誘導されたカルボン酸含有樹脂を用いたソルダーレジスト組成物は得られる硬化物の冷熱衝撃耐性とＰＣＴ耐性を向上させることが可能である。中でも、一般式（ＩＩＩ）より誘導されたカルボキシル基含有感光性樹脂は、非常に優れた絶縁信頼性、ＰＣＴ耐性を得ることができる。 In addition, the phenol resin having at least one skeleton of the general formulas (I) to (VI) used in the present invention is characterized in that the hydroxyl equivalent is larger than that of normal phenol or cresol type novolac resin. Can be mentioned. That is, a cured product using a carboxyl group-containing resin derived from the phenols has better flexibility than general novolak resins. Accordingly, compared to conventional novolak resins, a solder resist composition using a carboxylic acid-containing resin derived from a phenol resin having at least one skeleton of general formulas (I) to (VI) It is possible to improve the thermal shock resistance and PCT resistance of the resulting cured product. Among them, the carboxyl group-containing photosensitive resin derived from the general formula (III) can obtain very excellent insulation reliability and PCT resistance.
　以下、本発明の硬化性樹脂組成物について詳細に説明する。
　まず、本発明の硬化性樹脂組成物を構成するカルボキシル基含有感光性樹脂は、具体的には、以下に示す方法により容易に得ることができる。
（１）一般式（I）から（ＶＩ）のうちの少なくとも一つの骨格を有するフェノール樹脂と、アルキレンオキサイドとを反応させて得られる反応生成物に、不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
（２）一般式（I）から（ＶＩ）のうちの少なくとも一つの骨格を有するフェノール樹脂と、シクロカーボネート化合物とを反応させて得られる反応生成物に、不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 Hereinafter, the curable resin composition of the present invention will be described in detail.
First, specifically, the carboxyl group-containing photosensitive resin constituting the curable resin composition of the present invention can be easily obtained by the following method.
(1) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide, A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.
(2) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with a cyclocarbonate compound. A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.
　このように、本発明におけるカルボキシル基含有感光性樹脂は、種々の骨格を有するフェノール樹脂を出発原料として得られる。塩素イオン不純物がほとんど含まれないフェノール樹脂は容易に入手することができることから、得られるカルボキシル基含有感光性樹脂における塩素イオン不純物濃度を大幅に抑えることができる。このようなカルボキシル基含有感光性樹脂の塩素イオン不純物含有量は100ppm以下であることが好ましい。より好ましくは50ppm以下、更に好ましくは30ppm以下である。 Thus, the carboxyl group-containing photosensitive resin in the present invention is obtained using phenol resins having various skeletons as starting materials. Since the phenol resin containing almost no chloride ion impurities can be easily obtained, the chloride ion impurity concentration in the resulting carboxyl group-containing photosensitive resin can be greatly suppressed. The chloride ion content of such a carboxyl group-containing photosensitive resin is preferably 100 ppm or less. More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less.
　また、このようなカルボキシル基含有感光性樹脂は、実質的に水酸基を含まない樹脂であるという点でも特徴がある。なお、実質的に水酸基を含まないとは、微量の水酸基を含むことが許容されることを意味する。
　このように、カルボキシル基含有感光性樹脂における塩素イオン不純物を抑え、実質的に水酸基を含まないことにより、優れた絶縁信頼性、ＰＣＴ耐性を発現することが可能となる。 Further, such a carboxyl group-containing photosensitive resin is also characterized in that it is a resin that does not substantially contain a hydroxyl group. Note that “substantially free of hydroxyl groups” means that a trace amount of hydroxyl groups is allowed.
As described above, it is possible to exhibit excellent insulation reliability and PCT resistance by suppressing chlorine ion impurities in the carboxyl group-containing photosensitive resin and substantially not including a hydroxyl group.
　また、本発明におけるカルボキシル基含有樹脂は、用いるフェノール樹脂原料により１繰り返しユニットあたりの芳香環に対するエステル結合の数を大幅に低減化することが可能となった。 In addition, the carboxyl group-containing resin in the present invention can greatly reduce the number of ester bonds to the aromatic ring per repeating unit depending on the phenol resin raw material used.
　さて、優れた絶縁信頼性が要求されるソルダーレジストでは、非常にファインピッチなライン/スペースの銅張積層板上にレジスト硬化塗膜を形成し、電圧印加を行い、その絶縁信頼性を判断する。一般的に電圧印加することで、吸水した水分が電極間で電気分解を起こす。このとき陰極側ではアルカリ性、陽極側では酸性になる。 For solder resists that require excellent insulation reliability, a cured resist coating is formed on a copper-clad laminate with very fine pitch lines / spaces, and voltage is applied to judge the insulation reliability. . In general, when a voltage is applied, the absorbed water causes electrolysis between the electrodes. At this time, it becomes alkaline on the cathode side and acidic on the anode side.
　このような現象から、従来のソルダーレジストでは、陰極側でエステル結合のアルカリ加水分解が発生することでレジストの膜厚減少が確認されたり、さらに悪いものでは陰極側のレジストがほとんど無くなるなどの不良モードが確認される。さらには、加水分解された分子は親水性が高いために、塗膜の吸水性を増大させ、電気特性を悪化させるという現象に繋がると考えた。発明者らは、このような現象に着目し、１繰り返しユニットあたりのエステル結合を減少させることは、陰極側でのアルカリ加水分解を抑制するための非常に有効な手段であると考えたのである。 Due to this phenomenon, in conventional solder resists, it is confirmed that the ester film has undergone alkali hydrolysis on the cathode side, resulting in a decrease in resist film thickness. The mode is confirmed. Furthermore, since the hydrolyzed molecule has high hydrophilicity, it was considered that the water absorption of the coating film was increased and the electrical properties were deteriorated. The inventors focused on such a phenomenon and thought that reducing the ester bond per repeating unit is a very effective means for suppressing alkali hydrolysis on the cathode side. .
　以下に、従来のフェノールノボラック樹脂と本発明に用いられるカルボキシル基含有樹脂との違いについて、１繰り返しユニットあたりの芳香環に対するエステル結合の数に着目して説明する。 Hereinafter, the difference between the conventional phenol novolac resin and the carboxyl group-containing resin used in the present invention will be described by focusing on the number of ester bonds to the aromatic ring per one repeating unit.
　従来のフェノールノボラック型エポキシアクリレートは、フェノールノボラック樹脂より合成されたエポキシ樹脂にアクリル酸を付加させ、生成する水酸基に酸無水物を付加させることで得られる。従って、１繰り返しユニットあたりの芳香環に対するエステル結合の数は２となる。これに対し、フェノール樹脂より誘導される本発明にかかるカルボキシル基含有樹脂は、種々の骨格を有するフェノール樹脂に対し、アルキレンオキサイドあるいはシクロカーボネート化合物を反応させた後、アクリル酸、酸無水物を反応させるため、１繰り返しユニットあたりの芳香環に対するエステル結合の数は理論上１．０より大きくなることはない。前記一般式（I）、（ＩＩ）では１繰り返しユニットあたりの芳香環に対するエステル結合の数は１、また一般式（ＩＶ）では０．５、一般式（ＶＩ）では０．６６、さらに一般式（ＩＩＩ）では０．３３まで低減化することが可能となり、それ故に、優れた絶縁信頼性を発現することが可能となる。本発明に用いられるカルボキシル基含有樹脂の１繰り返しユニットあたりの芳香環に対するエステル結合の数は１以下、好ましくは０．７５以下、さらに好ましくは０．５以下である。 A conventional phenol novolac type epoxy acrylate is obtained by adding acrylic acid to an epoxy resin synthesized from a phenol novolac resin and adding an acid anhydride to the hydroxyl group to be produced. Therefore, the number of ester bonds to the aromatic ring per repeating unit is 2. On the other hand, the carboxyl group-containing resin according to the present invention derived from a phenol resin reacts with an acrylic acid or an acid anhydride after reacting an alkylene oxide or a cyclocarbonate compound with a phenol resin having various skeletons. Therefore, the number of ester bonds per aromatic ring per repeating unit is theoretically never greater than 1.0. In the general formulas (I) and (II), the number of ester bonds to the aromatic ring per repeating unit is 1, 0.5 in the general formula (IV), 0.66 in the general formula (VI), and the general formula In (III), it is possible to reduce to 0.33, and therefore it is possible to exhibit excellent insulation reliability. The number of ester bonds to the aromatic ring per repeating unit of the carboxyl group-containing resin used in the present invention is 1 or less, preferably 0.75 or less, more preferably 0.5 or less.
　また、本発明に用いられる種々の骨格を有するフェノール樹脂から誘導されるカルボキシル基含有樹脂から得られる硬化物は、従来のフェノールノボラック樹脂から誘導されるカルボキシル基含有樹脂から得られる硬化物と比較し、用いるフェノール樹脂原料由来の優れた特徴の発現が可能となる。例えば、ガラス転移温度（Ｔｇ）の向上、硬化塗膜の破断強度の向上や強靭性の付与、冷熱衝撃性の向上、耐加水分解性の向上、さらには難燃性の向上等、様々な特性の付与が可能となる。 In addition, a cured product obtained from a carboxyl group-containing resin derived from a phenol resin having various skeletons used in the present invention is compared with a cured product obtained from a carboxyl group-containing resin derived from a conventional phenol novolac resin. It is possible to develop excellent characteristics derived from the phenol resin raw material used. For example, various properties such as improvement of glass transition temperature (Tg), improvement of breaking strength of cured coating film and provision of toughness, improvement of thermal shock resistance, improvement of hydrolysis resistance, and further improvement of flame retardancy Can be granted.
　また、これら（１）及び（２）にて得られたカルボキシル基含有感光性樹脂に対し、１分子中に環状エーテル基とエチレン性不飽和基を併せ持つ化合物を反応させても良い。このような化合物としては、反応性、供給面より、グリシジル（メタ）アクリレート、４－ヒドロキシブチルアクリレートグリシジルエーテル、あるいは３、４－エポキシシクロヘキシルメチルメタアクリレートが好ましい。
　なお、（メタ）アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称するものであり、以下他の類似の表現についても同様である。 Moreover, you may make the compound which has both a cyclic ether group and an ethylenically unsaturated group in 1 molecule react with the carboxyl group-containing photosensitive resin obtained by these (1) and (2). As such a compound, glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, or 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of reactivity and supply.
(Meth) acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
　このような１分子中に環状エーテル基とエチレン性不飽和基を併せ持つ化合物の付加量は、カルボキシル基に対して５％当量から４０％当量が好ましい。５％当量よりも付加量が少ない場合、十分な感度上昇やソルダーレジスト特性の向上が得られず、４０％当量を超えると、最大現像ライフが短くなるとともに、指触乾燥性が劣化する。より好ましくは１０％当量から３０％当量である。 The addition amount of such a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is preferably 5% equivalent to 40% equivalent to the carboxyl group. When the added amount is less than 5% equivalent, sufficient sensitivity increase and improvement of the solder resist characteristics cannot be obtained, and when it exceeds 40% equivalent, the maximum development life is shortened and the dryness to the touch is deteriorated. More preferably, it is 10% equivalent to 30% equivalent.
　このようなカルボキシル基含有感光性樹脂を用いることにより、バックボーン・ポリマーの側鎖に多数の遊離のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。また、カルボキシル基含有感光性樹脂の酸価は、３０～１５０ｍｇＫＯＨ／ｇの範囲であることが好ましい。３０ｍｇＫＯＨ／ｇよりも低い場合には、アルカリ水溶液に対する溶解性が低下し、形成した塗膜の現像が困難になる。一方、１５０ｍｇＫＯＨ／ｇよりも高くなると、現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となる場合がある。そして、外観不良や電気特性の低下の原因となる。更に好ましくは４０～１３０ｍｇＫＯＨ／ｇの範囲である。 By using such a carboxyl group-containing photosensitive resin, since it has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible. The acid value of the carboxyl group-containing photosensitive resin is preferably in the range of 30 to 150 mgKOH / g. When it is lower than 30 mgKOH / g, the solubility in an aqueous alkali solution is lowered, and development of the formed coating film becomes difficult. On the other hand, if the concentration is higher than 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line fades more than necessary, or dissolution and peeling occurs with the developer without distinction between the exposed portion and the unexposed portion. It may be difficult to draw a resist pattern. And it causes the appearance defect and the deterioration of electrical characteristics. More preferably, it is in the range of 40 to 130 mgKOH / g.
　また、このようなカルボキシル基含有感光性樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に２，０００～１５０，０００の範囲にあるものが好ましい。重量平均分子量が２，０００未満であると、タックフリー性能が劣化し、露光後の塗膜の耐湿性が悪く、現像時に膜減りが生じ、解像度が大きく劣る場合がある。一方、重量平均分子量が１５０，０００を超えると、現像性が著しく悪くなり、貯蔵安定性が劣る場合がある。より好ましくは、５，０００～１００，０００である。 In addition, the weight average molecular weight of such a carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally preferably in the range of 2,000 to 150,000. When the weight average molecular weight is less than 2,000, tack-free performance is deteriorated, the moisture resistance of the coated film after exposure is poor, film loss occurs during development, and resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated and the storage stability may be inferior. More preferably, it is 5,000 to 100,000.
　このようなカルボキシル基含有感光性樹脂の配合量は、全組成物中に、２０～６０質量％であることが好ましい。２０質量％より少ない場合、塗膜強度が低下してしまう。一方、６０質量％より多い場合、粘性が高くなり、塗布性等が低下してしまう。より好ましくは３０～５０質量％である。 The blending amount of such a carboxyl group-containing photosensitive resin is preferably 20 to 60% by mass in the entire composition. When it is less than 20% by mass, the coating film strength is lowered. On the other hand, when it is more than 60% by mass, the viscosity becomes high, and the coating property and the like are lowered. More preferably, it is 30 to 50% by mass.
　本発明に用いられるカルボキシル含有樹脂は、一般式（I）～（ＶＩ）の構造を有するフェノール樹脂から誘導されるものであれば特に限定されない。
（一般式（III）、（IV）、（VI）のＲは水素、もしくはメチル基を表す。） The carboxyl-containing resin used in the present invention is not particularly limited as long as it is derived from a phenol resin having a structure of general formulas (I) to (VI).
(R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.)
　本発明に用いられるフェノール樹脂としてはビスフェノールＡ－ホルムアルデヒド型フェノール樹脂、サリチルアルデヒド型フェノール樹脂、フェニルアラルキル型フェノール樹脂、ビフェニルアラルキル型フェノール樹脂、フェニレンアラルキル型フェノール樹脂、α‐ナフトール、β‐ナフトール等のナフトールアラルキル型フェノール樹脂、ジシクロペンタジエン骨格含有フェノール樹脂等を用いることができる。
　一般式（I）の骨格を有する樹脂としては、例えば明和化成(株)製のＢＰＡ－Ｄを使用することができる。
　一般式(II)の骨格を有する樹脂としては、例えば明和化成(株)製のＭＥＨ－７５００を使用することができる。
　一般式(ＩＩＩ)の骨格を有する樹脂としては、例えば明和化成(株)製のＭＥＨ－８５１を使用することができる。
　一般式(ＩＶ)の骨格を有する樹脂としては、例えば明和化成(株)製のＭＥＨ－７８００を使用することができる。
　一般式(V)の骨格を有する樹脂としては、例えば新日本石油(株)製のＤＰＰ－６１１５Ｈを使用することができる。
　一般式(VI)の骨格を有する樹脂としては、例えば日本化薬(株)製のカヤハードＣＢＮを使用することができる。 Examples of the phenol resin used in the present invention include bisphenol A-formaldehyde type phenol resin, salicylaldehyde type phenol resin, phenyl aralkyl type phenol resin, biphenyl aralkyl type phenol resin, phenylene aralkyl type phenol resin, α-naphthol, β-naphthol and the like. A naphthol aralkyl type phenol resin, a dicyclopentadiene skeleton-containing phenol resin, or the like can be used.
As the resin having a skeleton of the general formula (I), for example, BPA-D manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having the skeleton of the general formula (II), for example, MEH-7500 manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having the skeleton of the general formula (III), for example, MEH-851 manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having a skeleton of the general formula (IV), for example, MEH-7800 manufactured by Meiwa Kasei Co., Ltd. can be used.
As the resin having a skeleton of the general formula (V), for example, DPP-6115H manufactured by Shin Nippon Oil Co., Ltd. can be used.
As the resin having a skeleton of the general formula (VI), for example, Kayahard CBN manufactured by Nippon Kayaku Co., Ltd. can be used.
　アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、トリメチレンオキシド、テトラヒドロフラン、テトラヒドロピラン等が挙げられ、価格、供給体制の面からエチレンオキシド、プロピレンオキシドが好ましい。また、シクロカーボネート化合物としては、公知のカーボネート化合物が使用でき、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、２，３－カーボネートプロピルメタクリレートなどが挙げられる。このうち、反応性、供給体制の面から５員環のエチレンカーボネート、プロピレンカーボネートが好ましい。これらアルキレンオキシド、シクロカーボネート化合物は単独で又は２種類以上を混合して用いることができる。 Examples of the alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and the like, and ethylene oxide and propylene oxide are preferable from the viewpoint of price and supply system. As the cyclocarbonate compound, known carbonate compounds can be used, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate. Among these, 5-membered ethylene carbonate and propylene carbonate are preferable from the viewpoint of reactivity and supply system. These alkylene oxides and cyclocarbonate compounds can be used alone or in admixture of two or more.
　アルキレンオキシド又はシクロカーボネート化合物は、一般式（I）～（ＶＩ）の構造を有するフェノール樹脂のフェノール性水酸基に、塩基性触媒を用いて、付加反応させることにより、フェノール性水酸基からアルコール性水酸基を持つ樹脂に変性させることができる。この時の付加量としては、フェノール性水酸基１当量当たり、０．３～１０モルの範囲であることが好ましい。付加量が０．３モルより少ないと、後述の不飽和基含有モノカルボン酸や多塩基酸無水物との反応が起こり難くなり、感光性及び希アルカリ水溶液に対する溶解性が低下する。一方、付加量が１０ モルを超えると、生成するエーテル結合により、耐水性が低下し、電気絶縁性、ＰＣＴ耐性等が低下する。より好ましくは０．８～５モルの範囲であり、さらに好ましくは１．０～３モルの範囲である。 An alkylene oxide or a cyclocarbonate compound is obtained by adding an alcoholic hydroxyl group from a phenolic hydroxyl group by an addition reaction using a basic catalyst to the phenolic hydroxyl group of a phenol resin having a structure of general formulas (I) to (VI). It can be modified to have a resin. The addition amount at this time is preferably in the range of 0.3 to 10 mol per equivalent of phenolic hydroxyl group. When the addition amount is less than 0.3 mol, a reaction with an unsaturated group-containing monocarboxylic acid or polybasic acid anhydride described later hardly occurs, and the photosensitivity and solubility in a dilute alkaline aqueous solution are lowered. On the other hand, when the addition amount exceeds 10 moles, water resistance decreases due to the ether bond to be generated, and electrical insulation, PCT resistance and the like decrease. The range is more preferably 0.8 to 5 mol, and still more preferably 1.0 to 3 mol.
