WO2022030445A1 - 共重合体、共重合体溶液、感光性樹脂組成物、硬化物、共重合体の製造方法、及び、共重合体溶液の製造方法 - Google Patents
共重合体、共重合体溶液、感光性樹脂組成物、硬化物、共重合体の製造方法、及び、共重合体溶液の製造方法 Download PDFInfo
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- WO2022030445A1 WO2022030445A1 PCT/JP2021/028611 JP2021028611W WO2022030445A1 WO 2022030445 A1 WO2022030445 A1 WO 2022030445A1 JP 2021028611 W JP2021028611 W JP 2021028611W WO 2022030445 A1 WO2022030445 A1 WO 2022030445A1
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- SBMDYEXGTIPPEO-UHFFFAOYSA-N C[NH+]([O-])OC1OCCCC1 Chemical compound C[NH+]([O-])OC1OCCCC1 SBMDYEXGTIPPEO-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- 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
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- 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
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention relates to copolymers. More specifically, a copolymer capable of giving a cured product having excellent solvent resistance even under low-temperature curing conditions, a copolymer solution, a photosensitive resin composition, a cured product, a method for producing the copolymer, and a copolymer weight.
- the present invention relates to a method for producing a coalesced solution.
- compositions containing curable resins include, for example, color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, organic insulating films, organic protective films, etc. used in liquid crystal display devices, solid-state image pickup devices, and the like.
- various applications to various applications such as various optical members and electric / electronic devices have been studied, and resins and resin compositions having excellent characteristics required for each application have been developed.
- optical members, electric / electronic devices, and the like have been made smaller, thinner, and energy-saving, and along with this, various members and the like used are required to have higher quality performance.
- curable resins used as materials for various members and the like are being conducted on curable resins used as materials for various members and the like.
- Patent Document 1 includes an oligomer having a carboxyl group and a photoreactive unsaturated group in the side chain and being soluble in an alkaline aqueous solution, a compound having an epoxy group, a sensitizer, and a dicyandiamide modified product.
- a photosensitive resin composition is described.
- Patent Document 2 describes a photosensitive composition containing an alkali-soluble polymer obtained by polymerizing a radically polymerizable monomer having an epoxy group or an oxetanyl group, a radically polymerizable monomer having a carboxyl group, or the like. There is.
- Patent Document 3 describes an addition copolymer such as a (meth) acrylate monomer having a glass transition temperature of 10 ° C. or lower, an epoxy group, or a (meth) acrylate monomer having a carboxyl group when a homopolymer is used.
- a curable polymer having an acid group, a hydroxy group and a polymerizable unsaturated bond in the side chain obtained by carrying out a specific modification reaction, and a photosensitive polymer composition containing the curable polymer are described.
- the curing reaction sufficiently proceeds even under relatively low temperature heating conditions of 200 ° C. or lower. Further, if the curable resin composition can be cured at a relatively low temperature, the production efficiency of the color filter can be improved.
- a high temperature is required in the synthesis of the resin. In addition, there was room for improvement in the curability of the resin.
- the present invention has been made in view of the above-mentioned current situation, and can provide a cured product having excellent solvent resistance even under low-temperature curing conditions, and is suitable as a thermosetting resin for various applications such as color filters. It is an object of the present invention to provide a copolymer that can be used.
- the present inventor has made various studies on curable resins and found that a copolymer having an epoxy group-containing group and a long-chain acid group in one molecule and having an epoxy equivalent in a specific range is used at 160 ° C. It has been found that the cross-linking reaction proceeds satisfactorily even under the following low-temperature curing conditions, and a cured product having excellent solvent resistance can be provided, and the present invention has been completed.
- the present invention has an epoxy group-containing structural unit (A) represented by the following general formula (1) and an acid group-containing structural unit (B) represented by the following general formula (2), and is an epoxy. It is a copolymer characterized by having an equivalent amount of 20000 or less.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a direct bond or a divalent organic group.
- X represents an epoxy group-containing group.
- R 3 represents a hydrogen atom or a methyl group.
- R 4 represents a direct bond or an organic group.
- R 5 represents a bond chain having a length of two or more atoms.
- Y represents an acid group.
- A represents 0 or 1.
- the above-mentioned structural unit (A) preferably contains the structural unit represented by the following general formula (1-1).
- R 1 represents a hydrogen atom or a methyl group.
- R 6 represents a direct bond or a divalent organic group.
- the above-mentioned structural unit (B) preferably contains the structural unit represented by the following general formula (2-1).
- R 3 represents a hydrogen atom or a methyl group.
- R 7 and R 8 represent the same or different, directly bonded or organic groups.
- B represents 0 or 1. show.
- the copolymer is more preferably a copolymer having a ring structure in the main chain.
- the copolymer preferably further contains a monomer having the longest side chain having 5 to 20 atoms or a structural unit derived from a monomer having a ring structure in the side chain.
- the present invention is also a copolymer solution characterized by containing the above-mentioned copolymer and a protic and aprotic solvent.
- the copolymer solution further preferably contains an acid compound having a pKa of 4.2 or less.
- the copolymer solution further contains a phosphoric acid derivative.
- the copolymer solution further contains a basic compound.
- the present invention is also a photosensitive resin composition
- a photosensitive resin composition comprising the above-mentioned copolymer or copolymer solution, a polymerizable compound, and a photopolymerization initiator.
- the photosensitive resin composition preferably further contains a coloring material.
- the photosensitive resin composition is preferably for a negative type.
- the present invention is also a cured product of the above-mentioned copolymer, the above-mentioned copolymer solution, or the above-mentioned photosensitive resin composition.
- the present invention also comprises a step of polymerizing a monomer component containing an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1), and the above. It is also a method for producing a copolymer, which comprises a step of reacting a polymer obtained in a polymerization step with an acid group-containing compound represented by the following formula (b2) or formula (b3).
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a direct bond or a divalent organic group.
- X represents an epoxy group-containing group.
- R 3 represents a hydrogen atom or a methyl group.
- R 4 represents a direct bond or an organic group.
- R 5 represents a bonded chain having a length of 2 atoms or more.
- Y represents an acid group.
- R5 represents a bound chain with a length of 2 or more atoms.
- the present invention also comprises a step of polymerizing a monomer component containing an epoxy group-containing monomer represented by the following formula (a) and a hydroxyl group-containing monomer represented by the following formula (b1), and the above.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a direct bond or a divalent organic group.
- X represents an epoxy group-containing group.
- R 3 represents a hydrogen atom or a methyl group.
