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WO2023218876A1 - Résine soluble dans les alcalis, composition de résine photosensible et produit durci associé - Google Patents

Résine soluble dans les alcalis, composition de résine photosensible et produit durci associé Download PDF

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Publication number
WO2023218876A1
WO2023218876A1 PCT/JP2023/015488 JP2023015488W WO2023218876A1 WO 2023218876 A1 WO2023218876 A1 WO 2023218876A1 JP 2023015488 W JP2023015488 W JP 2023015488W WO 2023218876 A1 WO2023218876 A1 WO 2023218876A1
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WIPO (PCT)
Prior art keywords
alkali
soluble resin
acid
group
epoxy
Prior art date
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Ceased
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PCT/JP2023/015488
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English (en)
Japanese (ja)
Inventor
信章 大槻
拓真 寺田
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2024520328A priority Critical patent/JPWO2023218876A1/ja
Publication of WO2023218876A1 publication Critical patent/WO2023218876A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08F290/08—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 side groups
    • C08F290/14—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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

Definitions

  • the present invention relates to an alkali-soluble resin and a photosensitive resin composition. More specifically, the present invention relates to an alkali-soluble resin, a photosensitive resin composition, and a cured product thereof, which can provide a cured product with excellent solvent resistance even under low-temperature curing conditions.
  • Alkali-soluble resins are compounds used in various fields ranging from the civil engineering and construction field to the electronic information field. Among them, alkali-soluble resins that are hardened by light or electron beam irradiation have the property that the parts irradiated with light or electron beams harden, while other parts remain soluble. It is preferably used as a material for resist compositions (also referred to as photosensitive resin compositions). Such resist compositions can be used in various applications such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, organic insulating films, and organic protective films used in liquid crystal display devices, solid-state image sensors, etc. It has been applied to optical components, electric/electronic equipment, etc., or various applications are being considered.
  • Patent Document 1 a photocurable type containing a compound having an epoxy group, a photobase generator, a curing agent having a thiol group, a monomer having an unsaturated bond, and a radical generator that generates radicals when exposed to light.
  • a resin composition has been disclosed, and a photocurable resin composition that does not have tackiness when formed into a coating film before exposure has been discovered.
  • Patent Document 2 a copolymer containing three types of (meth)acrylate repeating units categorized by the type of functional group present at the terminal and having all of alkali-soluble, photocurable, and thermosetting properties;
  • the photosensitive resin composition used is disclosed.
  • This pattern film has excellent thermosetting properties at relatively low temperatures, can also be photocured by light irradiation, has improved degree of curing, and has excellent durability and chemical resistance. is obtained.
  • the present invention was made in view of the above-mentioned current situation, and is an alkali that can provide a cured product with excellent solvent resistance even under low temperature curing conditions and can be suitably used for various uses such as color filters.
  • the present invention aims to provide a soluble resin and a photosensitive resin composition containing the resin.
  • an alkali having a specific epoxy group-containing structure, carboxyl group-containing structure, and polymerizable unsaturated bond-containing structure and having an epoxy equivalent of 50,000 g/equivalent or less Having obtained the knowledge that the above problems can be solved by using a soluble resin and further by using a photosensitive resin composition containing such a specific alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, The present invention has now been completed.
  • ⁇ 1> At least one epoxy group-containing structure selected from the structure represented by the following formula (1) and the structure represented by the following formula (2), and the structure represented by the following formulas (3) to (4') at least one carboxyl group-containing structure selected from the structure represented by the following formula (5) and at least one polymerizable unsaturated bond-containing structure selected from the structure represented by the following formula (5')
  • An alkali-soluble resin having the following structure and having an epoxy equivalent of 50,000 g/equivalent or less.
  • R 1 is the same or different represents a divalent organic group.
  • R 2 and R 3 are the same or different and are a hydrogen atom or a group represented by formula (6), and R 2 is a group represented by formula (6).
  • R 4 is the same or different and represents a trivalent organic group.
  • R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 8 and R 9 are the same or different and represent a direct bond or represents a divalent organic group.
  • R10 represents a divalent organic group.
  • the alkali-soluble resin according to ⁇ 1> which has an acid value of 30 to 200 mgKOH/g.
  • a photosensitive resin composition comprising the alkali-soluble resin described in ⁇ 1> or ⁇ 2> above, a polymerizable compound, and a photopolymerization initiator.
  • ⁇ 4> A cured product obtained by curing the alkali-soluble resin described in ⁇ 1> or ⁇ 2> above, or the photosensitive resin composition described in ⁇ 3>.
  • a member for a display device comprising the cured product according to ⁇ 4>.
  • a display device comprising the member for a display device according to ⁇ 5> above.
  • a method for producing an alkali-soluble resin comprising: The production method includes a first step in which an epoxy resin (a) having two or more epoxy groups in one molecule is reacted with a monobasic acid (b) having a primary alcoholic hydroxyl group and an unsaturated monocarboxylic acid (c).
  • a method for producing an alkali-soluble resin characterized in that the method is carried out by adjusting the method.
  • a method for producing a photosensitive resin composition comprising: The manufacturing method includes a step of manufacturing an alkali-soluble resin by the method for manufacturing an alkali-soluble resin according to ⁇ 7>; A method for producing a photosensitive resin composition, comprising the step of mixing an alkali-soluble resin having an epoxy equivalent of 50,000 g/equivalent or less, a polymerizable compound, and a photopolymerization initiator.
  • the alkali-soluble resin and photosensitive resin composition of the present invention can provide a cured product with excellent solvent resistance even under relatively low-temperature curing conditions.
  • the cured product of the present invention can be used in various applications such as various optical members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image sensors, touch panel display devices, etc., and structural members of electrical and electronic devices. It can be suitably used for.
  • Alkali-soluble resin The alkali-soluble resin of the present invention has at least one epoxy group-containing structure selected from the structure represented by the above formula (1) and the structure represented by the above formula (2), and the above formula (3). at least one carboxyl group-containing structure selected from the structures represented by (4') and at least one carboxyl group-containing structure selected from the structures represented by the above formula (5) and the above formula (5').
  • the resin has one polymerizable unsaturated bond-containing structure in the side chain of the polymer, and has an epoxy equivalent of 50,000 g/equivalent or less.
  • the alkali-soluble resin of the present invention When the alkali-soluble resin of the present invention is used as a resist material, the polymerizable unsaturated bonds react with light and the exposed area is cured, and then the epoxy group and carboxyl group react with each other through baking treatment. Then, post-curing is performed.
  • the alkali-soluble resin of the present invention has excellent alkali developability because the carboxyl group is located at a position distant from the main chain.
  • carboxyl groups located away from the main chain have good reactivity with epoxy groups, so during post-curing, the reaction with epoxy groups is good even under relatively low-temperature curing conditions (for example, below 160°C). The process progresses and a cured product with excellent solvent resistance can be obtained.
  • the alkali-soluble resin of the present invention has at least one epoxy group-containing structure selected from the structure represented by the above formula (1) and the structure represented by the above formula (2).
  • m in the above formula (2) is an integer of 1 to 10, preferably 2 to 8. More preferably, it is 3-6. The same applies to m in the above formulas (3'), (4') and (5').
  • the alkali-soluble resin of the present invention is selected from the structures represented by the above formulas (3) to (4') (that is, the above formulas (3), (3'), (4) and (4')). It has at least one carboxyl group-containing structure.
  • R 1 in formulas (3) and (3') are the same or different and represent a divalent organic group, and as a divalent organic group, the following formula (7):
  • R 11 represents a divalent hydrocarbon group which may have a substituent.
  • R 12 represents any structure of formula (8) or a direct bond.