　不飽和基含有モノカルボン酸としては、アクリル酸、メタアクリル酸、あるいはさらに、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、フェニルグリシジル（メタ）アクリレート、（メタ）アクリル酸カプロラクトン付加物などの水酸基含有アクリレートの不飽和二塩基酸無水物付加物などが挙げられ、より好ましくはアクリル酸及び／ 又はメタアクリル酸である。これら不飽和基含有モノカルボン酸は単独で又は２種以上を組み合わせて用いることができる。 Examples of unsaturated group-containing monocarboxylic acids include acrylic acid, methacrylic acid, or even hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adducts. More preferred are acrylic acid and / or soot or methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.
　多塩基酸無水物としてはメチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ナジック酸、３，６－エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸等の脂環式二塩基酸無水物；無水コハク酸、無水マレイン酸、無水イタコン酸、オクテニル無水コハク酸、ペンタドデセニル無水コハク酸、無水フタル酸、無水トリメリット酸等の脂肪族又は芳香族二塩基酸無水物、あるいはビフェニルテトラカルボン酸二無水物、ジフェニルエーテルテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物等の脂肪族又は芳香族四塩基酸二無水物が挙げられ、これらのうち１種又は２種以上を使用することができる。 Polybasic acid anhydrides include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydroanhydride Alicyclic dibasic acid anhydrides such as phthalic acid and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, etc. Aliphatic or aromatic dibasic acid anhydride, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, Benzophenone Tet Aliphatic or aromatic tetrabasic acid dianhydride such as dianhydrides may be mentioned, it is possible to use one or more of them.
　次に、本発明の硬化性樹脂組成物を構成する光重合開始剤としては、オキシムエステル基を有するオキシムエステル系光重合開始剤、α－アミノアセトフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤からなる群から選択される１種以上の光重合開始剤を使用することができる。
　オキシムエステル系光重合開始剤としては、市販品として、チバ・ジャパン社製のＣＧＩ－３２５、イルガキュアー ＯＸＥ０１、イルガキュアー ＯＸＥ０２、アデカ社製Ｎ－１９１９、アデカアークルズ ＮＣＩ－８３１などが挙げられる。また、分子内に２個のオキシムエステル基を有する光重合開始剤も好適に用いることが出来、具体的には、下記一般式で表されるカルバゾール構造を有するオキシムエステル化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000003
 （式中、Xは、水素原子、炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、フェニル基、フェニル基（炭素数1～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Y、Zはそれぞれ、水素原子、炭素数1～１７のアルキル基、炭素数１～８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１～１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５－ピロール－ジイル、４，４'－スチルベン－ジイル、４，２'－スチレン－ジイルで表される）。ｎは０か１の整数であらわされる。
　特に化式中、X、Yが、それぞれ、メチル基またはエチル基であり、Zはメチルまたはフェニルであり、ｎは０であり、Ａｒは、フェニレン、ナフチレン、チオフェンまたはチエニレンであることが好ましい。） Next, the photopolymerization initiator constituting the curable resin composition of the present invention includes an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. One or more photopolymerization initiators selected from the group consisting of initiators can be used.
Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, N-1919 manufactured by Adeka, and Adeka Arcles NCI-831. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
Figure JPOXMLDOC01-appb-C000003
 (Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1), and substituted with an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group. Alkyl group having 8 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms, or a dialkyl group) Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents an alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene , Furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl). n is represented by an integer of 0 or 1.
In particular, in the chemical formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is preferably phenylene, naphthylene, thiophene or thienylene. )
　このようなオキシムエステル系光重合開始剤の配合量は、カルボキシル基含有樹脂１００質量部に対して、０．０１～５質量部とすることが好ましい。０．０１質量部未満であると、銅上での光硬化性が不足し、塗膜が剥離するとともに、耐薬品性などの塗膜特性が低下する。一方、５質量部を超えると、ソルダーレジスト塗膜表面での光吸収が激しくなり、深部硬化性が低下する傾向がある。より好ましくは、０．５～３質量部である。 The blending amount of such oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.
　α－アミノアセトフェノン系光重合開始剤としては、具体的には２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、Ｎ，Ｎ－ジメチルアミノアセトフェノンなどが挙げられる。市販品としては、チバ・ジャパン社製のイルガキュアー９０７、イルガキュアー３６９、イルガキュアー３７９などが挙げられる。 Specific examples of α-aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.
　アシルホスフィンオキサイド系光重合開始剤としては、具体的には２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス(２，４，６－トリメチルベンゾイル)－フェニルホスフィンオキサイド、ビス(２，６－ジメトキシベンゾイル)－２，４，４－トリメチル－ペンチルホスフィンオキサイドなどが挙げられる。市販品としては、ＢＡＳＦ社製のルシリンＴＰＯ、チバ・ジャパン社製のイルガキュアー８１９などが挙げられる。 Specific examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.
　これらα－アミノアセトフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤の配合量は、カルボキシル基含有樹脂１００質量部に対して、０．０１～１５質量部であることが好ましい。０．０１質量部未満であると、同様に銅上での光硬化性が不足し、塗膜が剥離するとともに、耐薬品性などの塗膜特性が低下する。一方、１５質量部を超えると、アウトガスの低減効果が得られず、さらにソルダーレジスト塗膜表面での光吸収が激しくなり、深部硬化性が低下する傾向がある。より好ましくは０．５～１０質量部である。 The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.
　その他、本発明の光硬化性樹脂組成物に好適に用いることができる光重合開始剤、光開始助剤および増感剤としては、ベンゾイン化合物、アセトフェノン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、３級アミン化合物、およびキサントン化合物などを挙げることができる。 In addition, examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. Compounds, tertiary amine compounds, and xanthone compounds.
　ベンゾイン化合物としては、具体的には、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどが挙げられる。
　アセトフェノン化合物としては、具体的には、例えばアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノンなどが挙げられる。
　アントラキノン化合物としては、具体的には、例えば２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノンなどが挙げられる。
　チオキサントン化合物としては、具体的には、例えば２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントンなどが挙げられる。
　ケタール化合物としては、具体的には、例えばアセトフェノンジメチルケタール、ベンジルジメチルケタールなどが挙げられる。
　ベンゾフェノン化合物としては、具体的には、例えばベンゾフェノン、４－ベンゾイルジフェニルスルフィド、４－ベンゾイル－４’－メチルジフェニルスルフィド、４－ベンゾイル－４’－エチルジフェニルスルフィド、４－ベンゾイル－４’－プロピルジフェニルスルフィドなどが挙げられる。 Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
　３級アミン化合物としては、具体的には、例えばエタノールアミン化合物、ジアルキルアミノベンゼン構造を有する化合物、例えば、市販品では、４，４’－ジメチルアミノベンゾフェノン（日本曹達社製ニッソキュアーＭＡＢＰ）、４，４’－ジエチルアミノベンゾフェノン（保土ヶ谷化学社製ＥＡＢ）などのジアルキルアミノベンゾフェノン、７－（ジエチルアミノ）－４－メチル－２Ｈ－１－ベンゾピラン－２－オン（７－（ジエチルアミノ）－４－メチルクマリン）などのジアルキルアミノ基含有クマリン化合物、４－ジメチルアミノ安息香酸エチル（日本化薬社製カヤキュアーＥＰＡ）、２－ジメチルアミノ安息香酸エチル（インターナショナルバイオ－シンセエティックス社製Ｑｕａｎｔａｃｕｒｅ ＤＭＢ）、４－ジメチルアミノ安息香酸（ｎ－ブトキシ）エチル（インターナショナルバイオ－シンセエティックス社製Ｑｕａｎｔａｃｕｒｅ ＢＥＡ）、ｐ－ジメチルアミノ安息香酸イソアミルエチルエステル（日本化薬社製カヤキュアーＤＭＢＩ）、４－ジメチルアミノ安息香酸２－エチルヘキシル（Ｖａｎ Ｄｙｋ社製Ｅｓｏｌｏｌ ５０７）、４，４’－ジエチルアミノベンゾフェノン（保土ヶ谷化学社製ＥＡＢ）などが挙げられる。 Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure® DMB manufactured by International Bio-Synthetics), 4-dimethyl Minobenzoic acid (n-butoxy) ethyl (Quantacure® BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol® 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.
　これらの中でも、チオキサントン化合物および３級アミン化合物が好ましい。本実施形態の組成物には、チオキサントン化合物が含まれることが深部硬化性の面から好ましく、特に、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン化合物が好ましい。 Of these, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present embodiment preferably contains a thioxanthone compound from the viewpoint of deep curability, and in particular, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl. Thioxanthone compounds such as thioxanthone are preferred.
　このようなチオキサントン化合物の配合量としては、カルボキシル基含有樹脂１００質量部に対して、２０質量部以下であることが好ましい。チオキサントン化合物の配合量が２０質量部を超えると、厚膜硬化性が低下して、製品のコストアップに繋がる。より好ましくは１０質量部以下の割合である。 The compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product. More preferably, the ratio is 10 parts by mass or less.
　また、３級アミン化合物としては、ジアルキルアミノベンゼン構造を有する化合物が好ましく、中でも、ジアルキルアミノベンゾフェノン化合物、最大吸収波長が３５０～４５０ｎｍにあるジアルキルアミノ基含有クマリン化合物およびケトクマリン類が特に好ましい。 As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
　ジアルキルアミノベンゾフェノン化合物としては、４，４’－ジエチルアミノベンゾフェノンが、毒性も低く好ましい。ジアルキルアミノ基含有クマリン化合物は、最大吸収波長が３５０～４１０ｎｍと紫外線領域にあるため、着色が少なく、無色透明な感光性組成物はもとより、着色顔料を用い、着色顔料自体の色を反映した着色ソルダーレジスト膜を提供することが可能となる。特に、７－（ジエチルアミノ）－４－メチル－２Ｈ－１－ベンゾピラン－２－オンが、波長４００～４１０ｎｍのレーザー光に対して優れた増感効果を示すことから好ましい。 As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to provide a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
　このような３級アミン化合物の配合量としては、カルボキシル基含有樹脂１００質量部に対して、０．１～２０質量部であることが好ましい。３級アミン化合物の配合量が０．１質量部未満であると、十分な増感効果を得ることができない傾向にある。２０質量部を超えると、３級アミン化合物による乾燥ソルダーレジスト塗膜の表面での光吸収が激しくなり、深部硬化性が低下する傾向がある。より好ましくは０．１～１０質量部である。
　これらの光重合開始剤、光開始助剤および増感剤は、単独でまたは２種類以上の混合物として使用することができる。 The blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
　以上説明したような光重合開始剤、光開始助剤、および増感剤の総量は、前記カルボン酸含有樹脂１００質量部に対して３５質量部以下であることが好ましい。３５質量部を超えると、これらの光吸収により深部硬化性が低下する傾向にある。 The total amount of the photopolymerization initiator, the photoinitiator assistant, and the sensitizer as described above is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
　なお、これらの光重合開始剤、光開始助剤、および増感剤は、特定の波長を吸収するため、場合によっては感度が低くなり、紫外線吸収剤として働くことがある。しかしながら、これらは組成物の感度を向上させることだけの目的に用いられるものではない。必要に応じて特定の波長の光を吸収させて、表面の光反応性を高め、レジストのライン形状および開口を垂直、テーパー状、逆テーパー状に変化させるとともに、ライン幅や開口径の加工精度を向上させることができる。 In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and they may work as ultraviolet absorbers. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to enhance the photoreactivity of the surface, and changes the resist line shape and opening to vertical, tapered, and inversely tapered, and processing accuracy of line width and opening diameter Can be improved.
　本発明の硬化性樹脂組成物では、以下に説明する任意成分を配合することができる。 In the curable resin composition of the present invention, optional components described below can be blended.
　本発明の硬化性樹脂組成物では、耐熱性を付与するために、熱硬化性成分を配合することができる。
本発明に用いられる熱硬化性成分としては、ブロックイソシアネート化合物、アミノ樹脂、マレイミド化合物、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、多官能エポキシ化合物、多官能オキセタン化合物、エピスルフィド樹脂などの公知慣用の熱硬化性樹脂が使用できる。このような熱硬化成分は、単独又は２種以上を併用することができる。
　これらの中でも好ましい熱硬化成分は、１分子中に複数の環状エーテル基及び／又は環状チオエーテル基（以下、「環状（チオ）エーテル基」と略称する）を有する熱硬化性成分である。これら環状（チオ）エーテル基を有する熱硬化性成分は、市販されている種類が多く、その構造によって多様な特性を付与することができる。 In the curable resin composition of this invention, in order to provide heat resistance, a thermosetting component can be mix | blended.
Examples of the thermosetting component used in the present invention include known and commonly used blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like. A thermosetting resin can be used. Such thermosetting components can be used alone or in combination of two or more.
Among these, a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in one molecule. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
　このような分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分は、分子中に３、４又は５員環の環状エーテル基又は環状チオエーテル基のいずれか一方又は２種類の基を複数有する化合物であり、例えば、分子中に複数のエポキシ基を有する化合物、すなわち多官能エポキシ化合物、分子中に複数のオキセタニル基を有する化合物、すなわち多官能オキセタン化合物、分子中に複数のチオエーテル基を有する化合物、すなわちエピスルフィド樹脂などが挙げられる。 Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule contains either one of the three-, four- or five-membered cyclic ether groups or cyclic thioether groups or two types of groups in the molecule. A compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and a plurality of thioether groups in the molecule. A compound having the same, that is, an episulfide resin.
　前記多官能エポキシ化合物としては、例えば、ジャパンエポキシレジン社製のｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００４、ＤＩＣ社製のエピクロン８４０、エピクロン８５０、エピクロン１０５０、エピクロン２０５５、東都化成社製のエポトートＹＤ－０１１、ＹＤ－０１３、ＹＤ－１２７、ＹＤ－１２８、ダウケミカル社製のＤ．Ｅ．Ｒ．３１７、Ｄ．Ｅ．Ｒ．３３１、Ｄ．Ｅ．Ｒ．６６１、Ｄ．Ｅ．Ｒ．６６４、チバ・ジャパン社のアラルダイド６０７１、アラルダイド６０８４、アラルダイドＧＹ２５０、アラルダイドＧＹ２６０、住友化学工業社製のスミ－エポキシＥＳＡ－０１１、ＥＳＡ－０１４、ＥＬＡ－１１５、ＥＬＡ－１２８、旭化成工業社製のＡ．Ｅ．Ｒ．３３０、Ａ．Ｅ．Ｒ．３３１、Ａ．Ｅ．Ｒ．６６１、Ａ．Ｅ．Ｒ．６６４等（何れも商品名）のビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲＹＬ９０３、ＤＩＣ社製のエピクロン１５２、エピクロン１６５、東都化成社製のエポトートＹＤＢ－４００、ＹＤＢ－５００、ダウケミカル社製のＤ．Ｅ．Ｒ．５４２、チバ・ジャパン社製のアラルダイド８０１１、住友化学工業社製のスミ－エポキシＥＳＢ－４００、ＥＳＢ－７００、旭化成工業社製のＡ．Ｅ．Ｒ．７１１、Ａ．Ｅ．Ｒ．７１４等（何れも商品名）のブロム化エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲ１５２、ｊＥＲ１５４、ダウケミカル社製のＤ．Ｅ．Ｎ．４３１、Ｄ．Ｅ．Ｎ．４３８、ＤＩＣ社製のエピクロンＮ－７３０、エピクロンＮ－７７０、エピクロンＮ－８６５、東都化成社製のエポトートＹＤＣＮ－７０１、ＹＤＣＮ－７０４、チバ・ジャパン社製のアラルダイドＥＣＮ１２３５、アラルダイドＥＣＮ１２７３、アラルダイドＥＣＮ１２９９、アラルダイドＸＰＹ３０７、日本化薬社製のＥＰＰＮ－２０１、ＥＯＣＮ－１０２５、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０４Ｓ、ＲＥ－３０６、ＮＣ－３０００、住友化学工業社製のスミ－エポキシＥＳＣＮ－１９５Ｘ、ＥＳＣＮ－２２０、旭化成工業社製のＡ．Ｅ．Ｒ．ＥＣＮ－２３５、ＥＣＮ－２９９等（何れも商品名）のノボラック型エポキシ樹脂；ＤＩＣ社製のエピクロン８３０、ジャパンエポキシレジン社製ｊＥＲ８０７、東都化成社製のエポトートＹＤＦ－１７０、ＹＤＦ－１７５、ＹＤＦ－２００４、チバ・ジャパン社製のアラルダイドＸＰＹ３０６等（何れも商品名）のビスフェノールＦ型エポキシ樹脂；東都化成社製のエポトートＳＴ－２００４、ＳＴ－２００７、ＳＴ－３０００（商品名）等の水添ビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲ６０４、東都化成社製のエポトートＹＨ－４３４、チバ・ジャパン社製のアラルダイドＭＹ７２０、住友化学工業社製のスミ－エポキシＥＬＭ－１２０等（何れも商品名）のグリシジルアミン型エポキシ樹脂；チバ・ジャパン社製のアラルダイドＣＹ－３５０（商品名）等のヒダントイン型エポキシ樹脂；ダイセル化学工業社製のセロキサイド２０２１、チバ・ジャパン社製のアラルダイドＣＹ１７５、ＣＹ１７９等（何れも商品名）の脂環式エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ－９３３、ダウケミカル社製のＴ．Ｅ．Ｎ．、日本化薬社製のＥＰＰＮ－５０１、ＥＰＰＮ－５０２等（何れも商品名）のトリヒドロキシフェニルメタン型エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ－６０５６、ＹＸ－４０００、ＹＬ－６１２１（何れも商品名）等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物；日本化薬社製ＥＢＰＳ－２００、旭電化工業社製ＥＰＸ－３０、ＤＩＣ社製のＥＸＡ－１５１４（商品名）等のビスフェノールＳ型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲ１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲＹＬ－９３１、チバ・ジャパン社製のアラルダイド１６３等（何れも商品名）のテトラフェニロールエタン型エポキシ樹脂；チバ・ジャパン社製のアラルダイドＰＴ８１０、日産化学工業社製のＴＥＰＩＣ等（何れも商品名）の複素環式エポキシ樹脂；日本油脂社製ブレンマーＤＧＴ等のジグリシジルフタレート樹脂；東都化成社製ＺＸ－１０６３等のテトラグリシジルキシレノイルエタン樹脂；新日鐵化学社製ＥＳＮ－１９０、ＥＳＮ－３６０、ＤＩＣ社製ＨＰ－４０３２、ＥＸＡ－４７５０、ＥＸＡ－４７００等のナフタレン基含有エポキシ樹脂；ＤＩＣ社製ＨＰ－７２００、ＨＰ－７２００Ｈ等のジシクロペンタジエン骨格を有するエポキシ樹脂；日本油脂社製ＣＰ－５０Ｓ、ＣＰ－５０Ｍ等のグリシジルメタアクリレート共重合系エポキシ樹脂；さらにシクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂；ＣＴＢＮ変性エポキシ樹脂（例えば東都化成社製のＹＲ－１０２、ＹＲ－４５０等）等が挙げられるが、これらに限られるものではない。これらのエポキシ樹脂は、単独で又は２種以上を組み合わせて用いることができる。 Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011 manufactured by Tohto Kasei Co., Ltd. YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo A . E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); Hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd. Type A epoxy resin: jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names); YL-6056, YX-4000 and YL-6121 manufactured by Japan Epoxy Resin Co., Ltd. Bixylenol type or biphenol type epoxy resins such as trade name) or mixtures thereof; bisphenols such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC (trade name) S-type epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Japan (all trade names) Tetraphenylolethane type epoxy resin; Chiba Japan Heterocyclic epoxy resin such as Araldide PT810 manufactured by Nihon Kagaku Kogyo Co., Ltd. (both trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetra such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. Glycidyl xylenoyl ethane resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP-7200 manufactured by DIC Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN Modified epoxy resin (for example, YR-102 City Chemical Co., YR-450, etc.) and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more.