- R 4 represents a direct bond or an organic group.
- R 5 represents a bonded chain having a length of 2 atoms or more.
- Y represents an acid group.
- R5 represents a bound chain with a length of 2 or more atoms.
- the copolymer of the present invention can provide a cured product having excellent solvent resistance even under relatively low temperature curing conditions of 160 ° C. or lower.
- the copolymer of the present invention includes various optical members used in liquid crystal / organic EL / quantum dot / micro LED liquid crystal display devices, solid-state image pickup devices, touch panel type display devices, and various components such as electric / electronic devices. Suitable for use.
- (meth) acrylic acid means “acrylic acid and / or methacrylic acid”
- (meth) acrylate means “acrylate and / or methacrylate”.
- the copolymer of the present invention has an epoxy group-containing structural unit (A) represented by the following general formula (1) and an acid group-containing structural unit (B) represented by the following general formula (2).
- the epoxy equivalent is 20000 or less.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a direct bond or a divalent organic group.
- X represents an epoxy group-containing group.
- R 3 represents a hydrogen atom or a methyl group.
- R 4 represents a direct bond or an organic group.
- R 5 represents a bond chain having a length of two or more atoms.
- Y represents an acid group.
- A represents 0 or 1.
- the copolymer of the present invention is cured at a relatively low temperature of 160 ° C. or lower (preferably about 90 ° C.), it is possible to provide a cured product having excellent solvent resistance due to the epoxy group and the acid. Since it has a group and the acid group is a long-chain acid located relatively far from the main chain, the acid group is very easy to react with the epoxy group, and the cross-linking reaction proceeds even at a relatively low temperature. When the side chain of the acid group-containing structural unit becomes longer, the glass transition temperature becomes lower than that of the structural unit of acrylic acid or methacrylic acid, and the polymer side chain becomes more flexible. It is presumed that the above-mentioned cross-linking reaction tends to proceed at a low temperature.
- the copolymer of the present invention has the above-mentioned epoxy group-containing structural unit (A) and acid group-containing structural unit (B), and has an epoxy equivalent (g / equivalent) of 20000 or less. If the epoxy equivalent exceeds 20000, the curing may be insufficient and the solvent resistance may be lowered.
- the epoxy equivalent of the copolymer of the present invention is preferably 10,000 or less, more preferably 8,000 or less, further preferably 5,000 or less, still more preferably 4,000 or less, and 3,000 or less. It is particularly preferable to have it, and it is most preferably 2000 or less. Further, the epoxy equivalent is preferably 100 or more, more preferably 150 or more, and further preferably 200 or more in terms of storage stability.
- the epoxy equivalent can be determined by dividing the amount of solid content of the copolymer by the number of moles of epoxy groups contained in the copolymer. The epoxy equivalent can also be determined by a method based on JIS K7236: 2001.
- the copolymer of the present invention has an epoxy group-containing structural unit (A) represented by the above general formula (1).
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a direct bond or a divalent organic group.
- the organic group include chain or cyclic saturated or unsaturated hydrocarbon groups, -O-, -CO-, -COO-, -NH-, -S-, -SO-, -SO 2- , and. , A divalent group composed of a combination of these, and the like.
- the hydrocarbon group include a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group may be linear or branched, and may be, for example, an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, an ethylidene group, a propyridene group or an isopropyridene group, or vinylene.
- alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, an ethylidene group, a propyridene group or an isopropyridene group, or vinylene.
- Examples include a group, a propenylene group, a vinylidene group and the like.
- Examples of the alicyclic hydrocarbon group include cycloalkylene groups such as 1,2-cyclopentylene group, 1,2-cyclohexylene group, cyclopentylidene group and cyclohexylidene group.
- aromatic hydrocarbon group examples include 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, benzylidene group, cinnamylidene group, biphenylylene group and the like.
- At least one atom constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom.
- the above-mentioned hydrocarbon group may have a substituent.
- the substituent include a hydroxyl group, an alkoxy group, an alkyl group, an allyl group, an aryl group, a halogen atom and the like.
- the above-mentioned substituent may further have a substituent.
- divalent organic group examples include -R-, -CO-, -CO-R-, -R-CO-R'-, -COO-, -COO-R-,-.
- the number of atoms of the divalent organic group is preferably 0 to 10, more preferably 1 to 5, and even more preferably 2 to 4.
- R 2 is preferably -R-, -COO-, -COO-R-, and -COO-, -COO-R- (R has 1 carbon atom which may have a substituent). It represents a hydrocarbon group of about 4 and preferably an alkylene group having 1 to 2 carbon atoms).
- X represents an epoxy group-containing group.
- the above-mentioned epoxy group-containing group is a group containing an oxylan ring (epoxide group), such as a group having an oxylan ring bonded to carbon such as a glycidyl group, a glycidyl ether group and a glycidyl ester group.
- epoxide group such as a group having an oxylan ring bonded to carbon
- glycidyl group a group having an oxylan ring bonded to carbon
- n is an integer of 0 to 10, preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.
- m is an integer of 1 to 10, preferably an integer of 2 to 8, and more preferably an integer of 3 to 6.
- the structural unit (A) is preferably a structural unit (A-1) represented by the following general formula (1-1) in that the solvent resistance can be further improved.
- R 1 represents a hydrogen atom or a methyl group.
- R 6 represents a direct bond or a divalent organic group.
- R 1 represents a hydrogen atom or a methyl group. Of these, R 1 is preferably a methyl group.
- Examples of the divalent organic group represented by R 6 include the same groups as the above-mentioned divalent organic group represented by R 2 .
- the number of carbon atoms of the divalent organic group represented by R6 is preferably 0 to 10 , more preferably 1 to 4, and even more preferably 1 to 2.
- a divalent organic group represented by R6 a divalent aliphatic hydrocarbon group is preferable, a divalent aliphatic hydrocarbon group having no substituent is more preferable, and a methylene group is preferable. preferable.
- the copolymer having the structural unit (A) can be obtained by polymerizing a monomer component containing a monomer into which the structural unit (A) can be introduced.
- Examples of the monomer into which the structural unit (A) can be introduced include a compound represented by the following formula (a).
- R 1 , R 2 , and X are the same as R 1 , R 2 , and X in the above general formula (1), respectively.
- the monomer into which the structural unit (A) can be introduced include, for example, glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, and vinylbenzyl.
- examples thereof include glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide and the like.