  • the structures depicted are preferred.
  • the hydrocarbon group for R 11 is preferably a hydrocarbon group having 1 to 12 carbon atoms. More preferably, it is a hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the hydrocarbon group may have a chain structure, a cyclic structure, or a structure having both a chain part and a cyclic part.
  • the cyclic structure may be an alicyclic structure or an aromatic ring.
  • the substituent for R 11 include halogen atoms such as fluorine atom, chlorine atom, and bromine atom, and cyano group.
  • R 11 in the above formula (7) it is preferable that the end opposite to the R 12 side is a methylene group.
  • a structure in which R 2 is represented by formula (6) is preferable. That is, the terminal -R 1 -O-R 2 of the structure represented by formulas (3) and (3') is represented by the following formula (9)
  • R 11 ' represents a hydrocarbon group having 1 to 11 carbon atoms or a direct bond.
  • R 12 is the same as formula (7).
  • R 10 is the same as formula (6) ) is one of the preferred embodiments of the carboxyl group-containing structure represented by formulas (3) and (3'). This structure will be explained in "2. Method for producing alkali-soluble resin” below.
  • R 2 and R 3 in formulas (3) to (4') are the same or different and are a hydrogen atom or a group represented by the above formula (6), and at least one of R 2 is a group represented by the formula (6). is the group represented. That is, when the alkali-soluble resin of the present invention has only the structure represented by the above formula (3) or only the structure represented by (3') as the carboxyl group-containing structure, the alkali-soluble resin has the structure represented by the formula (3).
  • R 2 in the structure represented by formula (3) or the structure represented by (3') is a group represented by formula (6), and the alkali-soluble resin has a structure represented by formula (3) above and (3').
  • R 2 of either or both of the structure represented by the above formula (3) and the structure represented by (3') is a group represented by the formula (6).
  • the alkali-soluble resin has only the structure represented by the above formula (4) or only the structure represented by (4') as a carboxyl group-containing structure
  • the structure represented by the formula (4) that the alkali-soluble resin has or Either or both of the two R 2's in the structure represented by (4') are groups represented by formula (6)
  • the alkali-soluble resin has a structure represented by formula (4) above and (4 )
  • at least one of the four R2s in the structure represented by the above formula (4) and the structure represented by (4') is represented by the formula (6). This is the base.
  • the alkali-soluble resin has a structure represented by (3) and/or (3') as a carboxyl group-containing structure, and a structure represented by formula (4) and/or (4').
  • R2 present in the structure represented by formula (4) and/or is a group represented by formula (6).
  • R 3 may be a hydrogen atom or a group represented by formula (6).
  • R 4 in the above formulas (4) and (4') represents a trivalent organic group, and the trivalent organic group is represented by the following formula (10):
  • R 13 represents a trivalent hydrocarbon group which may have a substituent.
  • R 14 represents any structure of the above formula (8) or a direct bond.
  • p , q are the same or different integers of 0 to 3.
  • the hydrocarbon group for R 13 is preferably a hydrocarbon group having 1 to 10 carbon atoms. More preferred is a hydrocarbon group having 1 to 6 carbon atoms.
  • the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the hydrocarbon group may have a chain structure, a cyclic structure, or a structure having both a chain portion and a cyclic portion.
  • the cyclic structure may be an alicyclic structure or an aromatic ring. Examples of the substituent in the hydrocarbon group of R 13 include those similar to the substituents in the hydrocarbon group of R 11 described above.
  • R 15 represents a hydrogen atom or a monovalent hydrocarbon group that may have a substituent.
  • R 14 , p, and q are the same as in formula (10).
  • Examples include groups represented by:
  • the monovalent hydrocarbon group for R 15 is preferably a hydrocarbon group having 1 to 7 carbon atoms. More preferred is a hydrocarbon group having 1 to 3 carbon atoms.
  • the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the hydrocarbon group may have a chain structure, a cyclic structure, or a structure having both a chain portion and a cyclic portion.
  • the cyclic structure may be an alicyclic structure or an aromatic ring.
  • Examples of the substituent for the hydrocarbon group of R 15 include the same substituents as for the hydrocarbon group of R 11 described above.
  • the carboxyl group-containing structure represented by the above formula (4) or formula (4') is a structure in which R 4 is represented by the above formula (10), and either p or q is 1 or more.
  • a structure in which R 2 is represented by formula (6) is preferable. That is, the terminal structure after R4 of the structure represented by formula (4) or formula (4') is the following formula (12):
  • R 2 is the same as in formulas (3) to (4').
  • R 10 is the same as in formula (6).
  • R 13 and R 14 are as in formula (10) p is a number of 1 or more, and q is a number of 0 or more. This is one of the embodiments. This structure will be explained in "2. Method for producing alkali-soluble resin” below.
  • the alkali-soluble resin of the present invention further has at least one polymerizable unsaturated bond-containing structure selected from the structure represented by the above formula (5) and the structure represented by the formula (5').
  • R 3 in formula (5) and formula (5') may be a hydrogen atom or a group represented by formula (6).
  • R 5 , R 6 and R 7 in formula (5) and formula (5′) are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • the above hydrocarbon group having 1 to 6 carbon atoms includes a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms, preferably a chain hydrocarbon group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. -6 alkyl groups are more preferred.
  • R 5 , R 6 and R 7 are preferably the same or different and are hydrogen atoms or methyl groups, and R 5 and R 6 are hydrogen atoms. It is more preferable that R 7 is a hydrogen atom or a methyl group.
  • R 8 and R 9 in formula (5) and formula (5') are the same or different and represent a direct bond or a divalent organic group. Examples of divalent organic groups include hydrocarbon groups having 1 to 12 carbon atoms, -O-, -CO-, -NH-, -S-, -SO-, -SO 2 -, etc., and substituents bonded to these. The following can be mentioned. Examples of the substituent include the same substituents that the hydrocarbon group of R 11 above may have.
  • R 10 in the above formula (6) is a divalent organic group.
  • Examples of the divalent organic group include the same divalent organic groups as R 8 and R 9 in formula (5).
  • the alkali-soluble resin of the present invention may have the above-mentioned epoxy group-containing structure, carboxyl group-containing structure, and polymerizable unsaturated bond-containing structure at the end of the main chain structure of the resin (polymer) structure, although it may be included in the side chain, it is preferably included in the side chain.
  • the structure of the main chain of the polymer is not particularly limited, but the alkali-soluble resin of the present invention is preferably obtained by modifying an epoxy resin.
  • the alkali-soluble resin of the present invention has a structure in which the epoxy group-containing structure, carboxyl group-containing structure, and polymerizable unsaturated bond-containing structure are bonded as side chains to the main chain structure derived from the epoxy resin. is preferred.
  • the epoxy resin forming the main chain will be described later.
  • the alkali-soluble resin of the present invention has an epoxy equivalent of 50,000 g/equivalent or less.
  • the epoxy equivalent of the alkali-soluble resin is preferably 30,000 g/equivalent or less. More preferably, it is 10000 g/equivalent or less, and still more preferably 5000 g/equivalent or less.
  • the amount is more preferably 3000 g/equivalent or less, particularly preferably 2000 g/equivalent or less, and most preferably 1500 g/equivalent or less.
  • the alkali-soluble resin preferably has an epoxy equivalent of 400 g/equivalent or more, more preferably 550 g/equivalent or more, and even more preferably 700 g/equivalent or more. That is, the epoxy equivalent of the alkali-soluble resin is preferably 400 to 50,000 g/equivalent, more preferably 550 to 30,000 g/equivalent, still more preferably 700 to 10,000 g/equivalent, even more preferably 700 to 5,000 g/equivalent. equivalent, more preferably 700 to 3000 g/equivalent, particularly preferably 700 to 2000 g/equivalent, most preferably 700 to 1500 g/equivalent.