　前記多官能オキセタン化合物としては、ビス［（３－メチル－３－オキセタニルメトキシ）メチル］エーテル、ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エーテル、１，４－ビス［（３－メチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、（３－メチル－３－オキセタニル）メチルアクリレート、（３－エチル－３－オキセタニル）メチルアクリレート、（３－メチル－３－オキセタニル）メチルメタクリレート、（３－エチル－３－オキセタニル）メチルメタクリレートやそれらのオリゴマー又は共重合体等の多官能オキセタン類の他、オキセタンアルコールとノボラック樹脂、ポリ（ｐ－ヒドロキシスチレン）、カルド型ビスフェノール類、カリックスアレーン類、カリックスレゾルシンアレーン類、又はシルセスキオキサンなどの水酸基を有する樹脂とのエーテル化物などが挙げられる。その他、オキセタン環を有する不飽和モノマーとアルキル（メタ）アクリレートとの共重合体なども挙げられる。 Examples of the polyfunctional 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 and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphe Lumpur acids, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.
　前記分子中に複数の環状チオエーテル基を有するエピスルフィド樹脂としては、例えば、ジャパンエポキシレジン社製のＹＬ７０００（ビスフェノールＡ型エピスルフィド樹脂）などが挙げられる。また、同様の合成方法を用いて、ノボラック型エポキシ樹脂のエポキシ基の酸素原子を硫黄原子に置き換えたエピスルフィド樹脂なども用いることができる。 Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
　前記分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分の配合量は、前記カルボキシル基含有感光性樹脂のカルボキシル基１当量に対して、好ましくは０．６～２．５当量、より好ましくは、０．８～２当量となる範囲である。分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分の配合量が０．６未満である場合、ソルダーレジスト膜にカルボキシル基が残り、耐熱性、耐アルカリ性、電気絶縁性などが低下するので、好ましくない。一方、２．５当量を超える場合、低分子量の環状（チオ）エーテル基が乾燥塗膜に残存することにより、塗膜の強度などが低下するので、好ましくない。 The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing photosensitive resin. More preferably, it is in the range of 0.8 to 2 equivalents. When the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
　前記分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分を使用する場合、熱硬化触媒を含有することが好ましい。
　このような熱硬化触媒としては、例えば、イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、４－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾール等のイミダゾール誘導体；ジシアンジアミド、ベンジルジメチルアミン、４－（ジメチルアミノ）－Ｎ，Ｎ－ジメチルベンジルアミン、４－メトキシ－Ｎ，Ｎ－ジメチルベンジルアミン、４－メチル－Ｎ，Ｎ－ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物；トリフェニルホスフィン等のリン化合物などが挙げられる。また、市販されているものとしては、例えば四国化成工業社製の２ＭＺ－Ａ、２ＭＺ－ＯＫ、２ＰＨＺ、２Ｐ４ＢＨＺ、２Ｐ４ＭＨＺ（いずれもイミダゾール系化合物の商品名）、サンアプロ社製のＵ－ＣＡＴ（登録商標）３５０３Ｎ、Ｕ－ＣＡＴ３５０２Ｔ（いずれもジメチルアミンのブロックイソシアネート化合物の商品名）、ＤＢＵ、ＤＢＮ、Ｕ－ＣＡＴＳＡ１０２、Ｕ－ＣＡＴ５００２（いずれも二環式アミジン化合物及びその塩）などが挙げられる。特に、これらに限られるものではなく、エポキシ樹脂やオキセタン化合物の熱硬化触媒、もしくはエポキシ基及び／又はオキセタニル基とカルボキシル基の反応を促進するものであればよく、単独で又は２種以上を混合して使用してもかまわない。また、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、２，４－ジアミノ－６－メタクリロイルオキシエチル－Ｓ－トリアジン、２－ビニル－２，４－ジアミノ－Ｓ－トリアジン、２－ビニル－４，６－ジアミノ－Ｓ－トリアジン・イソシアヌル酸付加物、２，４－ジアミノ－６－メタクリロイルオキシエチル－Ｓ－トリアジン・イソシアヌル酸付加物等のＳ－トリアジン誘導体を用いることもでき、好ましくはこれら密着性付与剤としても機能する化合物を前記熱硬化触媒と併用する。 When using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst.
Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.
　これら熱硬化触媒の配合量は、通常の量的割合で充分であり、例えば前記カルボキシル基含有感光性樹脂又は分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分１００質量部に対して、好ましくは０．１～２０質量部、より好ましくは０．５～１５質量部である。 The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin or thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass.
　また、好適に用いることができる他の熱硬化成分として、メラミン誘導体、ベンゾグアナミン誘導体などのアミノ樹脂が挙げられる。
　このアミノ樹脂としては、例えば、メチロールメラミン化合物、メチロールベンゾグアナミン化合物、メチロールグリコールウリル化合物、メチロール尿素化合物などがある。さらに、アルコキシメチル化メラミン化合物、アルコキシメチル化ベンゾグアナミン化合物、アルコキシメチル化グリコールウリル化合物、アルコキシメチル化尿素化合物は、それぞれのメチロールメラミン化合物、メチロールベンゾグアナミン化合物、メチロールグリコールウリル化合物、メチロール尿素化合物のメチロール基をアルコキシメチル基に変換することにより得られる。このアルコキシメチル基の種類については特に限定されるものではなく、例えば、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基等とすることができる。特に、人体や環境に優しいホルマリン濃度が０．２％以下のメラミン誘導体が好ましい。 Moreover, amino resins, such as a melamine derivative and a benzoguanamine derivative, are mentioned as another thermosetting component which can be used suitably.
Examples of the amino resin include a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound, and alkoxymethylated urea compound are each methylol melamine compound, methylol benzoguanamine compound, methylol glycoluril compound, methylol group of methylol urea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration friendly to the human body and the environment of 0.2% or less is preferable.
　これらの市販品としては、例えば、サイメル３００、同３０１、同３０３、同３７０、同３２５、同３２７、同７０１、同２６６、同２６７、同２３８、同１１４１、同２７２、同２０２、同１１５６、同１１５８、同１１２３、同１１７０、同１１７４、同ＵＦＲ６５、同３００（以上、三井サイアナミッド（株）製）、ニカラックＭｘ－７５０、同Ｍｘ－０３２、同Ｍｘ－２７０、同Ｍｘ－２８０、同Ｍｘ－２９０、同Ｍｘ－７０６、同Ｍｘ－７０８、同Ｍｘ－４０、同Ｍｘ－３１、同Ｍｓ－１１、同Ｍｗ－３０、同Ｍｗ－３０ＨＭ、同Ｍｗ－３９０、同Ｍｗ－１００ＬＭ、同Ｍｗ－７５０ＬＭ（以上、（株）三和ケミカル製）等を挙げることができる。 Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mx-100 Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.).
　また、本発明の感光性樹脂組成物には、組成物の硬化性及び得られる硬化膜の強靭性を向上させるために、１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物を配合することができる。
　このような１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物は、１分子中に複数のイソシアネート基を有する化合物、すなわちポリイソシアネート化合物、又は１分子中に複数のブロック化イソシアネート基を有する化合物、すなわちブロックイソシアネート化合物などが挙げられる。 In addition, the photosensitive resin composition of the present invention contains a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule in order to improve the curability of the composition and the toughness of the resulting cured film. can do.
Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.
　前記ポリイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート又は脂環式ポリイソシアネートが用いられる。芳香族ポリイソシアネートの具体例としては、４，４’－ジフェニルメタンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ナフタレン－１，５－ジイソシアネート、ｏ－キシリレンジイソシアネート、ｍ－キシリレンジイソシアネート及び２，４－トリレンダイマーが挙げられる。脂肪族ポリイソシアネートの具体例としては、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、メチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、４，４－メチレンビス（シクロヘキシルイソシアネート）及びイソホロンジイソシアネートが挙げられる。脂環式ポリイソシアネートの具体例としてはビシクロヘプタントリイソシアネートが挙げられる。並びに先に挙げられたイソシアネート化合物のアダクト体、ビューレット体及びイソシアヌレート体が挙げられる。 As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.
　ブロックイソシアネート化合物に含まれるブロック化イソシアネート基は、イソシアネート基がブロック剤との反応により保護されて一時的に不活性化された基である。所定温度に加熱されたときにそのブロック剤が解離してイソシアネート基が生成する。
　このようなブロックイソシアネート化合物としては、イソシアネート化合物とイソシアネートブロック剤との付加反応生成物が用いられる。ブロック剤と反応し得るイソシアネート化合物としては、イソシアヌレート型、ビウレット型、アダクト型等が挙げられる。このイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート又は脂環式ポリイソシアネートが用いられる。芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネートの具体例としては、先に例示したような化合物が挙げられる。 The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
As such a blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
　イソシアネートブロック剤としては、例えば、フェノール、クレゾール、キシレノール、クロロフェノール及びエチルフェノール等のフェノール系ブロック剤；ε－カプロラクタム、δ－パレロラクタム、γ－ブチロラクタム及びβ－プロピオラクタム等のラクタム系ブロック剤；アセト酢酸エチル及びアセチルアセトンなどの活性メチレン系ブロック剤；メタノール、エタノール、プロパノール、ブタノール、アミルアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ベンジルエーテル、グリコール酸メチル、グリコール酸ブチル、ジアセトンアルコール、乳酸メチル及び乳酸エチル等のアルコール系ブロック剤；ホルムアルデヒドキシム、アセトアルドキシム、アセトキシム、メチルエチルケトキシム、ジアセチルモノオキシム、シクロヘキサンオキシム等のオキシム系ブロック剤；ブチルメルカプタン、ヘキシルメルカプタン、ｔ－ブチルメルカプタン、チオフェノール、メチルチオフェノール、エチルチオフェノール等のメルカプタン系ブロック剤；酢酸アミド、ベンズアミド等の酸アミド系ブロック剤；コハク酸イミド及びマレイン酸イミド等のイミド系ブロック剤；キシリジン、アニリン、ブチルアミン、ジブチルアミン等のアミン系ブロック剤；イミダゾール、２－エチルイミダゾール等のイミダゾール系ブロック剤；メチレンイミン及びプロピレンイミン等のイミン系ブロック剤等が挙げられる。 Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is done.
　ブロックイソシアネート化合物は市販のものであってもよく、例えば、スミジュールＢＬ－３１７５、ＢＬ－４１６５、ＢＬ－１１００、ＢＬ－１２６５、デスモジュールＴＰＬＳ－２９５７、ＴＰＬＳ－２０６２、ＴＰＬＳ－２０７８、ＴＰＬＳ－２１１７、デスモサーム２１７０、デスモサーム２２６５（以上、住友バイエルウレタン社製、商品名）、コロネート２５１２、コロネート２５１３、コロネート２５２０（以上、日本ポリウレタン工業社製、商品名）、Ｂ－８３０、Ｂ－８１５、Ｂ－８４６、Ｂ－８７０、Ｂ－８７４、Ｂ－８８２（以上、三井武田ケミカル社製、商品名）、ＴＰＡ－Ｂ８０Ｅ、１７Ｂ－６０ＰＸ、Ｅ４０２－Ｂ８０Ｔ（以上、旭化成ケミカルズ社製、商品名）等が挙げられる。なお、スミジュールＢＬ－３１７５、ＢＬ－４２６５はブロック剤としてメチルエチルオキシムを用いて得られるものである。 The blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.
　上記の１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物は、１種を単独で又は２種以上を組み合わせて用いることができる。
　このような１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物の配合量は、前記カルボキシル基含有感光性樹脂１００質量部に対して、１～１００質量部、より好ましくは、２～７０質量部の割合が適当である。前記配合量が、１質量部未満の場合、十分な塗膜の強靭性が得られず、好ましくない。一方、１００質量部を超えた場合、組成物の保存安定性が低下するので好ましくない。 The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 2 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. A proportion of 70 parts by weight is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, since the storage stability of a composition falls, it is unpreferable.
　本発明の感光性樹脂組成物には、水酸基やカルボキシル基とイソシアネート基との硬化反応を促進させるためにウレタン化触媒を配合することができる。
　このウレタン化触媒としては、錫系触媒、金属塩化物、金属アセチルアセトネート塩、金属硫酸塩、アミン化合物、又は／及びアミン塩から選択される１種以上のウレタン化触媒を使用することが好ましい。 In the photosensitive resin composition of the present invention, a urethanization catalyst can be blended in order to promote the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group.
As this urethanization catalyst, it is preferable to use one or more urethanization catalysts selected from tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. .
　前記錫系触媒としては、例えば、スタナスオクトエート、ジブチルすずジラウレートなどの有機すず化合物、無機すず化合物などが挙げられる。
　前記金属塩化物としては、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ又はＡｌからなる金属の塩化物で、例えば、塩化第二コバルト、塩化第一ニッケル、塩化第二鉄などが挙げられる。
　前記金属アセチルアセトネート塩としては、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ又はＡｌからなる金属のアセチルアセトネート塩であり、例えば、コバルトアセチルアセトネート、ニッケルアセチルアセトネート、鉄アセチルアセトネートなどが挙げられる。
　前記金属硫酸塩としては、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ又はＡｌからなる金属の硫酸塩で、例えば、硫酸銅などが挙げられる。
　前記アミン塩としては、例えば、ＤＢＵ（１，８－ジアザ－ビシクロ［５．４．０］ウンデセン－７）の有機酸塩系のアミン塩などが挙げられる。 Examples of the tin catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
The metal chloride is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.
The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Is mentioned.
The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.
Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).
　前記アミン化合物としては、例えば、従来公知のトリエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチル－１，６－ヘキサンジアミン、ビス（２－ジメチルアミノエチル）エーテル、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチルジエチレントリアミン、Ｎ－メチルモルフォリン、Ｎ－エチルモルフォリン、Ｎ，Ｎ－ジメチルエタノールアミン、ジモルホリノジエチルエーテル、Ｎ－メチルイミダゾール、ジメチルアミノピリジン、トリアジン、Ｎ’－（２－ヒドロキシエチル）－Ｎ，Ｎ，Ｎ’－トリメチルービス（２－アミノエチル）エーテル、Ｎ，Ｎ－ジメチルヘキサノールアミン、Ｎ，Ｎ－ジメチルアミノエトキシエタノール、Ｎ，Ｎ，Ｎ’－トリメチル－Ｎ’－（２－ヒドロキシエチル）エチレンジアミン、Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ’，Ｎ”，Ｎ”－テトラメチルジエチレントリアミン、Ｎ－（２－ヒドロキシプロピル）－Ｎ，Ｎ’，Ｎ”，Ｎ”－テトラメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’－トリメチル－Ｎ’－（２－ヒドロキシエチル）プロパンジアミン、Ｎ－メチル－Ｎ’－（２－ヒドロキシエチル）ピペラジン、ビス（Ｎ，Ｎ－ジメチルアミノプロピル）アミン、ビス（Ｎ，Ｎ－ジメチルアミノプロピル）イソプロパノールアミン、２－アミノキヌクリジン、３－アミノキヌクリジン、４－アミノキヌクリジン、２－キヌクリジオール、３－キヌクリジノール、４－キヌクリジノール、１－（２’－ヒドロキシプロピル）イミダゾール、１－（２’－ヒドロキシプロピル）－２－メチルイミダゾール、１－（２’－ヒドロキシエチル）イミダゾール、１－（２’－ヒドロキシエチル）－２－メチルイミダゾール、１－（２’－ヒドロキシプロピル）－２－メチルイミダゾール、１－（３’－アミノプロピル）イミダゾール、１－（３’－アミノプロピル）－２－メチルイミダゾール、１－（３’－ヒドロキシプロピル）イミダゾール、１－（３’－ヒドロキシプロピル）－２－メチルイミダゾール、Ｎ，Ｎ－ジメチルアミノプロピル－Ｎ’－（２－ヒドロキシエチル）アミン、Ｎ，Ｎ－ジメチルアミノプロピル－Ｎ’，Ｎ’－ビス（２－ヒドロキシエチル）アミン、Ｎ，Ｎ－ジメチルアミノプロピル－Ｎ’，Ｎ’－ビス（２－ヒドロキシプロピル）アミン、Ｎ，Ｎ－ジメチルアミノエチル－Ｎ’，Ｎ’－ビス（２－ヒドロキシエチル）アミン、Ｎ，Ｎ－ジメチルアミノエチル－Ｎ’，Ｎ’－ビス（２－ヒドロキシプロピル）アミン、メラミン又は／及びベンゾグアナミンなどが挙げられる。 Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′. , N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N′- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxy Chill) -N, N ′, N ″, N ″ -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ″, N ″ -tetramethyldiethylenetriamine, N, N, N′-trimethyl -N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1 -(2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imi Sol, 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′-amino) Propyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxyethyl) ) Amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N , N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′ , N'-bis (2-hydroxypropyl) amine, melamine or / and benzoguanamine.
　前記ウレタン化触媒の配合量は、通常の量的割合で充分であり、例えば、前記カルボキシル基含有感光性樹脂１００質量部に対して、好ましくは０．１～２０質量部、より好ましくは０．５～１０質量部である。 The compounding amount of the urethanization catalyst is sufficient in an ordinary quantitative ratio. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. 5 to 10 parts by mass.