- glycidyl (meth) acrylate and (3,4-epoxycyclohexyl) methyl (meth) acrylate are preferable, and glycidyl (meth) acrylate is more preferable, which can suppress side reactions and is expected to improve storage stability.
- Glycidyl methacrylate is more preferred in that it can.
- the copolymer of the present invention may have one kind or two or more kinds of the above structural units (A).
- the content ratio of the structural unit (A) is preferably 0.1 to 50% by mass, more preferably 0.5% by mass or more with respect to 100% by mass of all structural units. It is more preferably 1% by mass or more, more preferably 45% by mass or less, and further preferably 40% by mass or less.
- the copolymer of the present invention further has an acid group-containing structural unit (B) represented by the above general formula (2).
- R 3 represents a hydrogen atom or a methyl group.
- R4 represents a direct bond or an organic group. Examples of the organic group represented by R 4 include groups similar to the organic group represented by R 2 described above. The number of atoms of the organic group represented by R4 is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 5.
- R 4 a divalent organic group which may have a substituent is preferable, a divalent organic group containing an ester bond is preferable, and —CO—O—R— (R is Represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms), -CO-OR (-O-CO-R')-(R is a linear or branched group having 1 to 3 carbon atoms. It represents a chain-like divalent aliphatic hydrocarbon group. R'represents a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.) Is more preferable, and -CO-OR- (R is). , Representing a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.) Is more preferable.
- R 5 represents a bonded chain having a length of 2 or more atoms.
- the length of the bond chain is the number of atoms connected on the main chain of the bond chain, and does not include the number of atoms constituting the side chain of the bond chain.
- examples of the bond chain having a length of 3 atoms include -CH 2 -CH 2 -CH.
- the length of the bound chain represented by R5 is preferably 10 or less, more preferably 5 or less, and most preferably 2 in that the crosslinkability is more excellent.
- the bonded chain is preferably a divalent organic group.
- the divalent organic group include the same groups as the divalent organic group represented by R2 described above. Among them, the organic groups are -R-, -OR-, -OR-O-, -CO-R-, -OR-O-CO-R'-(R and R'are , The same or different, representing a divalent hydrocarbon group which may have a substituent.), Preferred: -R-, -OR-, -OR-O-CO-R. ''-(R and R'represent the same or different divalent aliphatic hydrocarbon group which may have a substituent), and more preferably an ethylene group.
- Y represents an acid group.
- the acid group include functional groups that neutralize with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and only one of these is present. You may have two or more of them. Of these, a carboxyl group or a carboxylic acid anhydride group is preferable, and a carboxyl group is more preferable. Further, it may have two or more acid groups.
- a 0 or 1. It is preferable that a is 1 in that the solvent resistance is further excellent.
- the structural unit (B) As the structural unit (B), the structural unit (B-1) represented by the following general formula (2-1) is preferably mentioned.
- R 3 represents a hydrogen atom or a methyl group.
- R 7 and R 8 represent the same or different, directly bonded or organic groups.
- B represents 0 or 1. show.
- R 3 represents a hydrogen atom or a methyl group.
- R 3 is preferably a methyl group in that the heat resistance and developability of the polymer are improved.
- Preferred examples of the organic group represented by R 7 and R 8 include the above-mentioned divalent organic group, and among them, R 7 is a divalent hydrocarbon group which may have a substituent. Is preferable, a divalent aliphatic hydrocarbon group which may have a substituent is more preferable, and an alkylene group is further preferable.
- R8 a divalent hydrocarbon group which may have a substituent is preferable, a divalent aliphatic hydrocarbon group which may have a substituent is more preferable, and an alkylene group is further preferable.
- the number of carbon atoms of the organic group represented by R 7 and R 8 is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
- b 0 or 1
- the copolymer having the structural unit (B) may polymerize a monomer component containing a monomer into which the structural unit (B) can be introduced, or a monomer component containing a hydroxyl group-containing monomer. It can be obtained by reacting an acid group-containing compound with a base polymer obtained by polymerizing.
- Examples of the monomer into which the structural unit (B) can be introduced include ⁇ -carboxyethyl (meth) acrylate, monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl) and the like. Examples thereof include long-chain unsaturated monocarboxylic acids in which the chain is extended between the unsaturated group and the carboxyl group.
- Examples of the hydroxyl group-containing monomer include compounds represented by the following formula (b1).
- R 3 and R 4 are the same as R 3 and R 4 in the above general formula (2), respectively.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate.
- Hydroxyalkyl (meth) acrylates such as butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-hydroxypropyl (meth) acrylate; glycerin mono (meth) acrylate, tri.
- Mono (meth) acrylates of polyols such as methylolpropane mono (meth) acrylates, mono (meth) acrylates of pentaerythritol, ditrimethylolpropane mono (meth) acrylates and dipentaerythritol mono (meth) acrylates; N-hydroxyethyl acrylamide and the like. Hydroxyalkylacrylamide of.
- Examples of the acid group-containing compound include compounds represented by the following formula (b2) or formula (b3).
- R5 and Y are the same as R5 and Y in the above general formula (2), respectively.
- R 5 is the same as R 5 in the above general formula (2).
- the acid group-containing compound examples include carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimellitic acid; succinic anhydride, maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride.
- carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimellitic acid
- succinic anhydride maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride.
- Hexahydrophthalic anhydrides, methyltetrahydrophthalic anhydrides, itaconic acid anhydrides, carboxylic acid anhydrides such as trimellitic acid anhydrides; and the like can be mentioned.
- carboxylic acid anhydrides are preferable, and succinic anhydride is more preferable, because the addition reactivity is higher.
- the copolymer of the present invention may have one kind or two or more kinds of structural units (B).
- the content ratio of the structural unit (B) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more with respect to 100% by mass of all structural units. It is more preferably 1% by mass or more, more preferably 45% by mass or less, and further preferably 40% by mass or less.
- the copolymer of the present invention is further preferably a copolymer having a ring structure in the main chain. That is, it is preferable that the copolymer further has a structural unit (C) having a ring structure in the main chain.
- a cured product having excellent heat resistance can be given.
- the ring structure include an imide ring, a tetrahydropyran ring, a tetrahydrofuran ring, a lactone ring and the like.
- a copolymer having the structural unit (C) can be obtained by polymerizing a monomer component containing a monomer capable of introducing a ring structure into the main chain.