  • the epoxy equivalent of the alkali-soluble resin can be determined by dividing the resin solid content by the number of moles of epoxy groups contained in the resin. Moreover, the above-mentioned epoxy equivalent can also be determined by a method based on JIS K7236:2001.
  • the alkali-soluble resin of the present invention preferably has an acid value of 30 to 200 mgKOH/g.
  • the acid value is 30 mgKOH/g or more, the alkali-soluble resin has excellent curability during post-curing and the alkali resistance and solvent resistance of the cured product.
  • the acid value is preferably 200 mgKOH/g or less.
  • the acid value of the alkali-soluble resin is more preferably 35 to 160 mgKOH/g, and still more preferably 40 to 140 mgKOH/g.
  • the acid value of the alkali-soluble resin can be measured by the method described in Examples below.
  • the alkali-soluble resin of the present invention preferably has a double bond equivalent (weight per chemical equivalent of a radically polymerizable double bond) of 100 to 3000 g/equivalent.
  • the double bond equivalent is 3000 g/equivalent or less, the alkali-soluble resin has better developability during exposure.
  • the double bond equivalent is preferably 100 g/equivalent or more.
  • the double bond equivalent of the alkali-soluble resin is more preferably 250 to 2000 g/equivalent, and even more preferably 400 to 1000 g/equivalent.
  • the double bond equivalent of the alkali-soluble resin can be measured by the method described in the Examples below. Alternatively, it may be calculated by measuring the number of ethylenic double bonds contained per gram of alkali-soluble resin in accordance with the iodine number test method described in JIS K 0070:1992.
  • the alkali-soluble resin of the present invention may have structures other than those represented by the above formulas (1) to (5') in the side chain of the polymer, but the proportion of the other structures is as follows: It is preferably 60 mol% or less based on the total number of moles of the structures represented by formulas (1) to (5') above, 100 mol%. More preferably, it is 40 mol% or less.
  • the alkali-soluble resin of the present invention has a carboxyl group, an epoxy group, and a radically polymerizable double bond, and since crosslinking reactions and polymerization reactions involving these are possible, it can be used alone as an alkali-soluble photosensitive resin. can do. In particular, it can be suitably used as a negative-type alkali-soluble photosensitive resin.
  • the method for producing the alkali-soluble resin is not particularly limited as long as an alkali-soluble resin having the above-mentioned structure can be obtained, but a method of producing the alkali-soluble resin by modifying the epoxy resin is preferred.
  • the alkali-soluble resin of the present invention can be produced by adjusting the amounts of the monobasic acid (b) and unsaturated monocarboxylic acid (c) used.
  • a monobasic acid (b) having a primary alcoholic hydroxyl group it is preferable to use as the monobasic acid (b) having a hydroxyl group.
  • the reaction product obtained is a polybasic acid anhydride compared to the secondary alcoholic hydroxyl group normally produced by the reaction between an epoxy group and a carboxylic acid. It has a primary alcohol with high reactivity. For this reason, the subsequent reaction with the polybasic acid anhydride progresses well, and acid groups can be introduced away from the main chain, making the resulting alkali-soluble resin superior in alkali solubility and curability. can do.
  • a method for producing such an alkali-soluble resin that is, a method for producing an alkali-soluble resin, in which an epoxy resin (a) having two or more epoxy groups in one molecule is mixed with a primary alcohol.
  • the monobasic acid (b) having a primary alcoholic hydroxyl group and the unsaturated monocarboxylic acid is Another aspect of the present invention.
  • Another aspect of the present invention is a method for producing an alkali-soluble resin, which is carried out by adjusting the amount of c) used.
  • the starting material epoxy resin (a) having two or more epoxy groups in one molecule is not particularly limited; Any known epoxy resin can be used as long as it has a bisphenol type epoxy resin; biphenyl type epoxy resin; alicyclic epoxy resin; polyfunctional glycidyl amine resin such as tetraglycidylamino diphenylmethane; tetraphenyl glycidyl ether ethane.
  • Polyfunctional glycidyl ether resins such as; phenol novolac type epoxy resins and cresol novolac type epoxy resins; condensation of phenolic compounds such as phenol, o-cresol, m-cresol, naphthol, and aromatic aldehydes having phenolic hydroxyl groups.
  • a reaction product between a polyphenol compound obtained by the reaction and epichlorohydrin a reaction product between a polyphenol compound obtained by an addition reaction between a phenol compound and a diolefin compound such as divinylbenzene or dicyclopentadiene, and epichlorohydrin; 4-vinylcyclohexene- Examples include ring-opening polymers of 1-oxide epoxidized with peracids; epoxy resins having a heterocycle such as triglycidyl isocyanurate; and the like.
  • those obtained by bonding two or more molecules of these epoxy resins with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol to extend the chain can also be used.
  • a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol to extend the chain
  • it may be a homopolymer or copolymer of a monomer having an epoxy group such as glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate.
  • novolac type epoxy resin is used as a raw material. It is preferable.
  • the above-mentioned starting material epoxy resin (a) having two or more epoxy groups in one molecule should have an epoxy equivalent of 500 g in order to make the resulting alkali-soluble resin more excellent in developability and low-temperature curability. / equivalent or less is preferable. More preferably, the epoxy equivalent is 400 g/equivalent or less, and even more preferably, the epoxy equivalent is 300 g/equivalent or less.
  • the monobasic acid (b) having a hydroxyl group is not particularly limited as long as it has a hydroxyl group and an acid group, but those having 2 to 12 carbon atoms are preferred. More preferably, it has 3 to 10 carbon atoms, and still more preferably 4 to 8 carbon atoms.
  • Examples of the acid group of the monobasic acid (b) having a hydroxyl group include a carboxyl group, a phenolic hydroxyl group, a phosphoric acid group, a sulfonic acid group, etc.
  • a carboxyl group or a phenolic hydroxyl group is preferable, and a carboxyl group is more preferable. preferable.
  • monobasic acids (b) having a hydroxyl group monocarboxylic acids having a hydroxyl group such as glycolic acid, hydroacrylic acid, glyceric acid, dimethylolpropionic acid, dimethylolbutanoic acid, lactic acid, and tartaric acid. can be mentioned.
  • those having a primary alcoholic hydroxyl group include monocarboxylic acids having one or more primary alcoholic hydroxyl groups such as glycolic acid, hydroacrylic acid, glyceric acid, dimethylolpropionic acid, and dimethylolbutanoic acid.
  • monocarboxylic acids having one or more primary alcoholic hydroxyl groups such as glycolic acid, hydroacrylic acid, glyceric acid, dimethylolpropionic acid, and dimethylolbutanoic acid.
  • glycolic acid, dimethylolbutanoic acid, and dimethylolpropionic acid are preferred. These can be used alone or in combination of two or more.
  • the unsaturated monocarboxylic acid (c) is not particularly limited as long as it has an unsaturated bond and a carboxyl group, but those having 3 to 20 carbon atoms are preferred. More preferably, it has 3 to 10 carbon atoms, and still more preferably 3 to 4 carbon atoms.
  • Examples of the unsaturated monocarboxylic acid (c) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -acryloxypropionic acid, and hydroxyalkyl having one hydroxyl group and one (meth)acryloyl group.
  • a reaction product of a (meth)acrylate and a dibasic acid anhydride, a reaction product of a polyfunctional (meth)acrylate having one hydroxyl group and two or more (meth)acryloyl groups and a dibasic acid anhydride, etc. Can be mentioned. Among these, preferred are those having a (meth)acryloyl group, such as acrylic acid and methacrylic acid.