　また、本発明の感光性樹脂組成物では、他の熱硬化成分として、ビスマレイミド化合物を配合することができる。
　このビスマレイミド化合物としては、多官能脂肪族／脂環族マレイミド、多官能芳香族マレイミドが挙げられる。
　多官能脂肪族／脂環族マレイミドとしては、例えば、Ｎ，Ｎ’－メチレンビスマレイミド、Ｎ，Ｎ’－エチレンビスマレイミド、トリス(ヒドロキシエチル)イソシアヌレートと脂肪族／脂環族マレイミドカルボン酸とを脱水エステル化して得られるイソシアヌレート骨格のマレイミドエステル化合物、トリス(カーバメートヘキシル)イソシアヌレートと脂肪族／脂環族マレイミドアルコールとをウレタン化して得られるイソシアヌレート骨格のマレイミドウレタン化合物等のイソシアヌル骨格ポリマレイミド類；イソホロンビスウレタンビス（Ｎ－エチルマレイミド）、トリエチレングリコールビス(マレイミドエチルカーボネート)、脂肪族／脂環族マレイミドカルボン酸と各種脂肪族／脂環族ポリオールとを脱水エステル化、又は脂肪族／脂環族マレイミドカルボン酸エステルと各種脂肪族／脂環族ポリオールとをエステル交換反応して得られる脂肪族／脂環族ポリマレイミドエステル化合物類；脂肪族／脂環族マレイミドカルボン酸と各種脂肪族／脂環族ポリエポキシドとをエーテル開環反応して得られる脂肪族／脂環族ポリマレイミドエステル化合物類、脂肪族／脂環族マレイミドアルコールと各種脂肪族／脂環族ポリイソシアネートとのウレタン化反応して得られる脂肪族／脂環族ポリマレイミドウレタン化合物類等がある。 Moreover, in the photosensitive resin composition of this invention, a bismaleimide compound can be mix | blended as another thermosetting component.
Examples of the bismaleimide compound include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide.
Examples of the polyfunctional aliphatic / alicyclic maleimide include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate, and aliphatic / alicyclic maleimide carboxylic acid. Isocyanurate skeletal polymide compounds such as isocyanurate skeleton maleimide urethane compounds obtained by urethanization of tris (carbamate hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol Maleimides; isophorone bisurethane bis (N-ethylmaleimide), triethylene glycol bis (maleimidoethyl carbonate), aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyols dehydrated or esterified Family / alicyclic Aliphatic / alicyclic polymaleimide ester compounds obtained by transesterification of maleimide carboxylic acid ester with various aliphatic / alicyclic polyols; aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic Aliphatic / alicyclic polymaleimide ester compounds obtained by ether ring-opening reaction with aliphatic polyepoxides, obtained by urethanization reaction between aliphatic / alicyclic maleimide alcohol and various aliphatic / alicyclic polyisocyanates Aliphatic / alicyclic polymaleimide urethane compounds and the like.
　多官能芳香族マレイミドとしては、マレイミドカルボン酸と各種芳香族ポリオールとを脱水エステル化、又はマレイミドカルボン酸エステルと各種芳香族ポリオールとをエステル交換反応して得られる芳香族ポリマレイミドエステル化合物類、マレイミドカルボン酸と各種芳香族ポリエポキシドとをエーテル開環反応して得られる芳香族ポリマレイミドエステル化合物類、マレイミドアルコールと各種芳香族ポリイソシアネートとのウレタン化反応して得られる芳香族ポリマレイミドウレタン化合物類の如き芳香族多官能マレイミド類等がある。 As the polyfunctional aromatic maleimide, aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols, maleimide Of aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides, and aromatic polymaleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates And aromatic polyfunctional maleimides.
　多官能芳香族マレイミドの具体例としては、例えば、Ｎ，Ｎ’－（４，４’－ジフェニルメタン）ビスマレイミド、Ｎ，Ｎ’－２，４－トリレンビスマレイミド、Ｎ，Ｎ’－２，６－トリレンビスマレイミド、１－メチル－２，４－ビスマレイミドベンゼン、Ｎ，Ｎ’－ｍ－フェニレンビスマレイミド、Ｎ，Ｎ’－ｐ－フェニレンビスマレイミド、Ｎ，Ｎ’－ｍ－トルイレンビスマレイミド、Ｎ，Ｎ’－４，４’－ビフェニレンビスマレイミド、Ｎ，Ｎ’－４，４’－〔３，３’－ジメチル－ビフェニレン〕ビスマレイミド、Ｎ，Ｎ’－４，４’－〔３，３’－ジメチルジフェニルメタン〕ビスマレイミド、Ｎ，Ｎ’－４，４’－〔３，３’－ジエチルジフェニルメタン〕ビスマレイミド、Ｎ，Ｎ’－４，４’－ジフェニルメタンビスマレイミド、Ｎ，Ｎ’－４，４’－ジフェニルプロパンビスマレイミド、Ｎ，Ｎ’－４，４’－ジフェニルエーテルビスマレイミド、Ｎ，Ｎ’－３，３’－ジフェニルスルホンビスマレイミド、Ｎ，Ｎ’－４，４’－ジフェニルスルホンビスマレイミド、２，２－ビス〔４－（４－マレイミドフェノキシ）フェニル〕プロパン、２，２－ビス〔３－ｔ－ブチル－４－（４－マレイミドフェノキシ）フェニル〕プロパン、２，２－ビス〔３－ｓ－ブチル－４－（４－マレイミドフェノキシ）フェニル〕プロパン、１，１－ビス〔４－（４－マレイミドフェノキシ）フェニル〕デカン、１，１－ビス〔２－メチル－４－（４－マレイミドフェノキシ）－５－ｔ－ブチルフェニル〕－２－メチルプロパン、４，４’－シクロヘキシリデン－ビス〔１－（４－マレイミドフェノキシ）－２－（１，１－ジメチルエチル）ベンゼン〕、４，４’－メチレン－ビス〔１－（４－マレイミドフェノキシ）－２，６－ビス（１，１－ジメチルエチル）ベンゼン〕、４，４’－メチレン－ビス〔１－（４－マレイミドフェノキシ）－２，６－ジ－ｓ－ブチルベンゼン〕、４，４’－シクロヘキシリデン－ビス〔１－（４－マレイミドフェノキシ）－２－シクロヘキシルベンゼン、４，４’－メチレンビス〔１－（マレイミドフェノキシ）－２－ノニルベンゼン〕、４，４’－（１－メチルエチリデン）－ビス〔１－（マレイミドフェノキシ）－２，６－ビス（１，１－ジメチルエチル）ベンゼン〕、４，４’－（２－エチルヘキシリデン）－ビス〔１－（マレイミドフェノキシ）－ベンゼン〕、４，４’－（１－メチルヘプチリデン）－ビス〔１－（マレイミドフェノキシ）－ベンゼン〕、４，４’－シクロヘキシリデン－ビス〔１－（マレイミドフェノキシ）－３－メチルベンゼン〕、２，２－ビス〔４－（４－マレイミドフェノキシ）フェニル〕ヘキサフルオロプロパン、２，２－ビス〔３－メチル－４－（４－マレイミドフェノキシ）フェニル〕プロパン、２，２－ビス〔３－メチル－４－（４－マレイミドフェノキシ）フェニル〕ヘキサフルオロプロパン、２，２－ビス〔３，５－ジメチル－４－（４－マレイミドフェノキシ）フェニル〕プロパン、２，２－ビス〔３，５－ジメチル－４－（４－マレイミドフェノキシ）フェニル〕ヘキサフルオロプロパン、２，２－ビス〔３－エチル－４－（４－マレイミドフェノキシ）フェニル〕プロパン、２，２－ビス〔３－エチル－４－（４－マレイミドフェノキシ）フェニル〕ヘキサフルオロプロパン、ビス〔３－メチル－（４－マレイミドフェノキシ）フェニル〕メタン、ビス〔３，５－ジメチル－（４－マレイミドフェノキシ）フェニル〕メタン、ビス〔３－エチル－（４－マレイミドフェノキシ）フェニル〕メタン、３，８－ビス〔４－（４－マレイミドフェノキシ）フェニル〕－トリシクロ〔５．２．１．０２，６〕デカン、４，８－ビス〔４－（４－マレイミドフェノキシ）フェニル〕－トリシクロ〔５．２．１．０２，６〕デカン、３，９－ビス〔４－（４－マレイミドフェノキシ）フェニル〕－トリシクロ〔５．２．１．０２，６〕デカン、４，９－ビス〔４－（４－マレイミドフェノキシ）フェニル〕－トリシクロ〔５．２．１．０２，６〕デカン、１，８－ビス〔４－（４－マレイミドフェノキシ）フェニル〕メンタン、１，８－ビス〔３－メチル－４－（４－マレイミドフェノキシ）フェニル〕メンタン、１，８－ビス〔３，５－ジメチル－４－（４－マレイミドフェノキシ）フェニル〕メンタン等を挙げることができる。 Specific examples of the polyfunctional aromatic maleimide include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2, 6-tolylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene Bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4′- [3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismale N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N ′ -4,4'-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl ] Propane, 2,2-bis [3-s-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-Methyl-4- (4-maleimidophenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4′-cyclohexylidene-bis [1- ( -Maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) ) -2-cyclohexylbenzene, 4,4′-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 ′-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2, 6-bis (1,1-dimethylethyl) benzene], 4,4 ′-(2-ethylhexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4 ′-( 1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4′-cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene], 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4 -Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4 -Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] pro 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl- (4-Maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1 .02,6] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 3,9-bis [4- (4-maleimide) Phenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [ 2.1.2,6] decane, 1,8-bis [4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] menthane 1,8-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] menthane and the like.
　これらの市販品としては、例えばＢＭＩ－１０００、ＢＭＩ－１０００Ｈ、ＢＭＩ－１０００Ｓ、ＢＭＩ－１１００、ＢＭＩ－１１００Ｈ、ＢＭＩ－２０００、ＢＭＩ－２３００、ＢＭＩ－３０００、ＢＭＩ－３０００Ｈ、ＢＭＩ－４０００、ＢＭＩ－５１００、ＢＭＩ－７０００、ＢＭＩ－７０００Ｈ、及びＢＭＩ－ＴＭＨ（以上、大和化成工業社製）、ＭＩＡ－２００（ＤＩＣ社製）等を挙げることができる。 Examples of these commercially available products include BMI-1000, BMI-1000H, BMI-1000S, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI- 5100, BMI-7000, BMI-7000H, BMI-TMH (manufactured by Daiwa Kasei Kogyo Co., Ltd.), MIA-200 (manufactured by DIC), and the like.
　これらのビスマレイミド化合物は常法により合成されてもよく、市販品を用いてもよい。特にビスマレイミド化合物の中で、環境に負荷をかけない点からは、分子内にハロゲン原子を含有しない物が好ましい。これらは１種を単独で又は２種以上を組み合わせて用いることができる。 These bismaleimide compounds may be synthesized by a conventional method, or commercially available products may be used. Particularly, among the bismaleimide compounds, those that do not contain a halogen atom in the molecule are preferable from the viewpoint of not placing a burden on the environment. These can be used individually by 1 type or in combination of 2 or more types.
　また、本発明の感光性樹脂組成物では、他の熱硬化成分として、ベンゾオキサジン化合物、オキサゾリン化合物、カルボジイミド化合物を配合することができる。
　ベンゾオキサジン化合物としては、ビスフェノールＡ型ベンゾオキサジン、ビスフェノールＦ型ベンゾオキサジン、ビスフェノールＳ型ベンゾオキサジン等が挙げられる。市販品としては、「Ｆ－ａ」（四国化成社製）を挙げることができる。
　オキサゾリン化合物としては、オキサゾリン基を含有していれば特に限定されない。市販品としては、エポクロス（日本触媒社製）のＫ－２０１０Ｅ、Ｋ－２０２０Ｅ、Ｋ－２０３０Ｅ、ＷＳ－５００、ＷＳ－７００、ＲＰＳ－１００５が挙げられる。
　シクロカーボネート化合物としては、環状化合物でカーボネート結合を有していれば特に限定されない。例えば、多官能構造を有するアルキレンカーボネート化合物が挙げられる。
　カルボジイミド化合物としては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド等が挙げられる。 Moreover, in the photosensitive resin composition of this invention, a benzoxazine compound, an oxazoline compound, and a carbodiimide compound can be mix | blended as another thermosetting component.
Examples of the benzoxazine compound include bisphenol A type benzoxazine, bisphenol F type benzoxazine, and bisphenol S type benzoxazine. Examples of commercially available products include “Fa” (manufactured by Shikoku Kasei Co., Ltd.).
The oxazoline compound is not particularly limited as long as it contains an oxazoline group. Examples of commercially available products include K-2010E, K-2020E, K-2030E, WS-500, WS-700, and RPS-1005 from Epocross (manufactured by Nippon Shokubai Co., Ltd.).
The cyclocarbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond. For example, the alkylene carbonate compound which has a polyfunctional structure is mentioned.
Examples of the carbodiimide compound include dicyclohexylcarbodiimide and diisopropylcarbodiimide.
　本発明の硬化性樹脂組成物には、感度を向上するために、連鎖移動剤として、公知のＮフェニルグリシン類、フェノキシ酢酸類、チオフェノキシ酢酸類、メルカプトチアゾール等を配合することができる。
　このような連鎖移動剤としては、例えば、メルカプト琥珀酸、メルカプト酢酸、メルカプトプロピオン酸、メチオニン、システイン、チオサリチル酸及びその誘導体等のカルボキシル基を有する連鎖移動剤；メルカプトエタノール、メルカプトプロパノール、メルカプトブタノール、メルカプトプロパンジオール、メルカプトブタンジオール、ヒドロキシベンゼンチオール及びその誘導体等の水酸基を有する連鎖移動剤；１－ブタンチオール、ブチル－３－メルカプトプロピオネート、メチル－３－メルカプトプロピオネート、２，２－（エチレンジオキシ）ジエタンチオール、エタンチオール、４－メチルベンゼンチオール、ドデシルメルカプタン、プロパンチオール、ブタンチオール、ペンタンチオール、１－オクタンチオール、シクロペンタンチオール、シクロヘキサンチオール、チオグリセロール、４，４－チオビスベンゼンチオール等が挙げられる。 In order to improve sensitivity, the curable resin composition of the present invention may contain known N phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like as chain transfer agents.
Examples of such chain transfer agents include chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.
　また、多官能性メルカプタン系化合物を用いることができ、特に限定されるものではないが、例えば、ヘキサン－１，６－ジチオール、デカン－１，１０－ジチオール、ジメルカプトジエチルエーテル、ジメルカプトジエチルスルフィド等の脂肪族チオール類、キシリレンジメルカプタン、４，４′-ジメルカプトジフェニルスルフィド、１，４－ベンゼンジチオール等の芳香族チオール類；エチレングリコールビス（メルカプトアセテート）、ポリエチレングリコールビス（メルカプトアセテート）、プロピレングリコールビス（メルカプトアセテート）、グリセリントリス（メルカプトアセテート）、トリメチロールエタントリス（メルカプトアセテート）、トリメチロールプロパントリス（メルカプトアセテート）、ペンタエリスリトールテトラキス（メルカプトアセテート）、ジペンタエリスリトールヘキサキス（メルカプトアセテート）等の多価アルコールのポリ（メルカプトアセテート）類；エチレングリコールビス（３－メルカプトプロピオネート）、ポリエチレングリコールビス（３－メルカプトプロピオネート）、プロピレングリコールビス（３－メルカプトプロピオネート） 、グリセリントリス（３－メルカプトプロピオネート）、トリメチロールエタントリス（メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）等の多価アルコールのポリ（３－メルカプトプロピオネート）類；１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１H，３H，５H）－トリオン、ペンタエリリトールテトラキス（３－メルタプトブチレート）等のポリ（メルカプトブチレート）類等が挙げられる。 Polyfunctional mercaptan compounds can be used and are not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide Aliphatic thiols such as xylylene dimercaptan, 4,4'-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) s of polyhydric alcohols such as tetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, and poly (mercaptobutyrate) s such as pentaerythritol tetrakis (3-mertabutbutyrate).
　さらに、連鎖移動剤として働くメルカプト基を有する複素環化合物としては、例えば、メルカプト－４－ブチロラクトン（別名：２－メルカプト－４－ブタノリド）、２－メルカプト－４－メチル－４－ブチロラクトン、２－メルカプト－４－エチル－４－ブチロラクトン、２－メルカプト－４－ブチロチオラクトン、２－メルカプト－４－ブチロラクタム、Ｎ－メトキシ－２－メルカプト－４－ブチロラクタム、Ｎ－エトキシ－２－メルカプト－４－ブチロラクタム、Ｎ－メチル－２－メルカプト－４－ブチロラクタム、Ｎ－エチル－２－メルカプト－４－ブチロラクタム、Ｎ－（２－メトキシ）エチル－２－メルカプト－４－ブチロラクタム、Ｎ－（２－エトキシ）エチル－２－メルカプト－４－ブチロラクタム、２－メルカプト－５－バレロラクトン、２－メルカプト－５－バレロラクタム、Ｎ－メチル－２－メルカプト－５－バレロラクタム、Ｎ－エチル－２－メルカプト－５－バレロラクタム、Ｎ－（２－メトキシ）エチル－２－メルカプト－５－バレロラクタム、Ｎ－（２－エトキシ）エチル－２－メルカプト－５－バレロラクタムおよび２－メルカプト－６－ヘキサノラクタム等が挙げられる。 Furthermore, examples of the heterocyclic compound having a mercapto group that functions as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2- Mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4 -Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy ) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5 Valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto -5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercapto-6-hexanolactam and the like.
　特に、光硬化性樹脂組成物の現像性を損なうことがない連鎖移動剤であるメルカプト基を有する複素環化合物として、メルカプトベンゾチアゾール、３－メルカプト－４－メチル－４Ｈ－１，２，４－トリアゾール、５－メチル－１，３，４－チアジアゾール－２－チオール、１－フェニル－５－メルカプト－１Ｈ－テトラゾールが好ましい。これらの連鎖移動剤は、単独または２種以上を併用することができる。 In particular, as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4- Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used alone or in combination of two or more.
　このようなメルカプト化合物の配合量は、前記カルボキシル基含有感光性樹脂１００質量部に対して、０．０１質量部以上、１０質量部以下が適当であり、さらに好ましくは０．０５質量部以上、５部質量部以下である。０．０１質量部未満では、メルカプト化合物添加の効果が確認されず、一方、１０質量部を超えると、感光性樹脂組成物の現像不良、乾燥管理幅の低下などを引き起こすおそれがあるので好ましくない。 The blending amount of such a mercapto compound is suitably 0.01 parts by weight or more and 10 parts by weight or less, more preferably 0.05 parts by weight or more, with respect to 100 parts by weight of the carboxyl group-containing photosensitive resin. 5 parts by mass or less. If it is less than 0.01 parts by mass, the effect of adding a mercapto compound is not confirmed. On the other hand, if it exceeds 10 parts by mass, it may cause development failure of the photosensitive resin composition, a decrease in the dry management width, etc., which is not preferable. .