- Examples of the monomer capable of introducing a ring structure into the main chain include a monomer having a double bond-containing ring structure in the molecule and a polymer having a ring structure in the main chain by cyclization polymerization. Examples thereof include a monomer that forms a ring structure after polymerization. From the viewpoint of good heat resistance, hardness, dispersibility of coloring material, etc., specifically, N-substituted maleimide-based monomer, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer, and At least one monomer selected from the group consisting of ⁇ - (unsaturated alkoxyalkyl) acrylate-based monomers is preferably mentioned. Of these, an N-substituted maleimide-based monomer is preferable because it has even better solvent resistance.
- N-substituted maleimide-based monomer examples include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, and N-dodecylmaleimide.
- Examples thereof include N-benzylmaleimide and N-naphthylmaleimide, and one or more of these can be used. Of these, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide are preferable, and N-benzylmaleimide is more preferable, from the viewpoint of heat resistance.
- N-benzylmaleimide examples include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide. , O-Dichlorobenzylmaleimide, halogen-substituted benzylmaleimide such as p-dichlorobenzylmaleimide; and the like.
- dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer examples include dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate and diethyl-2,2'-. [Oxybis (methylene)] bis-2-propenoate, di (n-propyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] )] Bis-2-propenoate, di (n-butyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis- 2-propenoate, di (t-butyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2- Prop
- Examples of the ⁇ - (unsaturated alkoxyalkyl) acrylate-based monomer include ⁇ - (allyloxymethyl) acrylate-based monomers.
- Specific examples of the ⁇ - (allyloxymethyl) acrylate-based monomer include ⁇ -allyloxymethylacrylic acid; methyl ⁇ -allyloxymethylacrylate, ethyl ⁇ -allyloxymethylacrylate, and ⁇ -allyl.
- alkyl- ( ⁇ -allyloxymethyl) acrylate-based monomer is preferable.
- the alkyl- ( ⁇ -allyloxymethyl) acrylate-based monomer includes methyl ⁇ -allyloxymethylacrylate (methyl- ( ⁇ -allyl)) from the viewpoints of transparency, dispersibility, and easy industrial availability. Oxymethyl) acrylate) is particularly suitable.
- the ⁇ - (unsaturated alkoxyalkyl) acrylate can be produced, for example, by the production method disclosed in International Publication No. 2010/114077.
- 2- (hydroxyalkyl) acrylic acid alkyl ester is also preferably mentioned.
- the 2- (hydroxyalkyl) acrylic acid alkyl ester can react with (meth) acrylic acid to form a lactone ring structure in the main chain.
- Examples of the 2- (hydroxyalkyl) acrylic acid alkyl ester include 2- (1-hydroxyalkyl) acrylic acid alkyl ester and 2- (2-hydroxyalkyl) acrylic acid alkyl ester, and specific examples thereof include, for example.
- Examples thereof include t-butyl 2- (1-hydroxymethyl) acrylate and 2-ethylhexyl 2- (1-hydroxymethyl) acrylate.
- methyl 2- (1-hydroxymethyl) acrylate and ethyl 2- (1-hydroxymethyl) acrylate are preferable. These may be used alone or in combination of two or more.
- the above-mentioned copolymer may have one kind or two or more kinds of structural units (C).
- the content ratio of the structural unit (C) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more, based on 100% by mass of the total structural unit. It is more preferably 5% by mass or more, more preferably 45% by mass or less, and further preferably 40% by mass or less.
- the copolymer may further have another structural unit (D) in addition to the above-mentioned structural units (A), (B) and (C).
- the structural unit (D) include, in addition to the above-mentioned hydroxyl group-containing monomer, an acid group-containing monomer other than the above-mentioned long-chain unsaturated monocarboxylic acids, and a (meth) acrylic acid ester-based monomer.
- examples thereof include a structural unit derived from a monomer having a group that produces an acid group, another copolymerizable monomer, and the like.
- Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, silicic acid, and vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
- unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, silicic acid, and vinyl benzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
- Unsaturated polyvalent carboxylic acids such as: Maleic anhydride, unsaturated acid anhydrides such as itaconic acid anhydride; phosphate group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.); and the like.
- Examples of the (meth) acrylic acid ester-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth).
- Examples of the monomer having a group that produces an acid group include a compound that has a polymerizable double bond with a group that produces an acid group by heat or acid.
- Examples of the polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, and a metharyl group.
- Examples of the group that generates an acid group by heat or acid include a tertiary carbon-containing group, a group in which the acid group is blocked by a vinyl ether compound, and a phenolic hydroxyl group by a protective group such as a t-butyl group or an acetyl group. Protected groups, etc. may be mentioned.
- the tertiary carbon-containing group is preferably a ⁇ COO * Ra (R a represents a monovalent organic group, and the carbon atom bonded to O * is a tertiary carbon atom).
- R a represents a monovalent organic group, and the carbon atom bonded to O * is a tertiary carbon atom.
- the groups represented are mentioned. Heating breaks the OC bond between —COO * and Ra and produces a carboxyl group.
- Ra of -COO * Ra represents a monovalent organic group, and the carbon atom bonded to O * is a tertiary carbon atom.
- the tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom.
- the monovalent organic group preferably includes a monovalent chain, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 91 carbon atoms.
- the organic group may have a substituent.
- the carbon number of Ra is more preferably 1 to 50 carbon atoms, further preferably 1 to 35 carbon atoms, still more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Most preferably, it has 1 to 9 carbon atoms.
- R a can preferably be represented by ⁇ C (R b ) (R c ) (R d ).
- R b , R c , and R d are preferably the same or different hydrocarbon groups having 1 to 30 carbon atoms.
- the hydrocarbon group may be a saturated hydrocarbon group, an unsaturated hydrocarbon group, a cyclic structure, or a substituent.
- R b , R c , and R d may be connected to each other at the terminal sites to form an annular structure.
- the tertiary carbon-containing group it is preferable that at least one of the adjacent carbon atoms of the tertiary carbon atom is bonded to the hydrogen atom.
- R a is a group represented by -C (R b ) (R c ) (R d )
- at least one of R b , R c and R d has one or more hydrogen atoms.
- the carbon atom is contained and the carbon atom is bonded to the tertiary carbon atom.
- the R b , R c and R d are preferably the same or different, saturated hydrocarbon groups having 1 to 15 carbon atoms, more preferably saturated hydrocarbon groups having 1 to 10 carbon atoms, and even more preferably carbon. It is a saturated hydrocarbon group having a number of 1 to 5, particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.
- the Ra is preferably a t-butyl group or a t-amyl group.
- Preferred examples of the tertiary carbon-containing monomer include t-butyl (meth) acrylate and t-amyl (meth) acrylate.