  • Methacrylic acid is particularly preferred from the viewpoint of producing a cured product of the resulting alkali-soluble resin with particularly excellent solvent resistance. These can be used alone or in combination of two or more.
  • an epoxy resin (a) having two or more epoxy groups in one molecule is reacted with a monobasic acid (b) having a hydroxyl group and an unsaturated monocarboxylic acid (c).
  • the epoxy resin (a) and the unsaturated monocarboxylic acid (c) may be reacted, and then the monobasic acid (b) having a hydroxyl group may be reacted with the epoxy resin (a).
  • the monocarboxylic acid (c) and the monobasic acid (b) having a hydroxyl group may be reacted all at once, or the epoxy resin (a) and the monobasic acid (b) having a hydroxyl group may be reacted, and then the unsaturated monocarboxylic acid (b) is reacted with the monobasic acid (b) having a hydroxyl group. It may be reacted with acid (c).
  • the total amount of the monobasic acid (b) having a hydroxyl group and the unsaturated monocarboxylic acid (c) used is 0.2 to 1 chemical equivalent (mole equivalent) of the epoxy group in the epoxy resin.
  • the amount is preferably 0.79 mol. When used in such a ratio, it becomes easier to improve the curability of the alkali-soluble resin finally obtained and the physical properties of the cured product.
  • the amount is preferably 0.3 to 0.76 mol, more preferably 0.4 to 0.73 mol.
  • the amount of the monobasic acid (b) having a hydroxyl group to be used is 0.01 to 0.5 mol, assuming that the total amount of the monobasic acid (b) having a hydroxyl group and the unsaturated monocarboxylic acid (c) is 1 mol. It is preferable that By using it in such a ratio, it is possible to more fully exhibit the effect of using the monobasic acid (b) having a hydroxyl group, while also ensuring a sufficient amount of polymerizable unsaturated double bonds to be introduced. This makes it possible to make the alkali-soluble resin finally obtained more excellent in curability and physical properties of the cured product.
  • the reaction of the monobasic acid (b) having a hydroxyl group and the unsaturated monocarboxylic acid (c) with respect to the epoxy resin (a) is carried out first.
  • the reaction may be carried out separately or at the same time.
  • These reactions are carried out using polymerization inhibitors such as hydroquinone and oxygen, and tertiary amines, trimethylphosphine, tributylphosphine, triphenylphosphine, etc., in the presence or absence of diluents such as polymerizable compounds and solvents, which will be described later.
  • reaction catalyst such as tertiary phosphine, lithium chloride, quaternary ammonium salt, or quaternary phosphonium salt.
  • reaction catalyst tertiary phosphine is preferred from the viewpoint of reaction efficiency, stability during reaction, and storage stability of the alkali-soluble resin, and triphenylphosphine is particularly preferred.
  • the amount of the reaction catalyst is not particularly limited, but it is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the epoxy resin (a) having two or more epoxy groups in one molecule. More preferably, it is 0.1 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass.
  • a polymerization inhibitor may be used.
  • the polymerization inhibitor is not particularly limited, and known ones can be used, such as benzoquinone, hydroquinones (e.g., hydroquinone, hydroquinone monomethyl ether, p-tert-butylhydroquinone, p-benzoquinone, etc.), phenol, etc.
  • catechols e.g., p-tert-butylcatechol, etc.
  • amines e.g., N,N-diethylhydroxylamine, etc.
  • 1,1-diphenyl-2-picrylhydrazyl tri-p-nitrophenyl Methyl, phenothiazine, piperidine 1-oxyls (eg, 2,2,6,6-tetramethylpiperidine 1-oxyl, etc.), oxygen, and the like can be used.
  • the amount of the polymerization inhibitor used is 0.001 to 1% by mass based on 100% by mass of the epoxy resin (a) having two or more epoxy groups in one molecule. It is preferable that it is mass %. More preferably, it is 0.01 to 0.5% by mass.
  • the reaction temperature in the first step is not particularly limited as long as the reaction proceeds, but is preferably 80 to 140°C. By carrying out the reaction at such a temperature, the reaction can proceed efficiently.
  • the reaction temperature is more preferably 85 to 135°C, even more preferably 90 to 130°C.
  • the reaction product obtained by the reaction in the first step may be referred to as a "modified epoxy resin intermediate."
  • polybasic acid anhydride (d) is present in the modified epoxy resin intermediate by reacting the polybasic acid anhydride (d) with the modified epoxy resin intermediate.
  • the alkali-soluble resin of the present invention into which a carboxyl group has been introduced can be obtained by reacting with the hydroxyl group. Since the resulting alkali-soluble resin can be developed with alkali, it can be used as an alkali-developable curable resin for image formation and the like.
  • the modified epoxy resin intermediate contains a monobasic acid having a primary alcoholic hydroxyl group.
  • the epoxy group is opened by reacting the primary hydroxyl group derived from the acid (b), the monobasic acid (b) having a primary alcoholic hydroxyl group, and the unsaturated monocarboxylic acid (c) with the epoxy group in the epoxy resin.
  • a hydroxyl group formed by a ring is present.
  • the polybasic acid anhydride (d) can react with any hydroxyl group, but the monobasic acid (b) having a primary alcoholic hydroxyl group is used as the monobasic acid (b) having a hydroxyl group.
  • the primary hydroxyl group derived from the monobasic acid (b) having a primary alcoholic hydroxyl group has less steric hindrance than the hydroxyl group generated by ring opening of the epoxy group. It is thought that the polybasic acid anhydride (d) reacts preferentially with the primary hydroxyl group derived from the monobasic acid (b) having a primary alcoholic hydroxyl group.
  • the terminal -R 1 -O-R 2 has a structure represented by the above formula (9), and in the formulas (4) and (4'), R A structure in which the terminal structure after 4 is a structure represented by the above formula (12) is an example of a structure obtained by such a reaction.
  • the alkali-soluble resin obtained the double bond moiety introduced by the reaction with the remaining epoxy group or unsaturated monocarboxylic acid (c) and the polybasic acid anhydride (d) are removed.
  • the alkali-soluble resin has better curability and alkali developability because the carboxyl groups are present at a sufficient distance from each other and the functions of each functional group are more likely to be effectively exhibited.
  • the polybasic acid anhydride (d) is not particularly limited, but those having 3 to 30 carbon atoms are preferred. More preferably, it has 4 to 20 carbon atoms, even more preferably 4 to 10 carbon atoms.
  • polybasic acid anhydride (d) examples include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Dibasic acid anhydrides such as 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid; biphenyltetracarboxylic dianhydride, diphenyl ethertetracarboxylic dianhydride , butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and other ali
  • polybasic acid anhydrides can be used. Among these, it is preferable to use dibasic acid anhydrides.
  • alkali-soluble resins such as phthalic anhydride, which have a cyclic structure in their structure, may be used.
  • the polybasic acid anhydride (d) is added from 0.1 mol to 1.1 mol to 1 chemical equivalent of hydroxyl group in the modified epoxy resin intermediate obtained by the reaction in the first step. It is preferable to react at a ratio of .
  • the temperature of the reaction between the modified epoxy resin intermediate and the polybasic acid anhydride (d) in the second step is not particularly limited as long as the reaction proceeds, but is preferably 45 to 75°C. By performing the reaction at such a temperature, the reaction can proceed efficiently and while suppressing the formation of high molecular weight products and gelation due to the reaction between the epoxy group and the introduced carboxyl group.
  • the reaction temperature is more preferably 50 to 70°C, even more preferably 55 to 65°C.