　本発明の感光性樹脂組成物には、活性エネルギー線照射により、光硬化して、カルボキシル基含有感光性樹脂を、アルカリ水溶液に不溶化させる、又は不溶化を助けるために、反応性希釈剤を配合することができる。
　このような反応性希釈剤としては、例えば、分子中に複数のエチレン性不飽和基を有する化合物が挙げられ、慣用公知のポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ウレタン（メタ）アクリレート、カーボネート（メタ）アクリレート、エポキシ（メタ）アクリレートなどが使用でき、具体的には、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類；エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類；Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類；Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類；ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス－ヒドロキシエチルイソシアヌレートなどの多価アルコール又はこれらのエチレオキサイド付加物、プロピレンオキサイド付加物、もしくはε－カプロラクトン付加物などの多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート、及びこれらのフェノール類のエチレンオキサイド付加物もしくはプロピレンオキサイド付加物などの多価アクリレート類；グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類；上記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類及びメラミンアクリレート、及び／又は上記アクリレートに対応する各メタクリレート類などが挙げられる。 In the photosensitive resin composition of the present invention, a reactive diluent is blended in order to incur or insolubilize the carboxyl group-containing photosensitive resin in an alkaline aqueous solution by photocuring by irradiation with active energy rays. be able to.
Examples of such reactive diluents include compounds having a plurality of ethylenically unsaturated groups in the molecule, and commonly known polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates. , Carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol Diacrylates of glycols such as propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate; Multivalent acrylates such as these ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols Multivalent acrylates; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether Polyglycerides of glycidyl ethers such as triglycidyl isocyanurate; not limited to the above, polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes and polyester polyols may be directly acrylated or urethane acrylated via diisocyanate Acrylates and melamine acrylates and / or methacrylates corresponding to the above acrylates.
　さらに、クレゾールノボラック型エポキシ樹脂などの多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレートなどのヒドロキシアクリレートとイソホロンジイソシアネートなどのジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物などが、挙げられる。このようなエポキシアクリレート系樹脂は、指触乾燥性を低下させることなく、光硬化性を向上させることができる Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
　このような分子中に複数のエチレン性不飽和基を有する化合物の配合量は、前記カルボキシル基含有感光性樹脂１００質量部に対して、５～１００質量部の割合が望ましく、より好ましくは１～７０質量部の割合である。前記配合量が、５質量部未満の場合、光硬化性が低下し、活性エネルギー線照射後のアルカリ現像により、パターン形成が困難となるので、好ましくない。一方、１００質量部を超えた場合、アルカリ水溶液に対する溶解性が低下して、塗膜が脆くなるので、好ましくない。 The compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is desirably 5 to 100 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. The ratio is 70 parts by mass. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
　さらに、本発明の感光性樹脂組成物は、前記カルボキシル基含有感光性樹脂の合成や組成物の調製のため、又は基板やキャリアフィルムに塗布するための粘度調整のため、有機溶剤を使用することができる。 Furthermore, the photosensitive resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing photosensitive resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. Can do.
　このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などが挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類；オクタン、デカン等の脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などである。このような有機溶剤は、単独で又は２種以上の混合物として用いられる。 Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.
　本発明の感光性樹脂組成物は、着色剤を配合することができる。
　着色剤としては、赤、青、緑、黄などの慣用公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよい。但し、環境負荷低減並びに人体への影響の観点からハロゲンを含有しないことが好ましい。 The photosensitive resin composition of this invention can mix | blend a coloring agent.
As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
　赤色着色剤：
　赤色着色剤としては、モノアゾ系、ジスアゾ系、モノアゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などが挙げられる。
　具体的には以下のようなカラ－インデックス（Ｃ．Ｉ．；ザ　ソサイエティ　オブ　ダイヤーズ　アンド　カラリスツ（The Society of Dyers and Colourists）発行）番号が付されているものを使用することができる。
　モノアゾ系としては、Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269 等が用いられる。
　ジスアゾ系としては、Pigment Red 37, 38, 41 等が用いられる。
　モノアゾレーキ系としては、Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1,68 等が用いられる。
　ベンズイミダゾロン系としては、Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208 等が用いられる。
　ぺリレン系としては、Solvent Red 135、Solvent Red 179、Pigment Red 123、Pigment Red 149、Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 224 等が用いられる。
　ジケトピロロピロール系としては、Pigment Red 254、Pigment Red 255、Pigment Red 264、Pigment Red 270、Pigment Red 272 等が用いられる。
　縮合アゾ系としては、Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242 等が用いられる。
　アンスラキノン系としては、Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207 等が用いられる。
　キナクリドン系としては、Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209 等が用いられる。 Red colorant:
Examples of the red colorant include monoazo, disazo, monoazo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like.
Specifically, those having the following color index numbers (CI; issued by The Society of Dyers and Colorists) can be used.
Monoazo series includes Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. are used.
Pigment Red 37, 38, 41 etc. are used as the disazo system.
Monoazo lakes include Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2. , 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68 etc. are used.
Examples of benzimidazolone-based compounds include Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, and Pigment Red 208.
Examples of perylene systems include Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, and the like.
Examples of the diketopyrrolopyrrole include Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, and Pigment Red 272.
Examples of condensed azo compounds include Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, and Pigment Red 242.
Examples of anthraquinone include Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207, and the like.
As the quinacridone series, Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 and the like are used.
　青色着色剤：
　青色着色剤としては、フタロシアニン系、アントラキノン系が挙げられる。
　このうち、顔料系では、ピグメント（Pigment）に分類されている化合物、具体的には、Pigment Blue 15、Pigment Blue 15:1、Pigment Blue 15:2、Pigment Blue 15:3、Pigment Blue 15:4、Pigment Blue 15:6、Pigment Blue 16、Pigment Blue 60 等が用いられる。
　染料系では、Solvent Blue 35、Solvent Blue 63、Solvent Blue 68、Solvent Blue 70、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、Solvent Blue 70 等が用いられる。
　なお、これら以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Blue colorant:
Examples of blue colorants include phthalocyanine and anthraquinone.
Among these, in the pigment system, compounds classified as Pigment, specifically, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, etc. are used.
Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 67 70 etc. are used.
Besides these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
　緑色着色剤：
　緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系が挙げられる。具体的には、具体的にはPigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 5、Solvent Green 20、Solvent Green 28等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Green colorant:
Similarly, examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
　黄色着色剤：
　黄色着色剤としては、モノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等が挙げられる。具体的には、
　アントラキノン系としては、Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202 等が用いられる。
　イソインドリノン系としては、Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185 等が用いられる。
　縮合アゾ系としては、Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180 等が用いられる。
　ベンズイミダゾロン系としては、Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181 等が用いられる。
　モノアゾ系としては、Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183 等が用いられる。
　ジスアゾ系としては、Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 等が用いられる。 Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. In particular,
As an anthraquinone series, Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202, and the like are used.
Examples of isoindolinone compounds include Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, and Pigment Yellow 185.
Examples of condensed azo compounds include Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, and Pigment Yellow 180.
As the benzimidazolone series, Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 and the like are used.
As monoazo series, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 116, 167, 168, 169, 182, 183, etc. are used.
As the disazo group, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and the like are used.
　その他、色調を調整する目的で、紫やオレンジ、茶色、黒などの着色剤を配合してもよい。このような着色剤としては、例えば、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、C.I.ピグメントオレンジ１、C.I.ピグメントオレンジ５、C.I.ピグメントオレンジ１３、C.I.ピグメントオレンジ１４、C.I.ピグメントオレンジ１６、C.I.ピグメントオレンジ１７、C.I.ピグメントオレンジ２４、C.I.ピグメントオレンジ３４、C.I.ピグメントオレンジ３６、C.I.ピグメントオレンジ３８、C.I.ピグメントオレンジ４０、C.I.ピグメントオレンジ４３、C.I.ピグメントオレンジ４６、C.I.ピグメントオレンジ４９、C.I.ピグメントオレンジ５１、C.I.ピグメントオレンジ６１、C.I.ピグメントオレンジ６３、C.I.ピグメントオレンジ６４、C.I.ピグメントオレンジ７１、C.I.ピグメントオレンジ７３、C.I.ピグメントブラウン２３、C.I.ピグメントブラウン２５、C.I.ピグメントブラック１、C.I.ピグメントブラック７等がある。 Other colorants such as purple, orange, brown and black may be added for the purpose of adjusting the color tone. Examples of such colorants include Pigment® Violet® 19, 23, 29, 32, 36, 38, 42, Solvent® Violet® 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, and CI Pigment Orange. 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 2 , C.I. Pigment Black 1, there is a C.I. Pigment Black 7 and the like.
　前記したような着色剤の配合割合は、特に制限はないが、前記カルボキシル基含有感光性樹脂１００質量部に対して、好ましくは１０質量部以下、特に好ましくは０．１～５質量部の割合で充分である。 The blending ratio of the colorant as described above is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. Is enough.
　本発明の感光性樹脂組成物は、その塗膜の物理的強度等を上げるために、必要に応じて、フィラーを配合することができる。このようなフィラーとしては、公知慣用の無機又は有機フィラーが使用できるが、特に硫酸バリウム、球状シリカ及びタルクが好ましく用いられる。さらに、白色の外観や難燃性を得るために酸化チタンや金属酸化物、水酸化アルミニウムなどの金属水酸化物を体質顔料フィラーとしても使用することができる。これらフィラーの配合量は、前記カルボキシル基含有感光性樹脂１００質量部に対して、好ましくは２００質量部以下、より好ましくは０．１～１５０質量部、特に好ましくは、１～１００質量部である。フィラーの配合量が、２００質量部を超えた場合、組成物の粘度が高くなり、印刷性が低下したり、硬化物が脆くなるので好ましくない。 In the photosensitive resin composition of the present invention, a filler can be blended as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers. The amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. . When the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.
　さらに本発明の感光性樹脂組成物は、指触乾燥性の改善、ハンドリング性の改善などを目的にバインダーポリマーを使用することができる。例えばポリエステル系ポリマー、ポリウレタン系ポリマー、ポリエステルウレタン系ポリマー、ポリアミド系ポリマー、ポリエステルアミド系ポリマー、アクリル系ポリマー、セルロース系ポリマー、ポリ乳酸系ポリマー、フェノキシ系ポリマーなどを用いることができる。これらのバインダーポリマーは、単独で又は２種類以上の混合物として使用することができる。 Furthermore, in the photosensitive resin composition of the present invention, a binder polymer can be used for the purpose of improving the touch drying property and the handling property. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.
　さらに本発明の感光性樹脂組成物は、柔軟性の付与、硬化物の脆さを改善することなどを目的にエラストマーを使用することができる。例えばポリエステル系エラストマー、ポリウレタン系エラストマー、ポリエステルウレタン系エラストマー、ポリアミド系エラストマー、ポリエステルアミド系エラストマー、アクリル系エラストマーなどを使用することができる。また、種々の骨格を有するエポキシ樹脂の一部又は全部のエポキシ基を両末端カルボン酸変性型ブタジエン－アクリロニトリルゴムで変性したエラストマーなども使用できる。更にはエポキシ含有ポリブタジエン系エラストマー、アクリル含有ポリブタジエン系エラストマー、水酸基含有ポリブタジエン系エラストマー、水酸基含有イソプレン系エラストマー等も使用することができる。これらのエラストマーは、単独で又は２種類以上の混合物として使用することができる。 Furthermore, the photosensitive resin composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or the like can be used. In addition, an elastomer in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. These elastomers can be used alone or as a mixture of two or more.
　一般に、高分子材料の多くは、一度酸化が始まると、次々と連鎖的に酸化劣化が起き、高分子素材の機能低下をもたらすことから、本発明の感光性樹脂組成物には、酸化を防ぐために（１）発生したラジカルを無効化するようなラジカル捕捉剤又は／及び（２）発生した過酸化物を無害な物質に分解し、新たなラジカルが発生しないようにする過酸化物分解剤などの酸化防止剤を添加することができる。特に本発明に用いられるブタジエン系エラストマーを使用する組成物に、酸化防止剤を使用すると、ＰＣＴ耐性が向上し、ＨＡＳＴ時の剥がれや変色が少なくなり、効果的である。 Generally, in many polymer materials, once oxidation starts, oxidative degradation successively occurs one after another, resulting in a decrease in the function of the polymer material. Therefore, the photosensitive resin composition of the present invention prevents oxidation. (1) A radical scavenger that invalidates the generated radicals and / or (2) a peroxide decomposer that decomposes the generated peroxide into harmless substances and prevents the generation of new radicals. An antioxidant can be added. In particular, when an antioxidant is used in a composition that uses a butadiene-based elastomer used in the present invention, PCT resistance is improved, and peeling and discoloration during HAST are reduced, which is effective.
　ラジカル捕捉剤として働く酸化防止剤の具体的な化合物としては、ヒドロキノン、４－ｔ－ブチルカテコール、２－ｔ－ブチルヒドロキノン、ヒドロキノンモノメチルエーテル、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、２，２－メチレン－ビス（４－メチル－６－ｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－Ｓ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）トリオン等のフェノール系、メタキノン、ベンゾキノン等のキノン系化合物、ビス（２，２，６，６－テトラメチル－４－ピペリジル）－セバケート、フェノチアジン等のアミン系化合物等などが挙げられる。 Specific compounds of antioxidants that act as radical scavengers include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxy) Benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as methaquinone and benzoquinone, bis (2,2,6,6-teto Methyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.
　ラジカル捕捉剤は市販のものであってもよく、例えば、アデカスタブＡＯ－３０、アデカスタブＡＯ－３３０、アデカスタブＡＯ－２０、アデカスタブＬＡ－７７、アデカスタブＬＡ－５７、アデカスタブＬＡ－６７、アデカスタブＬＡ－６８、アデカスタブＬＡ－８７（以上、旭電化社製、商品名）、ＩＲＧＡＮＯＸ１０１０、ＩＲＧＡＮＯＸ１０３５、ＩＲＧＡＮＯＸ１０７６、ＩＲＧＡＮＯＸ１１３５、ＴＩＮＵＶＩＮ　１１１ＦＤＬ、ＴＩＮＵＶＩＮ　１２３、ＴＩＮＵＶＩＮ　１４４、ＴＩＮＵＶＩＮ　１５２、ＴＩＮＵＶＩＮ　２９２、ＴＩＮＵＶＩＮ　５１００（以上、チバ・ジャパン社製、商品名）などが挙げられる。 The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, TINUVIN 5100 Japan) Product name).
　過酸化物分解剤として働く酸化防止剤の具体的な化合物としては、トリフェニルフォスファイト等のリン系化合物、ペンタエリスリトールテトララウリルチオプロピオネート、ジラウリルチオジプロピオネート、ジステアリル３，３’－チオジプロピオネート等の硫黄系化合物などが挙げられる。 Specific examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.
　過酸化物分解剤は市販のものであってもよく、例えば、アデカスタブＴＰＰ（旭電化社製、商品名）、マークＡＯ－４１２Ｓ（アデカ・アーガス化学社製、商品名）、スミライザーＴＰＳ（住友化学社製、商品名）などが挙げられる。
　上記の酸化防止剤は、１種を単独で又は２種以上を組み合わせて用いることができる。 The peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilizer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.
　また一般に、高分子材料は光を吸収し、それにより分解・劣化を起こすことから、本発明の感光性樹脂組成物には、紫外線に対する安定化対策を行うために、上記酸化防止剤の他に、紫外線吸収剤を使用することができる。 In general, since the polymer material absorbs light and thereby decomposes and deteriorates, the photosensitive resin composition of the present invention includes, in addition to the above antioxidant, in order to take a countermeasure against stabilization against ultraviolet rays. UV absorbers can be used.
　紫外線吸収剤としては、ベンゾフェノン誘導体、ベンゾエート誘導体、ベンゾトリアゾール誘導体、トリアジン誘導体、ベンゾチアゾール誘導体、シンナメート誘導体、アントラニレート誘導体、ジベンゾイルメタン誘導体などが挙げられる。ベンゾフェノン誘導体の具体的な例としては、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－ｎ－オクトキシベンゾフェノン、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン及び２，４－ジヒドロキシベンゾフェノンなどが挙げられる。ベンゾエート誘導体の具体的な例としては、２－エチルヘキシルサリチレート、フェニルサリチレート、ｐ－ｔ－ブチルフェニルサリチレート、２，４－ジ－ｔ－ブチルフェニル－３，５－ジ－ｔ－ブチル－４－ヒドロキシベンゾエート及びヘキサデシル－３，５－ジ－ｔ－ブチル－４－ヒドロキシベンゾエートなどが挙げられる。ベンゾトリアゾール誘導体の具体的な例としては、２－（２’－ヒドロキシ－５’－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－メチルフェニル）べンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール及び２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－アミルフェニル）ベンゾトリアゾールなどが挙げられる。トリアジン誘導体の具体的な例としては、ヒドロキシフェニルトリアジン、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジンなどが挙げられる。 Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
　紫外線吸収剤としては市販のものであってもよく、例えば、ＴＩＮＵＶＩＮ　ＰＳ、ＴＩＮＵＶＩＮ　９９－２、ＴＩＮＵＶＩＮ　１０９、ＴＩＮＵＶＩＮ　３８４－２、ＴＩＮＵＶＩＮ　９００、ＴＩＮＵＶＩＮ　９２８、ＴＩＮＵＶＩＮ　１１３０、ＴＩＮＵＶＩＮ　４００、ＴＩＮＵＶＩＮ　４０５、ＴＩＮＵＶＩＮ　４６０、ＴＩＮＵＶＩＮ　４７９（以上、チバ・ジャパン社製、商品名）などが挙げられる。
　上記の紫外線吸収剤は、１種を単独で又は２種以上を組み合わせて用いることができ、前記酸化防止剤と併用することで本発明の感光性樹脂組成物より得られる成形物の安定化が図れる。 Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Japan, trade name) and the like.
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, the molding obtained from the photosensitive resin composition of this invention can be stabilized. I can plan.
　本発明の感光性樹脂組成物には、層間の密着性、又は感光性樹脂層と基材との密着性を向上させるためにを用いることができる。
　具体的に例を挙げ密着付与剤ると、例えば、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾチアゾール（商品名：川口化学工業（株）製アクセルＭ）、３－モルホリノメチル－１－フェニル－トリアゾール－２－チオン、５－アミノ－３－モルホリノメチル－チアゾール－２－チオン、２－メルカプト－５－メチルチオ－チアジアゾール、トリアゾール、テトラゾール、ベンゾトリアゾール、カルボキシベンゾトリアゾール、アミノ基含有ベンゾトリアゾール、シランカップリング剤などがある。 In order to improve the adhesiveness between layers or the adhesiveness between the photosensitive resin layer and the substrate, the photosensitive resin composition of the present invention can be used.
Specific examples of adhesion promoters include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical Industry Co., Ltd.) Axel M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzo Examples include triazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.
　本発明の感光性樹脂組成物は、さらに必要に応じて、微粉シリカ、有機ベントナイト、モンモリロナイト、ハイドロタルサイトなどのチキソ化剤を添加することができる。チキソ化剤としての経時安定性は有機ベントナイト、ハイドロタルサイトが好ましく、特にハイドロタルサイトは電気特性に優れている。また、熱重合禁止剤や、シリコーン系、フッ素系、高分子系などの消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、防錆剤、更にはビスフェノール系、トリアジンチオール系などの銅害防止剤などのような公知慣用の添加剤類を配合することができる。 The photosensitive resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary. Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics. In addition, thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, and bisphenols Known and conventional additives such as copper damage prevention agents such as those based on triazine and triazine thiols can be blended.