- Examples of the group in which the acid group is blocked by the vinyl ether compound include a group in which a vinyl ether compound is bonded to the above-mentioned acid group such as a carboxyl group.
- Examples of the vinyl ether compound include aliphatic groups such as methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether.
- Examples thereof include vinyl ether compounds and cyclic ether compounds such as dihydropyran that can be opened to form vinyl ether.
- dihydropyran is preferable because the protecting group is easily removed at a lower temperature.
- the group in which the acid group is blocked by the above dihydropyran is preferably a group represented by the following formula.
- Preferred examples of the group in which the phenolic hydroxyl group is protected by a protecting group such as a t-butyl group or an acetyl group include a group represented by the following formula.
- n represents the number of substituents and is an integer of 1 to 5.
- the group represented by the above formula is, for example, reacted in a solvent under an acid catalyst such as hydrochloric acid or sulfuric acid at a temperature of 50 to 150 ° C. for 1 to 30 hours to desorb the protecting group and generate an acid group. Will be done.
- an acid catalyst such as hydrochloric acid or sulfuric acid
- the monomer having a group represented by the above formula examples include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o.
- -Examples include a monomer in which the hydroxyl group of an aromatic vinyl compound having a phenolic hydroxyl group such as isopropenylphenol is protected by a t-butyl group and an acetyl group.
- the monomer having a group having an acid group blocked by dihydropyran is a monomer having a group having an acid group in that an acid group can be generated at a lower temperature. preferable.
- Examples of the other copolymerizable monomer include one or more of the following compounds.
- (Meta) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropylacrylamide; polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, Macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as polycaprolactam; conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; vinyl acetate, vinyl propionate, vinyl butyrate, benzoic acid Vinyl esters such as vinyl; aromatic vinyls such as styrene, vinyl toluene, ⁇ -methylstyrene, xylene, methoxystyrene, ethoxystyrene
- the monomer giving the structural unit (D) for example, by copolymerizing a monomer having an amide group such as (meth) acrylamides, addition without using a basic catalyst such as an amine is added. The reaction can be carried out and the storage stability of the copolymer can be improved. Further, when a monomer having an amine group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate is used, the addition reaction should be carried out without using a catalyst. It is possible to improve the storage stability of the copolymer.
- the monomer giving the structural unit (D) a monomer having a long side chain or a monomer having a large steric hindrance is used in that gelation is suppressed and storage stability is good. Is preferable.
- the monomer having a long side chain those having the longest side chain of the monomer having 5 to 20 atoms are preferable, those having 6 to 20 atoms are more preferable, and those having 7 to 10 atoms are further preferable.
- the side chain may be linear or branched. Specific examples of the monomer having a long side chain include 2-ethylhexyl (meth) acrylate.
- those having a ring structure in the side chain are preferably mentioned, and for example, those having a structure such as cyclohexyl, bicyclo, phenyl, biphenyl, dicyclopentanyl, furan, pyran, piperidine and the like. Can be mentioned.
- the monomer having a large steric disorder examples include vinyl toluene, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, ( Phenoxyethyl (meth) acrylate (meth) acrylate, (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth) acrylic Examples thereof include isobornyl acid acid, pentamethylpiperidinyl (meth) acrylate, and the like. Of these, dicyclopentanyl (meth) acrylate, vinyltoluene, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate are preferable.
- the above-mentioned copolymer is selected from the group consisting of vinyltoluene, 2-ethylhexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate because the storage stability can be further improved. It is preferable to have a structural unit derived from at least one monomer. Further, when the above-mentioned copolymer has a structural unit derived from 2-ethylhexyl (meth) acrylate, the glass transition temperature of the copolymer is lowered and the developability can be improved.
- the above-mentioned copolymer may have one kind or two or more kinds of structural units (D).
- the content ratio of the structural unit (D) is preferably 0.1 to 50% by mass, more preferably 0.2% by mass or more, based on 100% by mass of the total structural unit. It is more preferably 5% by mass or more, more preferably 45% by mass or less, and further preferably 40% by mass or less.
- the acid value of the copolymer is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 30 mgKOH / g or more. Further, it is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and even more preferably 100 mgKOH / g or less.
- the acid value is a value obtained by measuring by a neutralization titration method using a potassium hydroxide (KOH) solution, and is an acid value per 1 g of polymer solid content.
- the weight average molecular weight of the copolymer is preferably 2000 or more, more preferably 3000 or more, and further preferably 4000 or more. Further, it is preferably 250,000 or less, more preferably 100,000 or less, further preferably 50,000 or less, still more preferably 20,000 or less.
- the weight average molecular weight of the copolymer can be measured by a gel permeation chromatography (GPC) method, and specifically, can be measured by the method described in Examples.
- the above-mentioned copolymer may have a polymerizable double bond (carbon-carbon double bond) in the side chain.
- a polymerizable double bond in the side chain, the photocurability of the copolymer can be improved.
- the polymerizable double bond include those described above, and among them, a (meth) acryloyl group is preferable.
- the double bond equivalent of the copolymer is preferably 200 to 20000 g / equivalent.
- the double bond equivalent is more preferably 250 to 15,000 g / equivalent, further preferably 300 to 10,000 g / equivalent, and further preferably 300 to 4000 g / equivalent, in terms of improving curability. More preferred.
- the double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of the double bond of the copolymer.
- the mass of the solid content of the polymer solution is the sum of the mass of the monomer components constituting the copolymer and the mass of the polymerization inhibitor.
- the double bond equivalent can be obtained by dividing the mass (g) of the polymer solid content of the polymer solution by the double bond amount (mol) of the copolymer.
- the amount of the double bond of the copolymer can be determined from the amount of the monomer containing an acid group used in the polymerization and the compound having a polymerizable double bond.
- various analyzes such as titration and elemental analysis, NMR and IR, and differential scanning calorimetry can be used for measurement. For example, it may be calculated by measuring the number of ethylenic double bonds contained in 1 g of the copolymer according to the test method of iodine value as described in JIS K 0070: 1992.
- the method for producing the copolymer of the present invention is any method that has at least the above-mentioned structural unit (A) and structural unit (B) and can obtain a copolymer having an epoxy equivalent in a predetermined range.
- the above-mentioned method is not particularly limited, and for example, a method of polymerizing a monomer component containing a monomer into which each structural unit can be introduced, or a method of polymerizing a monomer component to obtain a base polymer is obtained, and the above-mentioned base polymer is obtained. Examples thereof include a method of adding another compound to the group having a predetermined structural unit to obtain a polymer having a predetermined structural unit.