  • the reaction between the modified epoxy resin intermediate and the polybasic acid anhydride (d) in the second step is carried out in the presence or absence of a diluent such as a polymerizable compound or a solvent, which will be described later, to inhibit the polymerization of hydroquinone, oxygen, etc. It is preferable to carry out the reaction in the presence of an agent. Further, at this time, if necessary, the reaction catalyst used in obtaining the modified epoxy resin intermediate may be added, and here too, tertiary phosphine is preferred, and triphenylphosphine is particularly preferred. Note that the reaction between the modified epoxy resin intermediate and the polybasic acid anhydride (d) is carried out by adding the polybasic acid anhydride (d) to the reaction solution following the reaction for producing the modified epoxy resin intermediate. is simple.
  • a tertiary amine may be added to the reaction between the modified epoxy resin intermediate and the polybasic acid anhydride (d) in the second step.
  • a tertiary amine By adding a tertiary amine, the reaction efficiency is improved and the second step can be performed in a shorter time.
  • the tertiary amine one or more of trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, etc. can be used.
  • the amount of the tertiary amine used is 0.05 to 5 parts by mass per 100 parts by mass of the epoxy resin (a) having two or more epoxy groups in one molecule. Preferably. More preferably, it is 0.1 to 3 parts by weight, and even more preferably 0.15 to 1 part by weight.
  • the method for producing an alkali-soluble resin may include other steps as long as it includes the first step and second step.
  • Other steps include a step of linking molecules.
  • the alkali-soluble resin of the present invention can be used alone as a resist material, but the resin composition preferably contains at least an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. Then, a coating film having a crosslinked structure is obtained through heat and photoreaction.
  • a photosensitive resin composition containing at least the alkali-soluble resin, polymerizable compound, and photopolymerization initiator of the present invention is also one of the present invention.
  • the alkali-soluble resin of the present invention is also referred to as alkali-soluble resin (A) in the photosensitive resin composition.
  • the content of the alkali-soluble resin (A) is not particularly limited, and may be appropriately set depending on the use and the combination of other components. It is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 80% by mass or less, based on 100% by mass of the total solid content of the product. It is preferably 75% by mass or less, more preferably 70% by mass or less. That is, the content of the alkali-soluble resin (A) is preferably 5 to 80% by mass, and preferably 10 to 75% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. The content is more preferably 15 to 70% by mass.
  • total solid content refers to the total amount of components forming the cured product, that is, the total amount of components (solid content, nonvolatile content) excluding solvents etc. that volatilize during formation of the cured product.
  • total solid of the alkali-soluble resin, polymerizable compound, photopolymerization initiator, and other cured product forming components for example, coloring material, dispersant, etc.
  • total solid of the alkali-soluble resin, polymerizable compound, photopolymerization initiator, and other cured product forming components for example, coloring material, dispersant, etc.
  • the polymerizable compound contained in the photosensitive resin composition of the present invention is a polymerizable unsaturated bond that can be polymerized by free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), irradiation with active energy rays such as electron beams, etc. (also referred to as a polymerizable unsaturated group), examples of which include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.
  • electromagnetic waves e.g., infrared rays, ultraviolet rays, X-rays, etc.
  • active energy rays such as electron beams, etc.
  • Examples of the above-mentioned monofunctional compounds include N-substituted maleimide monomers; (meth)acrylic esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated groups and carboxyl Unsaturated monocarboxylic acids with chain extension between groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc. can be mentioned. Furthermore, monomers having an active methylene group or an active methine group can also be used.
  • polyfunctional compound examples include the following compounds. Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol Bifunctional (meth)acrylate compounds such as di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate; Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,
  • Ethylene glycol divinyl ether diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide trimethylolpropane trivinyl ether, ethylene oxide ditrimethylolpropane tetravinyl ether, ethylene oxide pentaerythritol tetravinyl
  • Ethylene glycol diallyl ether diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide added trimethylolpropane triallyl ether, ethylene oxide added ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol te
  • Polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymerizable compounds may be used alone or in combination of two or more.
  • polyfunctional polymerizable compounds are preferred as the polymerizable compound contained in the photosensitive resin composition of the present invention, from the viewpoint of further enhancing the curability of the photosensitive resin composition.
  • the functional number (number of functional groups) of the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more. Further, the functional number is preferably 10 or less, more preferably 8 or less. From the viewpoint of reactivity, economy, availability, etc., the polyfunctional polymerizable compound is preferably a polyfunctional (meth)acrylate compound, a polyfunctional urethane (meth)acrylate compound, or a (meth)acryloyl group-containing isocyanurate compound.
  • Examples include compounds having a (meth)acryloyl group such as, and more preferably polyfunctional (meth)acrylate compounds.
  • a compound having a (meth)acryloyl group By including a compound having a (meth)acryloyl group, the photosensitive resin composition becomes more excellent in photosensitivity and curability, and a cured product with even higher hardness and higher transparency can be obtained.
  • the polyfunctional polymerizable compound it is more preferable to use a trifunctional or more polyfunctional (meth)acrylate compound.
  • the above-mentioned polymerizable compounds include those with various structures, and their molecular weights are not particularly limited, but from the viewpoint of handling, the polymerizable compounds contained in the photosensitive resin composition of the present invention, for example, have a molecular weight of 2000 or less. Preferably.
  • a polymer having a vinyl ether group in its side chain improves the curability of the resin composition, but may reduce storage stability. It is preferable that the polymerizable compound does not contain a polymer having a vinyl ether group in its side chain.
  • the content of the polymerizable compound is not particularly limited and may be set as appropriate as long as the effects of the present invention are exhibited.
  • viscosity it is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition.
  • the photopolymerization initiator contained in the photosensitive resin composition of the present invention is preferably a radically polymerizable photopolymerization initiator.
  • a radically polymerizable photopolymerization initiator is one that generates polymerization initiation radicals by irradiation with active energy rays such as electromagnetic waves and electron beams.
  • the photopolymerization initiator examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF), 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholinophenyl) Aminoketone compounds such as phosphorus-4-yl-phenyl)-butan-1-one ("IRGACURE379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE651", Benzyl ketal compounds such as phenylglyoxylic acid methyl ester (“DAROCUR MBF”, manufactured by BASF); 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2- Hydroxy-2
  • the content of the photopolymerization initiator is not particularly limited and may be set appropriately as long as the effects of the present invention are exhibited.
  • the total solid content of the photosensitive resin composition of the present invention is 100 It is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass.
  • the photosensitive resin composition (also simply referred to as a resin composition) of the present invention has an epoxy group-containing structure, a carboxyl group-containing structure, and a polymerizable unsaturated bond-containing structure, and has an epoxy equivalent of 50,000 g/equivalent or less.
  • a resin composition has an epoxy equivalent of 50,000 g/equivalent or less.
  • the photosensitive resin composition of the present invention further contains a photoacid generator.
  • a photoacid generator By further containing a photoacid generator, the curability of the photosensitive resin composition can be further improved.
  • Photoacid generators are compounds that generate acids when exposed to active energy rays such as radiation, and include strong acids such as toluenesulfonic acid or boron tetrafluoride, sulfonium salts, ammonium salts, phosphonium salts, and iodonium salts.
  • Onium salts such as salts or selenium salts; iron-alene complexes; silanol-metal chelate complexes; sulfones such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoinsulfonates
  • sulfones such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoinsulfonates
  • acids include acid derivatives; organic halogen compounds; and the like.
  • the content of the photoacid generator is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. It is preferably 1 to 8% by mass, and more preferably 1 to 8% by mass.