　前記熱重合禁止剤は、前記重合性化合物の熱的な重合又は経時的な重合を防止するために用いることができる。熱重合禁止剤としては、例えば、４－メトキシフェノール、ハイドロキノン、アルキル又はアリール置換ハイドロキノン、ｔ－ブチルカテコール、ピロガロール、２－ヒドロキシベンゾフェノン、４－メトキシ－２－ヒドロキシベンゾフェノン、塩化第一銅、フェノチアジン、クロラニル、ナフチルアミン、β－ナフトール、２，６－ジ－ｔ－ブチル－４－クレゾール、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、ピリジン、ニトロベンゼン、ジニトロベンゼン、ピクリン酸、４－トルイジン、メチレンブルー、銅と有機キレート剤反応物、サリチル酸メチル、及びフェノチアジン、ニトロソ化合物、ニトロソ化合物とＡｌとのキレートなどが挙げられる。 The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
　このように構成される本発明の硬化性樹脂組成物は、例えば有機溶剤で塗布方法に適した粘度に調整され、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布される。 The curable resin composition of the present invention configured as described above is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method It is applied by a method such as screen printing or curtain coating.
　そして、約６０～１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることにより、タックフリーの塗膜を形成する。このとき、揮発乾燥は、熱風循環式乾燥炉、ＩＲ炉、ホットプレート、コンベクションオーブンなど（蒸気による空気加熱方式の熱源を備えたものを用い乾燥機内の熱風を向流接触させる方法およびノズルより支持体に吹き付ける方式）を用いて行うことができる。 Then, a tack-free coating film is formed by volatilizing and drying (preliminary drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. At this time, the volatile drying is supported by a hot air circulation drying furnace, IR furnace, hot plate, convection oven or the like (a method equipped with an air heating type heat source by steam and contacting the hot air in the dryer countercurrently and the nozzle. Can be performed using a method of spraying on the body).
　また、本発明の硬化性樹脂組成物をキャリアフィルム上に塗布し、乾燥させてフィルムとして巻き取ることにより、ドライフィルムを形成し、これを基材上に張り合わせることにより、樹脂絶縁層を形成してもよい。 In addition, the curable resin composition of the present invention is applied on a carrier film, dried and wound up as a film to form a dry film, and this is laminated on a substrate to form a resin insulation layer May be.
　このとき、塗膜が形成される、あるいはドライフィルムを張り合わせる基材としては、紙フェノール、紙エポキシ、ガラス布エポキシ、ガラスポリイミド、ガラス布／不繊布エポキシ、ガラス布／紙エポキシ、合成繊維エポキシ、フッ素・ポリエチレン・ＰＰＯ・シアネートエステル等を用いた高周波回路用銅張積層版等の材質を用いたもので全てのグレード（ＦＲ－４等）の銅張積層版、その他ポリイミドフィルム、ＰＥＴフィルム、ガラス基板、セラミック基板、ウエハ板等を挙げることができる。 At this time, as a base material on which a coating film is formed or a dry film is laminated, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy All grades (FR-4, etc.) of copper clad laminates, such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate esters, etc., other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer board, etc. can be mentioned.
　次に、接触式（又は非接触方式）により、パターンを形成したフォトマスクを通して選択的に活性エネルギー線により、露光もしくはレーザーダイレクト露光機により直接パターン露光（活性エネルギー線の照射）する。 Next, by a contact method (or non-contact method), pattern exposure (irradiation of active energy rays) is selectively performed by an active energy ray through a photomask on which a pattern is formed, or by exposure or a laser direct exposure machine.
　活性エネルギー線照射に用いられる露光機としては、直接描画装置（例えばコンピューターからのＣＡＤデータにより直接レーザーで画像を描くレーザーダイレクトイメージング装置）を用いることができる。例えば、日本オルボテック社製、ペンタックス社製等のものを使用することができ、最大波長が３５０～４１０ｎｍのレーザー光を発振する装置であれば、いずれの装置を用いてもよい。 As an exposure machine used for active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can be used. For example, devices manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device that oscillates laser light having a maximum wavelength of 350 to 410 nm may be used.
　活性エネルギー線としては、最大波長が３５０～４１０ｎｍの範囲にあるレーザー光であれば、ガスレーザー、固体レーザーのいずれを用いてもよい。また、その露光量は膜厚等によって異なるが、一般には５～１０００ｍＪ／ｃｍ2、好ましくは１０～５００ｍＪ／ｃｍ2、さらに好ましくは２０～４００ｍＪ／ｃｍ2の範囲内とすることができる。 As the active energy ray, either a gas laser or a solid-state laser may be used as long as it has a maximum wavelength in the range of 350 to 410 nm. The exposure amount varies depending on the film thickness and the like, but can generally be in the range of 5 to 1000 mJ / cm 2 , preferably 10 to 500 mJ / cm 2 , more preferably 20 to 400 mJ / cm 2 .
　このようにして露光することにより、露光部（活性エネルギー線により照射された部分）を硬化させ、次いで、未露光部を希アルカリ水溶液（例えば０．３～３％炭酸ソーダ水溶液）により現像することにより、レジストパターンが形成される。 By exposing in this way, the exposed portion (the portion irradiated by the active energy ray) is cured, and then the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a resist pattern is formed.
　このとき、現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができ、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。 At this time, the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developer is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicic acid. Alkaline aqueous solutions such as sodium, ammonia and amines can be used.
　さらに、熱硬化性成分を加えた場合、例えば約１４０～１８０℃の温度に加熱して、熱硬化させることにより、カルボキシル基含有感光性樹脂のカルボキシル基と、分子中に複数の環状エーテル基及び／又は環状チオエーテル基を有する熱硬化性成分が反応し、耐熱性、耐薬品性、耐吸湿性、密着性、電気特性などの諸特性に優れた硬化塗膜を形成することができる。 Further, when a thermosetting component is added, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing photosensitive resin and a plurality of cyclic ether groups in the molecule and A thermosetting component having a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
　このように、本発明の硬化性樹脂組成物において、カルボキシル基含有感光性樹脂、及び光重合開始剤と、必要に応じて希釈剤、熱硬化性成分、着色剤等を含有することにより、優れたアルカリ現像性、また優れた作業性、量産性を得ることができる。さらに、これを塗布して得られる塗膜に、選択的に露光、現像し、必要に応じて仕上げ硬化を行うことによって、密着性、耐薬品性、無電解金めっき耐性、冷熱衝撃耐性、ＰＣＴ耐性、電気絶縁性等に優れた硬化物を得ることができ、この硬化物をプリント配線板に用いることにより、高い信頼性を与えることができる。 Thus, in the curable resin composition of the present invention, by containing a carboxyl group-containing photosensitive resin, a photopolymerization initiator, and, if necessary, a diluent, a thermosetting component, a colorant, etc., it is excellent. Alkali developability, and excellent workability and mass productivity can be obtained. Furthermore, the coating film obtained by applying this is selectively exposed, developed, and finish-cured as necessary, so that adhesion, chemical resistance, electroless gold plating resistance, thermal shock resistance, PCT A cured product excellent in resistance, electrical insulation and the like can be obtained, and high reliability can be provided by using the cured product for a printed wiring board.
　以下、実施例及び比較例を示して本発明について具体的に説明するが、本発明が、以下の実施例に限定されるものではないことはもとよりである。
　（樹脂合成例１）
　温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、ビスフェノールＡ-ホルムアルデヒド型フェノール樹脂（明和化成（株）製、商品名「ＢＰＡ－Ｄ」、ＯＨ当量：１２０）１２０．０ｇ、水酸化カリウム１．２０ｇ及びトルエン１２０．０ｇを仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド６３．８ｇを徐々に滴下し、１２５～１３２℃、０～４．８ｋｇ／ｃｍ2で１６時間反応させた。
　その後、室温まで冷却し、この反応溶液に８９％リン酸１．５６ｇを添加混合して水酸化カリウムを中和し、不揮発分６２．１％、水酸基価が１８２．２ｇ／ｅｑ．であるビスフェノールＡ-ホルムアルデヒド型フェノール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基１当量当りアルキレンオキシドが平均１．０８モル付加しているものであった。
　得られたノボラック型クレゾール樹脂のアルキレンオキシド反応溶液２９３．０ｇ、アクリル酸４３．２ｇ、メタンスルホン酸１１．５３ｇ、メチルハイドロキノン０．１８ｇ及びトルエン２５２．９ｇを、撹拌機、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１１０℃で１２時間反応させた。
　反応により生成した水は、トルエンとの共沸混合物として１２．６ｇ留出した。その後、室温まで冷却し、得られた反応溶液を１５％水酸化ナトリウム水溶液３５．３５ｇで中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１１８．１ｇで置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。
　次に、得られたノボラック型アクリレート樹脂溶液３３２．５ｇ及びトリフェニルホスフィン１．２２ｇを、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物６０．８ｇを徐々に加え、９５～１０１℃で６時間反応させ、固形物の酸価８８ｍｇＫＯＨ／ｇ、不揮発分７１％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－１とする。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, it cannot be overemphasized that this invention is not limited to a following example.
(Resin synthesis example 1)
Into an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120) 0 g, 1.20 g of potassium hydroxide and 120.0 g of toluene were charged, and the system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours.
Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A propylene oxide reaction solution of bisphenol A-formaldehyde type phenol resin was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
293.0 g of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring.
12.6 g of water produced by the reaction was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%. . This is designated as resin solution A-1.
　（樹脂合成例２）
　ビスフェノールＡ-ホルムアルデヒド型フェノール樹脂（明和化成（株）製、商品名「ＢＰＡ－Ｄ」、ＯＨ当量：１２０）１２０部、トリフェニルホスフィン０．６部及びプロピレンカーボネート１１２部を反応釜に仕込み、撹拌しながら、１５０～１６０℃に加熱昇温して反応を開始させ、次いで２００～２２０℃で約２ 時間反応を続けた。反応の進行とともに炭酸ガスが発生するので、系外に除去した。
　その後、室温まで冷却し、水酸基当量が１８２．２ｇ／ｅｑ．であるビスフェノールＡ-ホルムアルデヒド型フェノール樹脂のプロピレンカーボネート反応物を得た。これは、フェノール性水酸基１当量当りプロピレンオキシドが平均１．０８モル付加しているものと同等であった。
　得られた反応物をトルエン１２０部に溶解させた後、この中にアクリル酸４３．２部、パラトルエンスルホン酸１．７部及びメチルハイドロキノン０．０４部を仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１００±１０℃で７時間反応させた。反応により生成した水は、トルエンとの共沸混合物として１１．６部留出した。その後、室温まで冷却し、得られた反応溶液を水洗し、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１１８．１部で置換しつつ留去し、アクリレート樹脂溶液を得た。
　次に、得られたアクリレート樹脂溶液３３２．５部及びトリフェニルホスフィン１．１部を、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物６０．８部を徐々に加え、９５～１０５℃で約６時間反応させ、固形物の酸価８８ｍｇＫＯＨ／ｇ、不揮発分７１％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－２とする。 (Resin synthesis example 2)
120 parts of bisphenol A-formaldehyde type phenolic resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate are charged into a reaction kettle and stirred. The reaction was started by heating to 150 to 160 ° C., and then continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system.
Then, it cooled to room temperature and a hydroxyl group equivalent was 182.2 g / eq. A propylene carbonate reaction product of bisphenol A-formaldehyde type phenol resin was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.6 parts of water produced by the reaction was distilled as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.
Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride is gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%. Obtained. This is designated as resin solution A-2.
　（樹脂合成例３）
　ビスフェノールＡ-ホルムアルデヒド型フェノール樹脂（明和化成（株）製、商品名「ＢＰＡ－Ｄ」、ＯＨ当量：１２０）１２０部、トリフェニルホスフィン０．６部及びエチレンカーボネート９６．９部を反応釜に仕込み、撹拌しながら、１５０～１６０℃に加熱昇温して反応を開始させ、次いで２００～２２０℃で約２時間反応を続けた。反応の進行とともに炭酸ガスが発生するので、系外に除去した。
　その後、室温まで冷却し、水酸基当量が１８２．２ｇ／ｅｑ．であるビスフェノールＡ－ホルムアルデヒド型フェノール樹脂のプロピレンカーボネート反応物を得た。これは、フェノール性水酸基１当量当りプロピレンオキシドが平均１．０８モル付加しているものと同等であった。
　得られた反応物をトルエン１２０部に溶解させた後、この中にアクリル酸４３．２部、パラトルエンスルホン酸１．７部及びメチルハイドロキノン０．０４部を仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１００±１０℃で７時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、１１．６部の水が留出した。その後、室温まで冷却し、得られた反応溶液を水洗し、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１１８．１部で置換しつつ留去し、アクリレート樹脂溶液を得た。
　次に、得られたアクリレート樹脂溶液３３２．５部及びトリフェニルホスフィン１．１部を、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物６０．８部を徐々に加え、９５～１０５℃で約６時間反応させ、固形物の酸価８９ｍｇＫＯＨ／ｇ、不揮発分７２％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－３とする。 (Resin synthesis example 3)
A reaction kettle is charged with 120 parts of bisphenol A-formaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “BPA-D”, OH equivalent: 120), 0.6 part of triphenylphosphine and 96.9 parts of ethylene carbonate. While stirring, the temperature was raised to 150 to 160 ° C. to start the reaction, and then the reaction was continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system.
Then, it cooled to room temperature and a hydroxyl group equivalent was 182.2 g / eq. A propylene carbonate reaction product of bisphenol A-formaldehyde type phenol resin was obtained. This was equivalent to an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid, and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.
Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 89 mgKOH / g and a nonvolatile content of 72%. Obtained. This is designated as Resin Solution A-3.
　（樹脂合成例４）
　サリチルアルデヒド型フェノール樹脂（明和化成（株）製、商品名「ＭＥＨ－７５００」、ＯＨ当量：９８）９８部、トリフェニルホスフィン０．６部及びプロピレンカーボネート１１２部を反応釜に仕込み、撹拌しながら、１５０～１６０℃に加熱昇温して反応を開始させ、次いで２００～２２０℃で約２時間反応を続けた。反応の進行とともに炭酸ガスが発生するので、系外に除去した。
　その後、室温まで冷却し、水酸基当量が１５９ｇ／ｅｑ．であるサリチルアルデヒド型フェノール樹脂のプロピレンカーボネート反応物を得た。これは、フェノール性水酸基１ 当量当りプロピレンオキシドが平均１．０５モル付加しているものと同等であった。
　得られた反応物をトルエン１２０部に溶解させた後、この中にアクリル酸４３．２部、パラトルエンスルホン酸１．７部及びメチルハイドロキノン０．０４部を仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１００±１０℃で７時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、１１．８部の水が留出した。その後、室温まで冷却し、得られた反応溶液を水洗し、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１１８．１部で置換しつつ留去し、アクリレート樹脂溶液を得た。
　次に、得られたアクリレート樹脂溶液３３２．５部及びトリフェニルホスフィン１．１部を、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物６０．８部を徐々に加え、９５～１０５℃で約６時間反応させ、固形物の酸価９２ｍｇＫＯＨ／ｇ、不揮発分７２％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－４とする。 (Resin synthesis example 4)
While charging 98 kg of salicylaldehyde type phenol resin (Maywa Kasei Co., Ltd., trade name “MEH-7500”, OH equivalent: 98), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, stirring them. The reaction was started by heating to 150 to 160 ° C. and then continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system.
Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 159 g / eq. A propylene carbonate reaction product of salicylaldehyde type phenol resin was obtained. This was equivalent to an average of 1.05 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the obtained reaction product was dissolved in 120 parts of toluene, 43.2 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone were charged therein, and air was supplied at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 11.8 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with diethylene glycol monoethyl ether acetate 118.1 parts, and the acrylate resin solution was obtained.
Next, 332.5 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride is gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 92 mgKOH / g and a nonvolatile content of 72%. Obtained. This is designated as Resin Solution A-4.
　（樹脂合成例５）
　一般式（III）のフェノール樹脂（明和化成社製、商品名「ＭＥＨ－７８５１」、ＯＨ当量：２０５）２０５部、トリフェニルホスフィン０．６部及びプロピレンカーボネート１１２部を反応釜に仕込み、撹拌しながら、１５０～１６０℃に加熱昇温して反応を開始させ、次いで２００～２２０℃で約２時間反応を続けた。反応の進行とともに炭酸ガスが発生するので、系外に除去した。その後、室温まで冷却し、水酸基当量が２６９ｇ／ｅｑ．である一般式（III）のフェノール樹脂のプロピレンカーボネート反応物を得た。これは、フェノール性水酸基１当量当りプロピレンオキサイドが平均１．１モル付加しているものと同等であった。
　上記反応物をトルエン１５０部に溶解させた後、この中にアクリル酸３６．０部、パラトルエンスルホン酸１．７部及びメチルハイドロキノン０．０４部を仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１００±１０℃で７時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、９．６部の水が留出した。その後、室温まで冷却し、得られた反応溶液を水洗し、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１５０部で置換しつつ留去し、アクリレート樹脂溶液を得た。
　次に、得られたアクリレート樹脂溶液４４２部及びトリフェニルホスフィン１．１部を、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物７６．０部を徐々に加え、９５～１０５℃で約６時間反応させ、固形物の酸価７９ｍｇＫＯＨ／ｇ、不揮発分７１％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－５とする。 (Resin synthesis example 5)
A reaction vessel was charged with 205 parts of a phenol resin of the general formula (III) (Maywa Kasei Co., Ltd., trade name “MEH-7851”, OH equivalent: 205), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, and stirred. The reaction was started by heating to 150 to 160 ° C., and then the reaction was continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 269 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (III) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After the above reactants were dissolved in 150 parts of toluene, 36.0 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone were charged therein, and air was blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 9.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, and the resulting reaction solution was washed with water and distilled off while replacing toluene with 150 parts of diethylene glycol monoethyl ether acetate by an evaporator to obtain an acrylate resin solution.
Next, 442 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 76.0 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 79 mgKOH / g and a nonvolatile content of 71%. . This is designated as Resin Solution A-5.