- the method for polymerizing the above-mentioned monomer components is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Of these, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. Further, as the polymerization mechanism of the above-mentioned monomer component, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used, but the radical polymerization mechanism is industrially advantageous. The polymerization method based on is preferable. Further, the molecular weight of the polymer obtained by polymerizing the above-mentioned monomer components can be controlled by appropriately adjusting the amount and type of the polymerization initiator, the polymerization temperature, and the type and amount of the chain transfer agent.
- Examples of the polymerization initiator include peroxides and azo compounds usually used as the polymerization initiator.
- the chain transfer agent include compounds having a mercapto group such as alkyl mercaptans, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, which are usually used as chain transfer agents. These may be used alone or in combination of two or more. Further, the amount of these additions can be appropriately set from a known method.
- Examples of the solvent used for the above polymerization include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl.
- Examples thereof include esters such as acetate; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethylsulfoxide; dimethyl carbonate and the like. These solvents may be used alone or in combination of two or more.
- the polymerization concentration when polymerizing the monomer composition (reaction solution) containing the above-mentioned monomer component is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, and further preferably 10 It is about 60% by mass.
- the polymerization concentration is the mass% of the monomer used with respect to 100% by mass of the reaction solution.
- the polymerization temperature may be appropriately set according to the type and amount of the monomer used, the type and amount of the polymerization initiator, and the like, but for example, 50 to 130 ° C. is preferable, and 60 to 60 to 130 ° C. 120 ° C. is more preferable.
- the polymerization time can be appropriately set in the same manner, and for example, 1 to 5 hours is preferable, and 2 to 4 hours is more preferable.
- the copolymer for example, a monomer containing an epoxy group-containing monomer represented by the above formula (a) and a hydroxyl group-containing monomer represented by the above formula (b1).
- the method including is preferably mentioned.
- the present invention also polymerizes a monomer component containing an epoxy group-containing monomer represented by the formula (a) and a hydroxyl group-containing monomer represented by the formula (b1) (1).
- the copolymer is characterized by comprising a step (2) of reacting the polymer obtained in the above polymerization step (1) with an acid group-containing compound represented by the above formula (b2) or the above formula (b3). It is a manufacturing method of coalescence.
- Process (1) In the method for producing a copolymer of the present invention, a monomer component containing an epoxy group-containing monomer represented by the above formula (a) and a hydroxyl group-containing monomer represented by the above formula (b1) is used. Polymerize.
- the epoxy group-containing monomer represented by the above formula (a) include the monomers described as the monomers into which the structural unit (A) of the above-mentioned copolymer can be introduced.
- Examples of the hydroxyl group-containing monomer represented by the above formula (b1) include those described above.
- the content ratio of the epoxy group-containing monomer and the hydroxyl group-containing monomer is not particularly limited, and the content ratio of the structural unit (A) and the structural unit (B) described above is set in the obtained copolymer. It may be set appropriately to.
- the above-mentioned monomer component may contain a monomer component other than the acid group-containing compound used in the step (2) described later.
- Examples of the other monomer component include the above-mentioned monomer component.
- the method for polymerizing the above-mentioned monomer component is not particularly limited, and may be polymerized by the above-mentioned known method.
- the polymerization temperature and time are also as described above.
- Process (2) Next, the step of reacting the polymer obtained in the above step (1) with the acid group-containing compound represented by the above formula (b2) or the above formula (b3) is included.
- the above-mentioned acid group-containing compound can be added to the hydroxyl group of the coalesced (base polymer) to form a long-chain acid group.
- the reaction method is not particularly limited, and a known method can be used.
- the reaction temperature is, for example, preferably 25 to 100 ° C, more preferably 30 to 90 ° C.
- the reaction time is not particularly limited, and examples thereof include 1 to 20 hours.
- the step of reacting the acid group-containing compound may be carried out in the presence of the basic compound.
- the reaction between the hydroxyl group and the acid group can be carried out under lower temperature conditions such as 70 ° C. or lower.
- the reaction between the epoxy group and the acid group can be suppressed and only the reaction between the hydroxyl group and the acid group can proceed.
- a copolymer having a structural unit (B) can be produced more efficiently.
- step (2) the polymer (base polymer) obtained in step (1) may be reacted with the acid group-containing compound at 70 ° C. or lower in the presence of a basic compound.
- the temperature exceeds 70 ° C., the reaction between the epoxy group and the acid group tends to proceed, and the resin may gel.
- Examples of the acid group-containing compound represented by the above formula (b2) or the above formula (b3) include the above-mentioned acid group-containing compounds.
- Examples of the basic compound include ammonia; primary amines such as methylamine; secondary amines such as dimethylamine; tertiary amines such as triethylamine and diethylmethylamine; aliphatics such as dimethylethanolamine, n-butylamine and diethylamine.
- Cyclic aliphatic amines such as cyclohexylamines; Heterocyclic amines such as piperidine, morpholine, N-ethylpiperidine, N-ethylmorpholine, pyridine; Fragrances such as benzylamine, N-methylaniline, N, N-dimethylaniline Amine; Tetraalkylammonium halides such as tetramethylammonium chloride and tetraethylammonium chloride; Tetraalkylammonium organic acid salts such as tetramethylammonium acetate; Tetraalkylammonium inorganic acid salts such as tetramethylammonium hydrogensulfate and tetraethylammonium hydrogensulfate; (Hydroxy) alkylammonium hydroxides such as methylammonium hydroxides, tetraethylammonium hydroxides, monohydroxyethy
- secondary amines tertiary amines, heterocyclic amines, and phosphorus compounds are preferable in terms of ease of evaporation and handling, and side reactions can be suppressed, and the molecular weight of the polymer after addition can be adjusted. It is more preferable to use a tertiary amine or triphenylphosphine in that the increase can be suppressed.
- the amount of the basic compound used is not particularly limited, but is preferably 0 to 5 mol%, preferably 0 to 4 mol%, based on 100 mol% of the amount of the acid group-containing compound used, from the viewpoint of reaction efficiency. %, More preferably 0 to 3 mol%.
- the amount of the acid group-containing compound used may be such that the content ratio of the structural unit (B) is within a desired range, or the copolymer contains, depending on the purpose and use of the copolymer to be obtained. It may be appropriately set so that the acid value is in a desired range.
- the total monomer component concentration in the total amount of the polymerization solution at the time of the addition reaction of the acid group-containing compound is preferably 40% by mass or more, more preferably 50% by mass or more.