  • the photosensitive resin composition of the present invention preferably contains a solvent.
  • a solvent By including a solvent, it becomes possible to apply the photosensitive resin composition onto a base material to form a film.
  • the solvent is not particularly limited, and includes hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; cellosolve acetate, carbitol acetate, (di)propylene glycol monomethyl Esters such as ether acetate, (di)methyl glutarate, (di)methyl succinate, (di)methyl adipate; Ketones such as methyl isobutyl ketone and methyl ethyl ketone; Ethers such as (di)ethylene glycol dimethyl ether, etc. Can be mentioned.
  • the content of the above-mentioned solvent is not particularly limited, and is preferably set appropriately depending on the usage form (for example, application, etc.) of the photosensitive resin composition.
  • the total solid content in 100% by mass of the photosensitive resin composition is more preferably 5 to 70% by mass, particularly preferably 10 to 50% by mass.
  • the photosensitive resin composition of the present invention may further contain, if necessary, a phosphoric acid derivative, a coloring material, a photoacid generator, a photobase generator, a polyfunctional thiol compound, a dispersant, talc, clay, barium sulfate, silica, etc.
  • a phosphoric acid derivative a coloring material
  • a photoacid generator a photobase generator
  • a polyfunctional thiol compound a dispersant
  • talc clay
  • barium sulfate silica
  • additives may also be added.
  • various reinforcing fibers can be used as reinforcing fibers to produce a fiber-reinforced composite material.
  • the content of the above-mentioned known additive in the photosensitive resin composition of the present invention is preferably 70% by mass or less based on 100% by mass of the photosensitive resin composition. More preferably, it is 60% by mass or less, and still more preferably 50% by mass or less.
  • the lower limit can be set depending on the application, but is 0% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more. That is, the content of the above additive is preferably 0 to 70% by mass, more preferably 0.1 to 60% by mass, and even more preferably 1 to 60% by mass, based on 100% by mass of the photosensitive resin composition. It is 50% by mass.
  • the method for preparing the photosensitive resin composition of the present invention is not particularly limited, and any known method may be used. For example, there is a method of mixing and dispersing the above-mentioned components using various mixers and dispersers. Further, the method for preparing the photosensitive resin composition of the present invention may include steps other than the step of mixing and dispersing each component. Other steps include, for example, a coloring material dispersion treatment step when the photosensitive resin composition contains a coloring material.
  • the film thickness is preferably 0.1 ⁇ m or more. When the film thickness is 0.1 ⁇ m or more, even more excellent solvent resistance can be exhibited.
  • the film thickness is more preferably 0.5 ⁇ m or more, and even more preferably 1 ⁇ m or more.
  • the upper limit of the film thickness is not particularly limited and may be set appropriately depending on the purpose and use of the cured film, but for example, it is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and 10 ⁇ m or less. It is even more preferable that there be. That is, the film thickness is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 15 ⁇ m, and even more preferably 1 to 10 ⁇ m.
  • the thickness of the cured film can be measured using a commercially available film thickness measuring device.
  • the method for obtaining the cured product is not particularly limited, and any known method may be used.
  • the above-mentioned alkali-soluble resin (solution) or photosensitive resin composition is applied or molded onto a base material and cured by drying, heating, irradiation with energy rays such as ultraviolet rays, or a combination thereof.
  • a method for obtaining a cured product can be mentioned.
  • the method for producing a cured product includes a step of coating the photosensitive resin composition on a substrate to form a coating film, a step of irradiating the formed coating film with light, and a step of exposing the irradiated coating film to light.
  • a method including a step of heating at 160° C. or lower is preferred.
  • the base material include those similar to the color filter substrate described below.
  • the method of coating the photosensitive resin composition on a substrate to form a coating film is not particularly limited, and can be performed by known methods such as spin coating, slit coating, roll coating, and cast coating.
  • the above-mentioned drying can be performed by a known method, and specifically, it can be performed by a method similar to the drying method described in "Arrangement step" of "Color filter manufacturing method” described below.
  • the method of irradiating the formed coating film with light is not particularly limited and can be carried out by any known method. Specifically, the method described in "Light irradiation step" in “Production method of color filter” described below This can be done in a similar way.
  • the irradiation may be performed through a photomask.
  • the photomask it is preferable to use a mask in which a light-shielding portion is formed according to the intended pattern.
  • light irradiation is performed through a photomask, it is preferable to perform a development step after that. By performing the development process, a desired pattern can be formed in the coating film.
  • the developing method is not particularly limited and can be carried out by any known method. Specifically, it can be carried out by the same method as described in "Developing step” in "Color filter manufacturing method” described below. can.
  • the above manufacturing method also includes a step of heating the light-irradiated coating film at 160° C. or lower. Since the above-mentioned manufacturing method uses the above-described photosensitive resin composition, the heating step (post-curing step) after irradiation with light can be performed under relatively low-temperature conditions such as 160° C. or lower.
  • the heating temperature is preferably 155°C or lower, more preferably 150°C or lower.
  • the lower limit of the heating temperature is preferably 70° C. or higher, more preferably 90° C. or higher in terms of maintaining curability. That is, the heating temperature is preferably 70 to 160°C, more preferably 90 to 155°C, even more preferably 90 to 150°C.
  • the above-mentioned heating method other than temperature is not particularly limited and can be carried out by any known method, for example, by the same method as described in "Heating step” of "Color filter manufacturing method” described below. I can do it.
  • the alkali-soluble resin of the present invention and the photosensitive resin composition containing the same have excellent alkali developability. Furthermore, even under low-temperature curing conditions of 160° C. or lower, for example about 90° C., the curing reaction can proceed sufficiently and a cured product with excellent solvent resistance can be obtained. Therefore, it can be suitably used in applications that require sufficient curing under low-temperature conditions and applications that require solvent resistance.
  • the alkali-soluble resin and photosensitive resin composition of the present invention are used in color filters used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image sensors, touch panel display devices, etc.
  • the photosensitive resin composition of the present invention is suitably used as an optical material, and also suitably used as a negative type.
  • a color filter having a cured product of the above-mentioned photosensitive resin composition on a substrate is also one of the preferred uses of the alkali-soluble resin of the present invention and the photosensitive resin composition containing the same.
  • the cured product formed from the photosensitive resin composition of the present invention is particularly suitable for use as a black matrix or segments that require coloring such as red, green, blue, yellow, etc. pixels.
  • it is also suitable as a material for segments that do not necessarily require coloring, such as photo spacers, protective layers, and alignment control ribs.
  • Substrates used in the above color filters include, for example, glass substrates such as white glass, blue glass, alkali-strengthened glass, and silica-coated blue glass; ring-opening polymers of polyester, polycarbonate, polyolefin, polysulfone, and cyclic olefin, and their hydrogen Sheets, films, or substrates made of thermoplastic resins such as additives; Sheets, films, or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates.
  • glass substrates such as white glass, blue glass, alkali-strengthened glass, and silica-coated blue glass
  • Ceramic substrates Semiconductor substrates having photoelectric conversion elements; Members made of various materials such as glass substrates with coloring material layers on their surfaces (for example, color filters for LCDs); and the like.
  • glass substrates and sheets, films, or substrates made of heat-resistant resin are preferred.
  • the substrate is a transparent substrate.
  • the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent, etc., as necessary.
  • a step (also referred to as an arrangement step) of disposing the above-mentioned photosensitive resin composition on a substrate for each pixel of one color (that is, for each pixel of one color), and a step of disposing the above-mentioned photosensitive resin composition on the substrate.