　（樹脂合成例６）
　一般式（IV）のフェノール樹脂（明和化成社製、商品名「ＭＥＨ－７８００」、ＯＨ当量：１８０）１８０部、トリフェニルホスフィン０．６部及びプロピレンカーボネート１１２部を反応釜に仕込み、撹拌しながら、１５０～１６０℃に加熱昇温して反応を開始させ、次いで２００～２２０℃で約２時間反応を続けた。反応の進行とともに炭酸ガスが発生するので、系外に除去した。その後、室温まで冷却し、水酸基当量が２４４ｇ／ｅｑ．である一般式（IV）のフェノール樹脂のプロピレンカーボネート反応物を得た。これは、フェノール性水酸基１当量当りプロピレンオキシドが平均１．１モル付加しているものと同等であった。
　上記反応物をトルエン１２０部に溶解させた後、この中にアクリル酸３６．０部、パラトルエンスルホン酸１．７部及びメチルハイドロキノン０．０４部を仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１００±１０℃で７時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、９．７部の水が留出した。その後、室温まで冷却し、得られた反応溶液を水洗し、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１２０部で置換しつつ留去し、アクリレート樹脂溶液を得た。次に、得られたアクリレート樹脂溶液３８８部及びトリフェニルホスフィン１．１部を、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物７６．０部を徐々に加え、９５～１０５℃で約６時間反応させ、固形物の酸価８３ｍｇＫＯＨ／ｇ、不揮発分７４％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－６とする。 (Resin synthesis example 6)
A reaction vessel was charged with 180 parts of a phenol resin of general formula (IV) (Maywa Kasei Co., Ltd., trade name “MEH-7800”, OH equivalent: 180), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate, and stirred. The reaction was started by heating to 150 to 160 ° C., and then the reaction was continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 244 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (IV) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After dissolving the above reactants in 120 parts of toluene, 36.0 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone are charged into it, and air is blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. The water produced | generated by reaction distills 9.7 parts of water as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with 120 parts of diethylene glycol monoethyl ether acetate, and the acrylate resin solution was obtained. Next, 388 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 76.0 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 83 mg KOH / g and a nonvolatile content of 74%. . This is designated as Resin Solution A-6.
　（樹脂合成例７）
　一般式（V）のフェノール樹脂（新日本石油社製、商品名「ＤＰＰ－６１１５Ｈ」、ＯＨ当量：１８０）１８０部、トリフェニルホスフィン０．６部及びプロピレンカーボネート１１２部を反応釜に仕込み、撹拌しながら、１５０～１６０℃に加熱昇温して反応を開始させ、次いで２００～２２０℃で約２時間反応を続けた。反応の進行とともに炭酸ガスが発生するので、系外に除去した。その後、室温まで冷却し、水酸基当量が２４３ｇ／ｅｑ．である一般式（V）のフェノール樹脂のプロピレンカーボネート反応物を得た。これは、フェノール性水酸基１当量当りプロピレンオキサイドが平均１．１モル付加しているものと同等であった。
　上記反応物をトルエン１２０部に溶解させた後、この中にアクリル酸３６．０部、パラトルエンスルホン酸１．７部及びメチルハイドロキノン０．０４部を仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１００±１０℃で７時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、９．８部の水が留出した。その後、室温まで冷却し、得られた反応溶液を水洗し、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１２０部で置換しつつ留去し、アクリレート樹脂溶液を得た。
　次に、得られたアクリレート樹脂溶液３８８部及びトリフェニルホスフィン１．１部を、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物７６．０部を徐々に加え、９５～１０５℃で約６時間反応させ、固形物の酸価８２ｍｇＫＯＨ／ｇ、不揮発分７３％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－７とする。 (Resin synthesis example 7)
A reaction kettle was charged with 180 parts of a phenol resin of the general formula (V) (trade name “DPP-6115H”, OH equivalent: 180, manufactured by Nippon Oil Corporation), 0.6 part of triphenylphosphine, and 112 parts of propylene carbonate. The reaction was started by heating to 150 to 160 ° C. and then continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 243 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (V) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After dissolving the above reactants in 120 parts of toluene, 36.0 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone are charged into it, and air is blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 9.8 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with 120 parts of diethylene glycol monoethyl ether acetate, and the acrylate resin solution was obtained.
Next, 388 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 76.0 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 82 mgKOH / g and a nonvolatile content of 73%. . This is designated as Resin Solution A-7.
　（樹脂合成例８）
　一般式（VI）のフェノール樹脂（日本化薬社製、商品名「カヤハードＣＢＮ」、ＯＨ当量：１４０）１４０部、トリフェニルホスフィン０．６部及びプロピレンカーボネート１１２部を反応釜に仕込み、撹拌しながら、１５０～１６０℃に加熱昇温して反応を開始させ、次いで２００～２２０℃で約２時間反応を続けた。反応の進行とともに炭酸ガスが発生するので、系外に除去した。その後、室温まで冷却し、水酸基当量が２０４ｇ／ｅｑ．である一般式（VI）のフェノール樹脂のプロピレンカーボネート反応物を得た。これは、フェノール性水酸基１当量当りプロピレンオキサイドが平均１．１モル付加しているものと同等であった。
　上記反応物をトルエン１２０部に溶解させた後、この中にアクリル酸３９．６部、パラトルエンスルホン酸１．７部及びメチルハイドロキノン０．０４部を仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１００±１０℃で７時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、１０．５部の水が留出した。その後、室温まで冷却し、得られた反応溶液を水洗し、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１２０部で置換しつつ留去し、アクリレート樹脂溶液を得た。
　次に、得られたアクリレート樹脂溶液３１２部及びトリフェニルホスフィン１．１部を、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物６８．４部を徐々に加え、９５～１０５℃で約６時間反応させ、固形物の酸価８５ｍｇＫＯＨ／ｇ、不揮発分７３％のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ａ－８とする。 (Resin synthesis example 8)
Charge 140 parts of phenolic resin of general formula (VI) (Nippon Kayaku Co., Ltd., trade name “Kayahard CBN”, OH equivalent: 140), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate to a reaction kettle and stir. The reaction was started by heating to 150 to 160 ° C., and then the reaction was continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 204 g / eq. A propylene carbonate reaction product of a phenol resin of the general formula (VI) was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
After dissolving the above reactants in 120 parts of toluene, 39.6 parts of acrylic acid, 1.7 parts of paratoluenesulfonic acid and 0.04 part of methylhydroquinone are charged into it, and air is blown at a rate of 10 ml / min. The mixture was reacted at 100 ± 10 ° C. for 7 hours with stirring. 10.5 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with 120 parts of diethylene glycol monoethyl ether acetate, and the acrylate resin solution was obtained.
Next, 312 parts of the obtained acrylate resin solution and 1.1 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min and stirred. Then, 68.4 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin having a solid acid value of 85 mgKOH / g and a non-volatile content of 73%. . This is designated as Resin Solution A-8.
　（比較樹脂合成例１）
　ジエチレングリコールモノエチルエーテルアセテート６００ｇにオルソクレゾールノボラック型エポキシ樹脂〔ＤＩＣ社製、ＥＰＩＣＬＯＮ　Ｎ－６９５、軟化点９５℃、エポキシ当量２１４、平均官能基数７．６〕１０７０ｇ（グリシジル基数（芳香環総数）：５．０モル）、アクリル酸３６０ｇ（５．０モル）、及びハイドロキノン１．５ｇを仕込み、１００℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン４．３ｇを仕込み、１１０℃に加熱して２時間反応後、１２０℃に昇温してさらに１２時間反応を行った。得られた反応液に芳香族系炭化水素（ソルベッソ１５０）４１５ｇ、テトラヒドロ無水フタル酸４５６．０ｇ（３．０モル）を仕込み、１１０℃で４時間反応を行い、冷却後、固形分酸価８９ｍｇＫＯＨ／ｇ、固形分６５％の樹脂溶液を得た。これを樹脂溶液Ｒ－１とする。 (Comparative resin synthesis example 1)
Orthocresol novolac type epoxy resin (produced by DIC, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average number of functional groups 7.6) to 1070 g of diethylene glycol monoethyl ether acetate (number of glycidyl groups (total number of aromatic rings): 5) 0.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This is designated as resin solution R-1.
　（比較樹脂合成例２）
　エポキシ当量８００、軟化点７９℃のビスフェノールＦ型固形エポキシ樹脂４００gをエピクロロヒドリン９２５gとジメチルスルホキシド４６２．５gを溶解させた後、攪拌下７０℃で９８．５％ＮａＯＨ８１．２gを１００分かけて添加した。添加後さらに７０℃で３時間反応を行なった。次いで過剰の未反応エピクロロヒドリンおよびジメチルスルホキシドの大半を減圧下に留去し、副生塩とジメチルスルホキシドを含む反応生成物をメチルイソブチルケトン７５０gに溶解させ、さらに３０％ＮａＯＨ１０部を加え７０℃で１時間反応させた。反応終了後、水２００gで２回水洗を行った。油水分離後、油層よりメチルイソブチルケトンを蒸留回収して、エポキシ当量２９０、軟化点６２℃のエポキシ樹脂３７０gを得た。
　このエポキシ樹脂２９００g（１０当量）、アクリル酸７２０g（１０当量）、メチルハイドロキノン２．８g、カルビトールアセテート１９５０gを仕込み、９０℃に加熱、攪拌し、反応混合物を溶解した。次いで、反応液を６０℃に冷却し、トリフェニルホスフィン１６．７gを仕込み、１００℃に加熱し、約３２時間反応し、酸価が１．０ｍｇＫＯＨ／ｇの反応物を得た。次に、これに無水コハク酸７８６g（７．８６モル）、カルビトールアセテート４２３gを仕込み、９５℃に加熱し、約６時間反応を行い、固形分酸価１００ｍｇＫＯＨ／ｇ、固形分６５％の樹脂溶液を得た。これを樹脂溶液Ｒ－２とする。 (Comparative resin synthesis example 2)
After dissolving 925 g of epichlorohydrin and 462.5 g of dimethyl sulfoxide in 400 g of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 g of 98.5% NaOH was added for 100 minutes at 70 ° C. with stirring. Added. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 g of methyl isobutyl ketone, and further 10 parts of 30% NaOH was added and added. The reaction was carried out at 1 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 g of water. After the oil / water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain 370 g of an epoxy resin having an epoxy equivalent of 290 and a softening point of 62 ° C.
2900 g (10 equivalents) of this epoxy resin, 720 g (10 equivalents) of acrylic acid, 2.8 g of methylhydroquinone, and 1950 g of carbitol acetate were charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 16.7 g of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 g (7.86 mol) of succinic anhydride and 423 g of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, and a resin having a solid content acid value of 100 mgKOH / g and a solid content of 65%. A solution was obtained. This is designated as resin solution R-2.
　これらの樹脂溶液を用い、表1，２に示す種々の成分とともに表1，２に示す割合（質量部）にて配合し、攪拌機にて予備混合した後、３本ロールミルで混練し、ソルダーレジスト用光硬化性樹脂組成物を調製した。ここで、得られた光硬化性樹脂組成物の分散度を、エリクセン社製グラインドメータによる粒度測定にて評価したところ、１５μｍ以下であった。 Using these resin solutions, the various components shown in Tables 1 and 2 are blended in the proportions (parts by mass) shown in Tables 1 and 2, premixed with a stirrer, kneaded with a three-roll mill, and solder resist A photocurable resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer made from an Eriksen company.
Figure JPOXMLDOC01-appb-T000001
 ＊1  2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン
　(イルガキュア907: チバ・ジャパン製)
＊2  2,4-ジエチルチオキサントン(KAYACURE DETX-S:日本化薬社製)
＊3  2-(アセチルオキシイミノメチル)チオキサンテン-9-オン
＊4  エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-, 1-(0-アセチルオキシム)
　(イルガキュア OXE 02:チバ・ジャパン製)
＊5  アデカアークルズ ＮＣＩ－８３１（(株）ＡＤＥＫＡ製）
＊6  変性ノボラック型エポキシ樹脂(EPICLON N-865:DIC社製)
＊7  ビキシレノール型エポキシ樹脂(YX-4000：ジャパンエポキシレジン（株）製)
＊8  エポキシ化ポリブタジエン（エポリードPB3600：ダイセル化学工業社製）
＊9  メチル化メラミン樹脂（（株）三和ケミカル製）
＊10  ブロックイソシアネート(旭化成ケミカルズ社製)
＊11  ジペンタエリスリトールヘキサアクリレート(DPHA:日本化薬社製)
＊12  C.I.Pigment Blue 15:3
＊13  C.I.Pigment Yellow147
＊14  2-メルカプトベンゾチアゾール
＊15  酸化防止剤（チバ・ジャパン社製）
＊16  B-30 (堺化学（株）製)
＊17  ハイドロタルサイト（協和化学工業（株）製）
＊18  ジエチレングリコールモノエチルエーテールアセテート
　
Figure JPOXMLDOC01-appb-T000001
 * 1 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: Ciba Japan)
* 2 2,4-Diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3 2- (Acetyloxyiminomethyl) thioxanthen-9-one * 4 Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0 -Acetyloxime)
(Irgacure OXE 02: made by Ciba Japan)
* 5 Adeka Arcles NCI-831 (manufactured by ADEKA Corporation)
* 6 Modified novolac epoxy resin (EPICLON N-865: manufactured by DIC)
* 7 Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.)
* 8 Epoxidized polybutadiene (Epolide PB3600: manufactured by Daicel Chemical Industries)
* 9 Methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)
* 10 Block isocyanate (Asahi Kasei Chemicals)
* 11 Dipentaerythritol hexaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 12 CIPigment Blue 15: 3
* 13 CIPigment Yellow147
* 14 2-mercaptobenzothiazole * 15 Antioxidant (Ciba Japan)
* 16 B-30 (manufactured by Sakai Chemical Co., Ltd.)
* 17 Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 18 Diethylene glycol monoethyl ether acetate
Figure JPOXMLDOC01-appb-T000002
 ＊1  2-メチル-1-(4-メチルチオフェニル)-2-モルホリノプロパン-1-オン
　(イルガキュア907: チバ・ジャパン社製)
＊2  2,4-ジエチルチオキサントン(KAYACURE DETX-S:日本化薬社製)
＊3  2-(アセチルオキシイミノメチル)チオキサンテン-9-オン
＊4  エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)
　(イルガキュア OXE 02:チバ・ジャパン社製)
＊5  アデカアークルズ ＮＣＩ－８３１（（株）ＡＤＥＫＡ製）
＊6  ビフェニルノボラック変性型エポキシ樹脂(NC3000:日本化薬社製)
＊7  ビキシレノール型エポキシ樹脂(YX-4000：ジャパンエポキシレジン社製)
＊8  エポキシ化ポリブタジエン（エポリードPB3600：ダイセル化学工業社製）
＊9  メチル化メラミン樹脂（MW-100LM：三和ケミカル社製）
＊10　ブロックイソシアネート(TPA-B80E：旭化成ケミカルズ社製)
＊11　ジペンタエリスリトールヘキサアクリレート(DPHA:日本化薬社製)
＊12　C.I.Pigment Blue 15:3
＊13　C.I.Pigment Yellow147
＊14　2-メルカプトベンゾチアゾール
＊15　酸化防止剤（チバ・ジャパン社製）
＊16　B-30 (堺化学社製)
＊17　ハイドロタルサイト（協和化学工業社製）
＊18　ジエチレングリコールモノエチルエーテルアセテート
Figure JPOXMLDOC01-appb-T000002
 * 1 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: manufactured by Ciba Japan)
* 2 2,4-Diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3 2- (Acetyloxyiminomethyl) thioxanthen-9-one * 4 Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O -Acetyloxime)
(Irgacure OXE 02: Ciba Japan)
* 5 Adeka Arkles NCI-831 (manufactured by ADEKA Corporation)
* 6 Biphenyl novolac modified epoxy resin (NC3000: Nippon Kayaku Co., Ltd.)
* 7 Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin)
* 8 Epoxidized polybutadiene (Epolide PB3600: manufactured by Daicel Chemical Industries)
* 9 Methylated melamine resin (MW-100LM: manufactured by Sanwa Chemical Co., Ltd.)
* 10 Block isocyanate (TPA-B80E: Asahi Kasei Chemicals)
* 11 Dipentaerythritol hexaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 12 CIPigment Blue 15: 3
* 13 CIPigment Yellow147
* 14 2-mercaptobenzothiazole * 15 Antioxidant (Ciba Japan)
* 16 B-30 (manufactured by Sakai Chemical)
* 17 Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 18 Diethylene glycol monoethyl ether acetate
　このようにして得られた実施例１～２７および比較例１～４について、以下のような評価を行った。これらの評価結果を表３および表４に示す。
　（性能評価）
　〈最適露光量〉
　得られた実施例及び比較例の硬化性樹脂組成物を、銅厚３５μｍの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスクリーン印刷法により全面に塗布し、８０℃の熱風循環式乾燥炉で６０分間乾燥させた。乾燥後、高圧水銀灯搭載の露光装置を用いてステップタブレット（ＫｏｄａｋＮｏ２）を介して露光し、現像（３０℃、０．２ＭＰａ、１質量％炭酸ナトリウム水溶液）を９０秒で行った際残存するステップタブレットのパターンが７段の時を最適露光量とした。
　　<現像性>
　各実施例及び比較例の硬化性樹脂組成物を、銅ベタ基板上にスクリーン印刷法により、乾燥後に約２５μｍになるように塗布し、８０℃の熱風循環式乾燥炉で３０分間乾燥させた。乾燥後、１質量％炭酸ナトリウム水溶液によって現像を行い、乾燥塗膜が除去されるまでの時間をストップウォッチにより計測した。
　〈最大現像ライフ〉
　各実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で全面塗布し、８０℃で乾燥し２０分から８０分まで１０分おきに基板を取り出し、室温まで放冷した。この基板に、３０℃の１質量％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａの条件で９０秒間現像を行い、残渣が残らない最大許容乾燥時間を最大現像ライフとした。
　〈タック性〉
　各実施例及び比較例の組成物をパターン形成された銅箔基板上にスクリーン印刷で全面塗布し、８０℃の熱風循環式乾燥炉で３０分間乾燥させ、室温まで放冷した。この基板にＰＥＴ製ネガフィルムを当て、ＯＲＣ社製（ＨＭＷ－ＧＷ２０）で１分間減圧条件下で圧着させ、その後、ネガフィルムを剥がしたときのフィルムの張り付き状態を評価した。
　○：フィルムを剥がす時に、全く抵抗が無いが、塗膜に跡が少しついている。（全く抵抗が無く、塗膜に跡が残らない場合を含む。）
　△：フィルムを剥がす時に、僅かに抵抗があり、塗膜に跡が少しついている。
　×：フィルムを剥がす時に、抵抗があり、塗膜にはっきり跡がついている。 Examples 1 to 27 and Comparative Examples 1 to 4 thus obtained were evaluated as follows. These evaluation results are shown in Tables 3 and 4.
(Performance evaluation)
<Optimal exposure>
The obtained curable resin compositions of Examples and Comparative Examples were subjected to circuit printing with a copper thickness of 35 μm after buffing, washed with water, dried and then applied to the entire surface by a screen printing method. It was dried for 60 minutes in a drying furnace. After drying, the step tablet remaining after exposure through a step tablet (Kodak No. 2) using an exposure device equipped with a high-pressure mercury lamp and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) in 90 seconds. The optimal exposure amount was obtained when the pattern was 7 steps.
<Developability>
The curable resin compositions of each Example and Comparative Example were applied to a copper solid substrate by screen printing so that the thickness was about 25 μm after drying, and was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, development was performed with a 1% by mass aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured with a stopwatch.
<Maximum development life>
The composition of each example and comparative example was applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 20 minutes from 20 to 80 minutes, and allowed to cool to room temperature. . The substrate was developed with a 1% by weight aqueous sodium carbonate solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.