- the acid group-containing compound can be added to the base polymer without using the basic compound as a catalyst, and the obtained copolymer can be stored and stabilized. It is possible to improve the sex.
- the acid group-containing compound can be added without a catalyst, and the storage stability of the copolymer can be improved.
- an acid group-containing monomer or an isocyanate group-containing polymerizable monomer is added to the hydroxyl group after the above step (1).
- a polymerizable double bond can be introduced into the side chain of the copolymer by subjecting the epoxy group to an addition reaction of an acid group-containing monomer after the above steps (1) or (2). ..
- the acid group-containing monomer include those described above, and preferably (meth) acrylic acid.
- Examples of the above-mentioned isocyanate group-containing polymerizable monomer include the above-mentioned unsaturated isocyanates, which are preferable (meth) in that they can undergo an addition reaction at a low temperature and the storage stability of the copolymer can be improved. ) Isocyanatoethyl acrylate can be mentioned.
- the above addition reaction is not particularly limited and can be carried out by a known method. Further, in the above addition reaction, commonly used compounds, catalysts, solvents and the like may be used.
- the above-mentioned basic compound is preferably mentioned as the catalyst, preferably a secondary amine, a tertiary amine, a heterocyclic amine or a phosphorus compound, and more preferably a tertiary amine or triphenylphosphine. ..
- dibutyltin dichloride dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, and tributyl, which are generally used as reaction catalysts for isocyanate monomers and hydroxyl groups.
- Tin-based compounds such as tin acetate, dioctyl tin oxide, and tributyl tin chloride can also be preferably used.
- the above-mentioned method for producing a copolymer may include steps other than the above-mentioned reaction steps. Examples thereof include an aging step, a neutralization step, a deactivation step of a polymerization initiator and a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step and the like. These steps can be performed by a known method.
- the present invention is also a copolymer solution characterized by containing the above-mentioned copolymer and a protictic polar solvent.
- the copolymer solution of the present invention is excellent in storage stability.
- the copolymer has an acid group and an epoxy group, and since these groups are highly reactive, the copolymer can be easily cured at a low temperature, while ensuring storage stability. That was difficult.
- the present inventor has found that the storage stability of the above-mentioned copolymer can be improved by adding a protonic polar solvent, and both high solvent resistance and storage stability can be achieved.
- the protonic polar solvent examples include water, an alcohol solvent, an amine solvent, and a phenol solvent.
- the protic and aprotic solvent is preferably an alcohol solvent.
- Saturated alcohols are preferably mentioned as the alcohol-based solvent, and monofunctional alcohols (monoalcohols), polyhydric alcohols, glycol monoethers and the like can be mentioned.
- the alcohol solvent include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono-n.
- ethylene glycol mono-n-butyl ether ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene Primary alcohols such as glycol monomethyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol mono-n-butyl ether; Isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, cyclohexanol, 2-heptanol, 3-heptanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n -Propylene Ether, Propylene Glycol Mono
- the carbon number of the alcohol solvent is preferably 1 to 10, more preferably 2 to 8, and 3 to 6 in that the boiling point is relatively low and the removal by heating is easy. Is more preferable.
- Propylene glycol monomethyl ether is particularly preferable as the alcohol solvent.
- amine-based solvent examples include diethylene amine, dimethylamine, oleylamine and the like.
- phenolic solvent examples include phenol, cresol, o-cresol, m-cresol, p-cresol, xylenol and the like.
- Only one kind of the protic and aprotic solvent may be used, or two or more kinds thereof may be used in combination.
- the boiling point of the protic and aprotic solvent is preferably 70 to 170 ° C., preferably 100 to 160 ° C., because it can be easily removed by heating, has a certain boiling point, and easily forms a flat film. It is more preferable that the temperature is 120 to 150 ° C.
- the content of the protonic polar solvent in the copolymer solution is preferably 10% by mass or more, more preferably 30% by mass, and 40% by mass with respect to 100% by mass of the solid content of the copolymer. % Or more is more preferable. Further, the content of the protonic polar solvent is preferably 1000% by mass or less with respect to 100% by mass of the copolymer solid content, in terms of facilitating the concentration adjustment in the curable resin composition, 300. It is more preferably mass% or less, and further preferably 200 mass% or less.
- the copolymer solution further contains another solvent capable of hydrogen bonding in addition to the protic and aprotic solvent from the viewpoint of stability.
- the other solvent include N, N-dimethylformamide and the like.
- ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate.
- 3-Esters such as methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform; dimethylsulfoxide; etc. may be contained.
- the content of the protonic polar solvent is 100% by mass based on the total amount of the protonic polar solvent and the other solvent. It is preferably 5 parts by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 99% by mass or less, and preferably 90% by mass or less. It is more preferably 80% by mass or less, and further preferably 80% by mass or less.
- the above-mentioned polymer solution may be prepared by mixing the above-mentioned copolymer purified from the polymerization solution containing the above-mentioned copolymer obtained at the time of polymerization with the above-mentioned protonic polar solvent, or the above-mentioned copolymer may be prepared.
- the above-mentioned protonic polar solvent may be added to the polymer solution containing the mixture to prepare the solution.
- the copolymer solution may contain the polymerization solvent.
- the above-mentioned copolymer solution may further contain other components.
- other components include components that improve the storage stability of the copolymer and components that improve curability.
- examples of the component that improves the storage stability of the copolymer include an acid compound and a phosphoric acid derivative.
- the component that improves the curability of the copolymer include basic compounds. These components may be used as appropriate depending on the purpose, or may be used in combination.
- the copolymer solution may further contain an acid compound having a pKa of 4.2 or less.
- the copolymer solution contains an acid compound having a pKa of 4.2 or less, the reaction between the acid group and the epoxy group of the copolymer is suppressed, and the storage stability of the copolymer is further improved. Can be made to.
- the storage stability of the copolymer can be improved from the acid group capable of forming the acid group-containing structural unit (B) of the copolymer.
- the presence of an acid compound having a strong acid strength reduces the anionic property of the acid group in the copolymer and suppresses the reactivity between the acid group and the epoxy group.
- the basic compound forming a salt with the carboxyl group is supplemented by the acid compound having a pKa of 4.2 or less, and the carboxyl in the copolymer is supplemented. It is considered that the nucleophilic force of the group is reduced and the reactivity between the acid group and the epoxy group can be suppressed.
- the reason why the pKa is set to 4.2 or less is that the pKa value of the monomer into which the structural unit (B) can be introduced or the acid group-containing monomer is set as the threshold value.