  • a step of irradiating the placed photosensitive resin composition with light also referred to as a light irradiation step
  • a step of developing with a developer also referred to as a developing step
  • a step of heat treatment also referred to as a heating step. It is preferable to adopt a manufacturing method in which the same method is repeated for each color. Note that the order in which pixels of each color are formed is not particularly limited. Each step will be explained below.
  • Placement process (preferably coating process)
  • the above-mentioned arrangement step is preferably performed by coating.
  • methods for applying the photosensitive resin composition onto the substrate include spin coating, slit coating, roll coating, and cast coating, and any of these methods can be preferably used.
  • the coating film can be dried using, for example, a hot plate, an IR oven, a convection oven, or the like. Drying conditions are appropriately selected depending on the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the dryer, etc., but it is usually carried out at a temperature of 50 to 160°C for about 10 seconds to 60 minutes. is suitable.
  • the active energy light source used includes, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure mercury lamp.
  • a lamp light source such as a carbon arc or a fluorescent lamp
  • a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, or a semiconductor laser.
  • the method of the exposure machine there are a proximity method, a mirror projection method, and a stepper method, and the proximity method is preferably used.
  • active energy light may be irradiated through a predetermined mask pattern depending on the application.
  • the exposed area is cured, and the cured area is made insoluble or poorly soluble in the developer.
  • the development process is a process in which, after the light irradiation process described above, development is performed using a developer to remove unexposed areas and form a pattern. Thereby, a patterned cured film can be obtained.
  • the development treatment can be carried out usually at a development temperature of 10 to 50° C. by methods such as immersion development, spray development, brush development, and ultrasonic development.
  • the developer used in the above development step is not particularly limited as long as it dissolves the photosensitive resin composition, but organic solvents and alkaline aqueous solutions are usually used, and mixtures thereof may also be used.
  • organic solvent and alkaline aqueous solution include those described in JP-A No. 2015-157909.
  • the heating process is a process (also referred to as a "post-curing process") of further curing the exposed area (cured area) by baking after the above-described development process.
  • Examples include a process of post-exposure at a light intensity of 0.5 to 5 J/cm 2 using a light source such as a high-pressure mercury lamp, and a process of post-heating at a temperature of 60 to 200°C for 10 seconds to 120 minutes. It will be done.
  • a post-curing step it is possible to further increase the hardness and adhesion of the patterned cured film.
  • the above heating step is generally carried out at a temperature of about 200 to 260°C, but if the above photosensitive resin composition is used, it can be carried out at a relatively low temperature of 200°C or lower, preferably 160°C or lower. Sufficient curing can be achieved. Therefore, a product with excellent solvent resistance can be obtained without impairing the properties held by the substrate or the cured product.
  • the heating temperature is preferably 160°C or lower, more preferably 155°C or lower, and even more preferably 150°C or lower.
  • the heating temperature is preferably 70°C or higher, more preferably 90°C or higher, and even more preferably 95°C or higher.
  • the heating temperature is preferably 70 to 160°C, more preferably 90 to 155°C, and even more preferably 95 to 150°C.
  • the heating time in the heating step is not particularly limited, but is preferably 5 to 60 minutes, for example.
  • the heating method is not particularly limited, but it can be performed using a heating device such as a hot plate, a convection oven, or a high-frequency heater.
  • the thickness of the cured film obtained by the heating step is preferably 0.1 to 20 ⁇ m.
  • the film thickness is more preferably 0.5 to 15 ⁇ m, and even more preferably 1 to 10 ⁇ m.
  • the color filter described above can be suitably used in a display device. That is, the cured product obtained by curing the alkali-soluble resin and photosensitive resin composition of the present invention can be suitably used as a member for a display device.
  • a display device member including a cured product obtained by curing the alkali-soluble resin and photosensitive resin composition of the present invention, and a display device including the display device member are also part of the present invention.
  • the cured product (cured film) formed from the above photosensitive resin composition is stable, has excellent adhesion and solvent resistance, and has high hardness, as well as high smoothness and high transmittance. Therefore, it is particularly suitable as a transparent member, and is also useful as a protective film or an insulating film in various display devices.
  • the display device for example, a liquid crystal display device, a solid-state image sensor, a touch panel type display device, etc. are suitable.
  • the above-mentioned cured product (cured film) is used as a member for a display device
  • the member may be a film-like single-layer or multi-layer member composed of the above-mentioned cured film, or the above-mentioned single-layer or multi-layer member. It may be a member in which another layer is combined with the above member, or it may be a member that includes the above-mentioned cured film in its structure.
  • the alkali-soluble resin and photosensitive resin composition of the present invention have excellent alkali developability and can provide a cured product with excellent solvent resistance even under low temperature curing conditions.
  • the alkali-soluble resin and photosensitive resin composition of the present invention can be used as various optical members and structural members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image sensors, touch panel display devices, etc. It can be suitably used in various applications such as electrical machinery and electronic equipment.
  • Double bond equivalent (g/equivalent) It was determined by dividing the mass (g) of the resin solid content by the double bond amount (mol) of the resin.
  • (4) Alkali Solubility Using each alkali soluble resin solution, the formulations shown in Table 1 were prepared to obtain photosensitive resin compositions. It was applied onto a glass plate by spin coating, dried at 80°C for 30 minutes, cooled to room temperature, immersed in a 1% by mass sodium carbonate aqueous solution at 30°C for 30 seconds, and the presence of the remaining coating film was visually checked using the following criteria. evaluated.
  • Example 1 Synthesis of alkali-soluble resin solution A-1
  • a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet 118.8 parts of propylene glycol monomethyl ether acetate and cresol novolac type epoxy resin YDCN- were added.
  • 207.6 parts of 704A manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent: 207.6 g/equivalent
  • 0.4 part of triphenylphosphine as a reaction catalyst
  • Antige W-400 Korean Chemical Industry Co., Ltd.
  • Example 2 Synthesis of alkali-soluble resin solution A-2 109.8 parts of propylene glycol monomethyl ether acetate used in Example 1 was placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet. 207.6 parts of the same cresol novolac type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.2 parts of Antige W-400 as a polymerization inhibitor were charged, and heated to 110°C. It was warm. While maintaining the same temperature, 20.1 parts of dimethylolpropionic acid and 20.2 parts of acrylic acid were added to carry out an addition reaction.
  • Example 3 Synthesis of alkali-soluble resin solution A-3 123.6 parts of propylene glycol monomethyl ether acetate was added to a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, as used in Example 1. 207.6 parts of the same cresol novolak type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.3 parts of Antige W-400 as a polymerization inhibitor were charged, and heated to 110°C. It was warm. While maintaining the same temperature, 26.8 parts of dimethylolpropionic acid and 38.7 parts of methacrylic acid were added to carry out an addition reaction.
  • Example 4 Synthesis of alkali-soluble resin solution A-4 129.1 parts of propylene glycol monomethyl ether acetate was added to a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, as used in Example 1. 207.6 parts of the same cresol novolak type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.3 parts of Antige W-400 as a polymerization inhibitor were charged, and heated to 110°C. It was warm. While maintaining the same temperature, 26.8 parts of dimethylolpropionic acid and 31.3 parts of acrylic acid were added to carry out an addition reaction.
  • Example 5 Synthesis of alkali-soluble resin solution A-5 Into a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, 112.4 parts of propylene glycol monomethyl ether acetate was added, and biphenyl-type epoxy resin YX4000 (Mitsubishi 187 parts of epoxy equivalent (manufactured by Chemical Co., Ltd., epoxy equivalent: 187 g/equivalent), 0.4 part of triphenylphosphine as a reaction catalyst, and 0.2 part of Antige W-400 as a polymerization inhibitor were charged, and the mixture was heated to 110°C.