<Tackiness>
The composition of each Example and Comparative Example was applied on the entire surface of a patterned copper foil substrate by screen printing, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and the film was pressure-bonded with ORC (HMW-GW20) under reduced pressure conditions for 1 minute. Thereafter, the state of the film when it was peeled off was evaluated.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark. (Including the case where there is no resistance and no mark is left on the coating.)
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.
　（特性試験）
　実施例及び比較例の各組成物を、パターン形成された銅箔基板上にスクリーン印刷で全面塗布し、８０℃で３０分乾燥し、室温まで放冷した。この基板に高圧水銀灯を搭載した露光装置をもちいて最適露光量でソルダーレジストパターンを露光し、３０℃の１質量％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａ/ｃｍ2の条件で９０秒間現像を行い、レジストパターンを得た。この基板を、ＵＶコンベア炉にて積算露光量１０００ｍＪ／ｃｍ2 の条件で紫外線照射した後、１５０℃で６０分加熱して硬化した。得られたプリント基板（評価基板）に対して以下のように特性を評価した。
　〈耐酸性〉
　評価基板を、１０ｖｏｌ％Ｈ2ＳＯ4水溶液に室温で３０分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープビールによる剥がれを確認した。
　なお、実施例１５～２７、比較例３，４については、１０質量％ＨＣｌ水溶液を用いたこと以外は同様に評価した。
　○：変化が認められないもの
　△：ほんの僅か変化しているもの
　×：塗膜に膨れあるいは膨潤脱落があるもの
　〈耐アルカリ性〉
　評価基板を、１０ｖｏｌ％ＮａＯＨ水溶液に室温で３０分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープビールによる剥がれを確認した。
　なお、実施例１５～２７、比較例３，４については、１０質量％ＮａＯＨ水溶液を用いたこと以外は同様に評価した。
　○：変化が認められないもの
　△：ほんの僅か変化しているもの
　×：塗膜に膨れあるいは膨潤脱落があるもの
　〈はんだ耐熱性〉
　ロジン系フラックスを塗布した評価基板を、予め２６０℃に設定したはんだ槽に浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
　○：１０秒間浸漬を３回以上繰り返しても剥がれが認められない。
　△：１０秒間浸漬を３回以上繰り返すと少し剥がれる。
　×：１０秒間浸漬を３回以内にレジスト層に膨れ、剥がれがある。
　〈無電解金めっき耐性〉
　市販品の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル５μｍ、金０．０５μｍの条件でめっきを行い、テープピーリングにより、レジスト層の剥がれの有無やめっきのしみ込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
　◎：染み込み、剥がれが見られない。
　○：めっき後に少し染み込みが確認されるが、テープピール後は剥がれない。
　△：めっき後にほんの僅かしみ込みが見られ、テープピール後に剥がれも見られる。
　×：めっき後に剥がれが有る。
　〈ＰＣＴ耐性〉
　ソルダーレジスト硬化塗膜を形成した評価基板を、ＰＣＴ装置（エスペック株式会社製 ＨＡＳＴ ＳＹＳＴＥＭ ＴＰＣ－４１２ＭＤ）を用いて、１２１℃、飽和、０．２ＭＰａの条件で１６８時間処理し、塗膜の状態を評価した。判定基準は以下の通りである。
　○：膨れ、剥がれ、変色、溶出のないもの
　△：若干の膨れ、剥がれ、変色、溶出があるもの
　×：膨れ、剥がれ、変色、溶出が多く見られるもの
　〈冷熱衝撃耐性〉
　□抜き、○抜きパターンを形成したソルダーレジスト硬化塗膜を有する評価基板を作製した。得られた評価基板を冷熱衝撃試験器（エタック株式会社製）で－５５ ℃／３０分　～ １５０ ℃／３０分を１サイクルとして１０００ サイクルの耐性試験を行った。試験後、処理後の硬化膜を目視により観察し、クラックの発生状況を下記の基準にて判断した。
　○ : クラック発生率３０％未満
　△ : クラック発生率３０～５０％
　× : クラック発生率５０％以上
　なお、実施例１５～２７、比較例３，４については、以下の基準にて判断した。
　◎ : クラック発生率２０％未満
　○ : クラック発生率２０～４０％
　△ : クラック発生率４０～６０％
　× : クラック発生率６０％以上
　〈ＨＡＳＴ特性〉
　クシ型電極（ライン／スペース＝５０ミクロン／５０ミクロン）が形成されたBT基板に、ソルダーレジスト硬化塗膜を形成し、評価基板を作成した。この評価基板を、１３０ ℃、湿度８５％の雰囲気下の高温高湿槽に入れ、電圧５Ｖを荷電し、１６８時間、槽内ＨＡＳＴ試験を行った。１６８時間経過時の槽内絶縁抵抗値を下記の判断基準に従い評価した。評価結果を表２に示す。
　○ ： １０8 Ω以上
　△ ： １０6～１０ 8Ω
　× ： １０6Ω以下 (Characteristic test)
Each composition of Examples and Comparative Examples was applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and a 1% by weight sodium carbonate aqueous solution at 30 ° C. is developed for 90 seconds under a spray pressure of 0.2 MPa / cm 2. A resist pattern was obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and the penetration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.
Examples 15 to 27 and Comparative Examples 3 and 4 were evaluated in the same manner except that a 10% by mass HCl aqueous solution was used.
○: No change is observed Δ: Only a slight change ×: The coating film is swollen or swelled off <Alkali resistance>
The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.
Examples 15 to 27 and Comparative Examples 3 and 4 were evaluated in the same manner except that a 10% by mass NaOH aqueous solution was used.
○: No change is observed Δ: Only a slight change ×: The coating film is swollen or swelled off <Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.
<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5μm and gold 0.05μm, and tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.
<PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation, 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film was determined. evaluated. Judgment criteria are as follows.
○: No swelling, peeling, discoloration, or elution △: Some swelling, peeling, discoloration, or elution ×: Many swelling, peeling, discoloration, or elution <Resistance to thermal shock>
The evaluation board | substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced. The obtained evaluation substrate was subjected to a 1000 cycle resistance test with a thermal shock tester (manufactured by ETAC Co., Ltd.) at a cycle of −55 ° C./30 minutes to 150 ° C./30 minutes. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.
○: Crack generation rate of less than 30% △: Crack generation rate of 30-50%
×: Crack occurrence rate of 50% or more Note that Examples 15 to 27 and Comparative Examples 3 and 4 were judged according to the following criteria.
◎: Crack generation rate less than 20% ○: Crack generation rate 20 to 40%
Δ: Crack generation rate 40-60%
×: Crack generation rate of 60% or more <HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-type electrodes (line / space = 50 microns / 50 microns) were formed, and an evaluation substrate was prepared. This evaluation substrate was placed in a high-temperature and high-humidity tank under an atmosphere of 130 ° C. and humidity 85%, charged with a voltage of 5 V, and subjected to an in-chamber HAST test for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria. The evaluation results are shown in Table 2.
○: 10 8 Ω or more △: 10 6 to 10 8 Ω
×: 10 6 Ω or less
[規則26に基づく補充 12.05.2010]　
Figure WO-DOC-TABLE-3
 [Supplement under rule 26 12.05.2010]
Figure WO-DOC-TABLE-3
　表３に示す結果から明らかなように、本実施形態の硬化性樹脂組成物は、ＩＣパッケージ用ソルダーレジストとして用いる際に必要とされる、ＰＣＴ耐性、冷熱衝撃耐性、電気特性に優れ、さらにはんだ耐熱性や無電解金めっき耐性においても充分な特性を有していることが分かった。一方、比較例１と２は、耐酸性や耐アルカリ性など良好な特性を得られるものもあったが、ＰＣＴ耐性や冷熱衝撃耐性、電気特性の充分な特性を得られなかった。 As is apparent from the results shown in Table 3, the curable resin composition of the present embodiment is excellent in PCT resistance, thermal shock resistance, electrical characteristics, and solder required for use as a solder resist for IC packages. It was found that it has sufficient characteristics in heat resistance and electroless gold plating resistance. On the other hand, Comparative Examples 1 and 2 had good characteristics such as acid resistance and alkali resistance, but sufficient characteristics such as PCT resistance, thermal shock resistance, and electrical characteristics could not be obtained.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４に示す結果から明らかなように、比較例３と４は、ＰＣＴ耐性、冷熱衝撃耐性、電気特性の面で良好な結果が得られなかった。しかし、実施例１５～２７では種々のフェノール骨格から誘導されたカルボキシル基含有感光性樹脂を使用することにより、優れたＰＣＴ耐性、冷熱衝撃耐性、電気特性を有することが明らかとなった。 As is clear from the results shown in Table 4, Comparative Examples 3 and 4 did not give good results in terms of PCT resistance, thermal shock resistance, and electrical characteristics. However, in Examples 15 to 27, it was revealed that the use of a carboxyl group-containing photosensitive resin derived from various phenol skeletons has excellent PCT resistance, thermal shock resistance, and electrical characteristics.
〈ドライフィルムでの評価〉
　実施例１～７、実施例１４と、実施例１５、実施例１８～２４、実施例２７及び比較例１～４の硬化性樹脂組成物をメチルエチルケトンにて希釈し、ＰＥＴフィルム上に塗布して８０℃で３０分乾燥し厚さ２０μｍの感光性樹脂組成物層を形成した。さらにその上にカバーフィルムを貼り合わせてドライフィルムを作製し、実施例１～７、実施例１４の組成物を用いたドライフィルムをそれぞれ実施例２８～３５とし、実施例１５、実施例１８～２４、実施例２７の組成物を用いたドライフィルムをそれぞれ実施例３６～４４とし、比較例１～４の組成物を用いたドライフィルムをそれぞれ比較例５～８とした。
　その後、カバーフィルムを剥がし、パターン形成された銅箔基板に、フィルムを熱ラミネートし、次いで、前述の組成物の塗膜特性評価に用いた基板と同様の条件で露光した。
　露光後、キャリアフィルムを剥がし、３０℃の１質量％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａ/ｃｍ2の条件で９０秒間現像を行い、レジストパターンを得た。
　この基板を、ＵＶコンベア炉にて積算露光量１０００ｍＪ／ｃｍ2の条件で紫外線照射した後、１５０℃で６０分加熱して硬化し、試験基板を作製した。得られた硬化皮膜を有する試験基板について、前述した試験方法及び評価方法にて、各特性の評価試験を行った。その結果を表５および表６に示す。 <Evaluation with dry film>
The curable resin compositions of Examples 1 to 7, Example 14, Example 15, Examples 18 to 24, Example 27 and Comparative Examples 1 to 4 were diluted with methyl ethyl ketone and applied onto a PET film. A photosensitive resin composition layer having a thickness of 20 μm was formed by drying at 80 ° C. for 30 minutes. Further, a dry film was prepared by laminating a cover film thereon, and the dry films using the compositions of Examples 1 to 7 and Example 14 were designated as Examples 28 to 35, respectively, Examples 15 and 18 to 24, dry films using the compositions of Example 27 were designated as Examples 36 to 44, respectively, and dry films using the compositions of Comparative Examples 1 to 4 were designated as Comparative Examples 5 to 8, respectively.
Then, the cover film was peeled off, the film was heat-laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the evaluation of the coating film properties of the above-mentioned composition.
After the exposure, the carrier film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was developed for 90 seconds under the condition of a spray pressure of 0.2 MPa / cm 2 to obtain a resist pattern.
This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Tables 5 and 6.
[規則26に基づく補充 12.05.2010]　
Figure WO-DOC-TABLE-5
 [Supplement under rule 26 12.05.2010]
Figure WO-DOC-TABLE-5
　表５に示す結果から明らかなように、実施例１～７と実施例１４の樹脂組成物を用いた実施例２８～３５のドライフィルムでの評価では、表３に示す結果と同様に何れも、ＰＣＴ耐性、冷熱衝撃耐性、電気特性について良好な評価結果が得られた。一方、比較例１、２の樹脂組成物を用いた比較例５、６のドライフィルムでは、耐酸性、耐アルカリ性、はんだ耐熱性については良好な結果が得られたが、十分なＰＣＴ耐性、冷熱衝撃耐性、電気特性を得ることができなかった。 As is clear from the results shown in Table 5, in the evaluations of the dry films of Examples 28 to 35 using the resin compositions of Examples 1 to 7 and Example 14, both were the same as the results shown in Table 3. Good evaluation results were obtained for PCT resistance, thermal shock resistance, and electrical characteristics. On the other hand, in the dry films of Comparative Examples 5 and 6 using the resin compositions of Comparative Examples 1 and 2, good results were obtained with respect to acid resistance, alkali resistance, and solder heat resistance, but sufficient PCT resistance, cold heat Impact resistance and electrical characteristics could not be obtained.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表６に示す結果より、表５同様、種々のフェノール骨格から誘導されたカルボキシル基含有感光性樹脂を使用したレジスト硬化物は、半導体パッケージなどの電子部品に用いられる際に要求されるＰＣＴ耐性、冷熱衝撃耐性などに優れるとともに、良好な電気特性を兼ね備えていることが分かる。 From the results shown in Table 6, as in Table 5, resist cured products using carboxyl group-containing photosensitive resins derived from various phenol skeletons are required to have PCT resistance when used for electronic components such as semiconductor packages, It can be seen that it has excellent thermal characteristics as well as excellent thermal shock resistance.
　〈難燃性の評価〉
　表７に示す種々の成分、割合（質量部）にて配合し、攪拌機にて予備混合した後、３本ロールミルで混練し、ソルダーレジスト用光硬化性樹脂組成物を調製した。調製した組成物を厚さ0.1mmFR-4材にスクリーン印刷で全面塗布し、８０℃で３０分乾燥した。この基板に高圧水銀灯を搭載した露光装置をもちいて最適露光量で全面露光し、３０℃の１質量％炭酸ナトリウム水溶液による現像をスプレー圧０．２ＭＰａ/ｃｍ2の条件にて９０秒間行った。この基板を、ＵＶコンベア炉にて積算露光量１０００ｍＪ／ｃｍ2 の条件で紫外線照射した後、１５０℃で６０分加熱して硬化した。得られた評価基板を米国のUnderwriters Laboratories Inc.（ＵＬと略す）の高分子材料の難燃性試験規格ＵＬ９４に準拠した方法、装置で難燃性を評価した。その評価結果を表８に示す。
　なお、評価基準は以下のとおりである。
○；ＵＬ９４Ｖ－０相当の難燃性
×；ＵＬ９４Ｖ－０相当でない <Evaluation of flame retardancy>
The various components and ratios (parts by mass) shown in Table 7 were blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photocurable resin composition for a solder resist. The prepared composition was applied onto the entire surface of a 0.1 mm thick FR-4 material by screen printing and dried at 80 ° C. for 30 minutes. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the entire surface was exposed at an optimum exposure amount, and development with a 1 mass% sodium carbonate aqueous solution at 30 ° C. was performed for 90 seconds under the condition of a spray pressure of 0.2 MPa / cm 2 . This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The obtained evaluation substrate was evaluated for flame retardancy by a method and apparatus conforming to the flame retardant test standard UL94 of a polymer material of United States Underwriters Laboratories Inc. (abbreviated as UL). The evaluation results are shown in Table 8.
The evaluation criteria are as follows.
○: Flame resistance equivalent to UL94V-0 ×: Not equivalent to UL94V-0
Figure JPOXMLDOC01-appb-T000007
 ＊1  イルガキュア OXE 02: チバ・ジャパン社製
＊2  ビフェニルノボラック変性型エポキシ樹脂(NC3000:日本化薬社製)
＊3  ジペンタエリスリトールペンタアクリレート(DPHA: 日本化薬（株）社製)
＊4  C.I.Pigment Blue 15:3
＊5  C.I.Pigment Yellow147
＊6  2-メルカプトベンゾチアゾール
＊7  酸化防止剤（チバ・ジャパン社製）
＊8  球状シリカ（（株）アドマテックス社製）
＊9  硫酸バリウム＃100（堺化学（株）社製）
＊10  ハイドロタルサイト化合物（協和化学工業（株）製）
Figure JPOXMLDOC01-appb-T000007
 * 1 Irgacure OXE 02: Ciba Japan * 2 Biphenyl novolak modified epoxy resin (NC3000: Nippon Kayaku)
* 3 Dipentaerythritol pentaacrylate (DPHA: Nippon Kayaku Co., Ltd.)
* 4 CIPigment Blue 15: 3
* 5 CIPigment Yellow147
* 6 2-Mercaptobenzothiazole * 7 Antioxidant (Ciba Japan)
* 8 Spherical silica (manufactured by Admatechs)
* 9 Barium sulfate # 100 (manufactured by Sakai Chemical Co., Ltd.)
* 10 Hydrotalcite compound (Kyowa Chemical Industry Co., Ltd.)
Figure JPOXMLDOC01-appb-T000008
 　
Figure JPOXMLDOC01-appb-T000008
 　
　表８に示す結果から明らかなように、本発明の硬化性樹脂組成物は、優れた難燃性も有する。


                                                                                As is clear from the results shown in Table 8, the curable resin composition of the present invention also has excellent flame retardancy.


Claims (5)

  1. 　一般式（I）から（VI）のうちの少なくとも一つの骨格を有するフェノール樹脂とアルキレンオキシド又はシクロカーボネート化合物とを反応させて得られる反応生成物に、不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に、多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂と、
    　光重合開始剤を含有することを特徴とする硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
     （一般式（III)、（IV）、（VI）のＲは水素、もしくはメチル基を表す。）
    An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a phenol resin having at least one skeleton of general formulas (I) to (VI) with an alkylene oxide or a cyclocarbonate compound, A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride;
    A curable resin composition comprising a photopolymerization initiator.
    Figure JPOXMLDOC01-appb-C000004
     (R in the general formulas (III), (IV), and (VI) represents hydrogen or a methyl group.)
  2. 　請求項１に記載の硬化性樹脂組成物を基材に塗布し、活性エネルギー線照射及び加熱もしくは活性エネルギー線照射又は加熱により硬化させて得られることを特徴とする硬化物。 A cured product obtained by applying the curable resin composition according to claim 1 to a substrate and curing the composition by irradiation with active energy rays and heating or irradiation with active energy rays or heating.
  3. 　請求項１に記載の硬化性樹脂組成物を、フィルム上に塗布し、乾燥して得られることを特徴とするドライフィルム。 A dry film obtained by applying the curable resin composition according to claim 1 onto a film and drying it.
  4. 　請求項３に記載のドライフィルムを基材に貼り付け、活性エネルギー線照射及び加熱もしくは活性エネルギー線照射又は加熱により硬化させて得られることを特徴とする硬化物。 A cured product obtained by attaching the dry film according to claim 3 to a substrate and curing it by irradiation with active energy rays and heating or irradiation with active energy rays or heating.
  5. 　請求項２または４に記載の硬化物を具備することを特徴とするプリント配線板。


                                                                                         A printed wiring board comprising the cured product according to claim 2.


PCT/JP2010/002305 2009-03-31 2010-03-30 Curable resin composition and printed wiring board WO2010113478A1 (en)

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