  • biphenyl-type epoxy resin YX4000 Mitsubishi 187 parts of epoxy equivalent (manufactured by Chemical Co., Ltd., epoxy equivalent: 187 g/equivalent)
  • triphenylphosphine as a reaction catalyst
  • Antige W-400 as a polymerization inhibitor
  • Example 6 Synthesis of alkali-soluble resin solution A-6 118.8 parts of propylene glycol monomethyl ether acetate was added to a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, as used in Example 1. 207.6 parts of the same cresol novolak type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.3 parts of Antige W-400 as a polymerization inhibitor were charged, and heated to 110°C. It was warm. While maintaining the same temperature, 20.1 parts of dimethylolpropionic acid and 40.4 parts of acrylic acid were added to carry out an addition reaction.
  • Example 7 Synthesis of alkali-soluble resin solution A-7
  • a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet add 115 parts of propylene glycol monomethyl ether acetate, the same as that used in Example 1.
  • 207.6 parts of cresol novolak type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.3 parts of Antige W-400 as a polymerization inhibitor were charged and heated to 110°C. . While maintaining the same temperature, 14.8 parts of dimethylolpropionic acid and 44.7 parts of acrylic acid were added to carry out an addition reaction.
  • Example 8 Synthesis of alkali-soluble resin solution A-8 In a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, add 123 parts of propylene glycol monomethyl ether acetate, the same as that used in Example 1. 207.6 parts of cresol novolak type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.3 parts of Antige W-400 as a polymerization inhibitor were charged and heated to 110°C. . While maintaining the same temperature, 20.1 parts of dimethylolpropionic acid and 49.9 parts of methacrylic acid were added to carry out an addition reaction.
  • Comparative example 1 Synthesis of Comparative Alkali-Soluble Resin Solution B-1 129.7 parts of propylene glycol monomethyl ether acetate was added to a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet used in Example 1. 207.6 parts of the same cresol novolak type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.3 parts of Antige W-400 as a polymerization inhibitor were charged and heated to 110°C. The temperature rose to . While maintaining the same temperature, 26.8 parts of dimethylolpropionic acid and 58.4 parts of acrylic acid were added to carry out an addition reaction.
  • Comparative example 2 Synthesis of comparative alkali-soluble resin solution B-2 115 parts of propylene glycol monomethyl ether acetate used in Example 1 was placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet. 207.6 parts of the same cresol novolak type epoxy resin YDCN-704A, 0.4 parts of triphenylphosphine as a reaction catalyst, and 0.3 parts of Antige W-400 as a polymerization inhibitor were charged, and heated to 110°C. It was warm. While maintaining the same temperature, 52.1 parts of acrylic acid was added to carry out an addition reaction.
  • Examples 9 to 16, Comparative Examples 3 and 4 Using the alkali-soluble resins A-1 to A-8 synthesized in Examples 1 to 8 and the comparative alkali-soluble resin solutions B-1 and B-2 synthesized in Comparative Examples 1 and 2, the Photosensitive resin compositions of Examples 9 to 16 and Comparative Examples 3 and 4 were prepared by mixing a polymerizable compound (polyfunctional monomer), a photopolymerization initiator, and the like. Table 2 shows the results of various characteristic evaluations of the obtained photosensitive resin composition.
  • a polymerizable compound polyfunctional monomer
  • Table 2 shows the results of various characteristic evaluations of the obtained photosensitive resin composition.
  • the photosensitive resin composition containing an alkali-soluble resin having a specific structure and an epoxy equivalent of 50,000 g/equivalent or less has good alkali solubility and photocurability, and is also resistant to curing at a low temperature of 90°C. It was found that a cured product with excellent solvent resistance can be obtained even when using the same method. Furthermore, since the photosensitive resin compositions of Examples 11, 12, and 16 showed particularly excellent solvent resistance, by using methacrylic acid as the unsaturated monocarboxylic acid and tetrahydrophthalic anhydride as the polybasic acid anhydride, It was suggested that the solvent resistance was more markedly expressed and that the alkali-soluble resin having an alkyl group and a cyclic structure had more superior properties.
  • the photosensitive resin composition of the present invention has excellent curability and alkali developability, is suitable for resists for forming members in the electronic information field, such as plating resists and resists for color filters, and has excellent solvent resistance. Therefore, it is particularly suitable for forming pixels (colored layers) of color filters.

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Abstract

La présente invention concerne : une résine soluble dans les alcalis qui peut donner des produits durcis hautement résistants aux solvants même dans des conditions de durcissement à basse température et peut être utilisée de manière appropriée pour diverses applications telles que des filtres colorés ; et une composition de résine photosensible contenant ladite résine. La présente invention concerne une résine soluble dans les alcalis ayant une structure spécifique d'une structure contenant un groupe époxyde, une structure contenant un groupe carboxyle, et une structure contenant une liaison insaturée polymérisable, et ayant un poids équivalent époxy de 50 000 g/éq ou moins.
PCT/JP2023/015488 2022-05-13 2023-04-18 Résine soluble dans les alcalis, composition de résine photosensible et produit durci associé Ceased WO2023218876A1 (fr)

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Cited By (1)

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CN118440295A (zh) * 2024-05-28 2024-08-06 广东三求光固材料股份有限公司 不饱和二元酸改性的碱溶性环氧丙烯酸树脂及其制备方法和应用

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WO2001053890A1 (fr) * 2000-01-17 2001-07-26 Showa Highpolymer Co., Ltd. Composition de resine photosensible
WO2009025190A1 (fr) * 2007-08-21 2009-02-26 Nippon Kayaku Kabushiki Kaisha Composé carboxylate réactif, composition de résine durcissable par rayonnement d'énergie active utilisant celui-ci et son utilisation
JP2009116110A (ja) * 2007-11-07 2009-05-28 Taiyo Ink Mfg Ltd 光硬化性樹脂組成物及びその硬化物パターン、並びに該硬化物パターンを具備するプリント配線板
JP2012159657A (ja) * 2011-01-31 2012-08-23 Asahi Kasei E-Materials Corp 光硬化型樹脂組成物及びそれを用いたパターン形成された基材の製造方法、並びに該基材を備える電子部品
WO2022107508A1 (fr) * 2020-11-19 2022-05-27 Dic株式会社 Résine (méth)acrylique possédant un groupe acide, composition de résine durcissable, objet durci, matériau isolant, et élément de réserve

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001053890A1 (fr) * 2000-01-17 2001-07-26 Showa Highpolymer Co., Ltd. Composition de resine photosensible
WO2009025190A1 (fr) * 2007-08-21 2009-02-26 Nippon Kayaku Kabushiki Kaisha Composé carboxylate réactif, composition de résine durcissable par rayonnement d'énergie active utilisant celui-ci et son utilisation
JP2009116110A (ja) * 2007-11-07 2009-05-28 Taiyo Ink Mfg Ltd 光硬化性樹脂組成物及びその硬化物パターン、並びに該硬化物パターンを具備するプリント配線板
JP2012159657A (ja) * 2011-01-31 2012-08-23 Asahi Kasei E-Materials Corp 光硬化型樹脂組成物及びそれを用いたパターン形成された基材の製造方法、並びに該基材を備える電子部品
WO2022107508A1 (fr) * 2020-11-19 2022-05-27 Dic株式会社 Résine (méth)acrylique possédant un groupe acide, composition de résine durcissable, objet durci, matériau isolant, et élément de réserve

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118440295A (zh) * 2024-05-28 2024-08-06 广东三求光固材料股份有限公司 不饱和二元酸改性的碱溶性环氧丙烯酸树脂及其制备方法和应用

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