- the pKa value of the above-mentioned monomer include acrylic acid (pKa4.35), methacrylic acid (pKa4.26), succinic acid mono (2-acroyloxyethyl) (pKa4.35), and succinic acid mono (2). -Metachromoxyethyl) (pKa4.35) and the like can be mentioned.
- the pKa of the acid compound is preferably 3 or less, and more preferably 2 or less.
- the lower limit of pKa of the acid compound is not particularly limited, but is preferably -3 or more, and more preferably 0 or more.
- pKa acid dissociation constant
- Ka equilibrium constant
- pKa inverse logarithm
- pKa for example, literatures such as Chemistry Handbook, Basic Edition II (Revised 5th Edition, Maruzen Co., Ltd.) can be referred to, and numerical values not published in the literature are calculated by the method described in the literature. can do.
- the acid compound having a pKa of 4.2 or less include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, phosphite, hypophosphite, phosphonic acid, phosphinic acid and pyrophosphate.
- Polyphosphoric acid sulfuric acid, sulfite, thiosulfate, dimethyl sulfite, diethyl sulfite, dipropyl sulfite, dibutyl sulfite, diphenyl sulfite, dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, diphenyl sulphonic acid, toluenesulfic acid, naphthalene.
- Aromatic sulfonic acids such as sulfinic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, diisobutylnaphthalenesulfonic acid, methylsulfonic acid, ethylsulfonic acid, propyl Examples thereof include alkyl sulfonic acids such as sulfonic acid, ⁇ -olefin sulfonic acids, sulfonated polystyrenes, methyl acrylate-sulfonated styrene copolymers and derivatives thereof.
- the molecular weight of the acid compound is preferably 400 or less, more preferably 350 or less.
- the molecular weight of the acid compound is preferably 150 or more, more preferably 250 or more.
- the above-mentioned copolymer solution may contain a phosphoric acid derivative.
- the copolymer solution further contains a phosphoric acid derivative, the storage stability of the copolymer can be improved.
- a phosphoric acid ester, a phosphite ester, a phosphite, a hypophobic acid, a phosphonic acid, and a phosphinic acid are preferably mentioned, and a phosphoric acid ester, a phosphonic acid, and a phosphinic acid are more preferable.
- the ester group of the phosphoric acid ester or subphosphate ester include an alkyl ester group, an aryl ester group, an aralkyl ester group, and an ester group having a polymerizable double bond.
- Examples of the alkyl of the above alkyl ester group include methyl, ethyl, octyl, 2-ethylhexyl and the like.
- Examples of the aryl of the aryl ester group include phenyl, trill, and naphthyl.
- Examples of the aralkyl of the aralkyl ester group include benzyl and the like.
- Examples of the ester group having a polymerizable double bond include a 2-acryloyloxyethyl ester group and a 2-methacryloyloxyethyl ester group.
- phosphoric acid ester examples include, for example, monoalkyl phosphates such as methyl phosphate; dialkyl phosphates such as dibutyl phosphate; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, and distearyl.
- Trialkyl phosphates such as pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; monoaryl phosphate; diaryl phosphate; triphenyl phosphate.
- Tricredyl phosphate tris (nonylphenyl) phosphate, triaryl phosphate such as 2-ethylphenyldiphenyl phosphate; 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, 3-methacryloxypropyl acid.
- Examples thereof include phosphoric acid esters containing an ester group having a polymerizable double bond, such as phosphate, methacrylooxypolyoxyethylene glycol acid phosphate, and methacrylooxypolyoxypropylene glycol acid phosphate.
- Specific examples of the phosphonic acid include alkylphosphonic acids such as methylphosphonic acid and arylphosphonic acids such as phenylphosphonic acid.
- Specific examples of the phosphinic acid include alkylphosphinic acid such as methylphosphinic acid and arylphosphinic acid such as phenylphosphinic acid.
- a phosphoric acid ester containing an ester group having a polymerizable double bond is preferable.
- a phosphoric acid ester containing an ester group having a polymerizable double bond is used, a crosslinked structure is formed together with the copolymer and the polymerizable compound when the curable resin composition containing the copolymer solution is cured. Volatilization and elution of contained components are suppressed, and problems such as contamination of the reaction system and deterioration of electrical insulation can be significantly suppressed.
- the phosphoric acid ester preferably contains two or three or more polymerizable double bonds.
- a commercially available product can be used as the phosphoric acid ester containing the ester group having a polymerizable double bond.
- light ester P-1M and light ester P-2M both manufactured by Kyoeisha Chemical Co., Ltd.
- Hosmer M manufactured by Unichemical
- light ester P-2M is preferable.
- the molecular weight of the phosphoric acid derivative is preferably 400 or less, more preferably 350 or less.
- the resin solid content at the time of addition can be lowered, and the storage stability is further improved.
- the effect of improving the anionic property of the acid group and reducing the nucleophilic force becomes greater.
- the molecular weight of the phosphoric acid derivative is preferably 150 or more, more preferably 250 or more. When the molecular weight of the phosphoric acid derivative is 150 or more, the compatibility with the resin composition can be further improved.
- the phosphoric acid derivative may be an acid compound having the above-mentioned pKa of 4.2 or less. That is, the copolymer solution of the present invention preferably contains an acid compound or a phosphoric acid derivative having a pKa of 4.2 or less, and phosphorus having a pKa of 4.2 or less, from the viewpoint of storage stability and compatibility. It is more preferable to include an acid derivative.
- the contents of the acid compound and the phosphoric acid derivative are not particularly limited and may be appropriately set according to the intended use, blending of other components, etc., but are preferably set with respect to 100% by mass of the total solid content of the copolymer solution. Usually, 0.01 to 5% by mass is preferable, 0.01 to 3% by mass is more preferable, and 0.02 to 2% by mass is further preferable.
- the content is the total amount of the acid compound and the phosphoric acid derivative when the acid compound and the phosphoric acid derivative are used in combination. Further, in the present specification, the "total amount of solid content" means the total amount of the components forming the cured product (excluding the solvent that volatilizes during the formation of the cured product).
- the content of the acid compound and the phosphoric acid derivative is preferably 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the copolymer in the copolymer solution. More preferably, it is more preferably 0.1 to 3 parts by mass.
- the content is the total amount of the acid compound and the phosphoric acid derivative when the acid compound and the phosphoric acid derivative are used in combination.
- the content of the acid compound and the phosphoric acid derivative is 50 to 200 mol% with respect to 100 mol% of the amount of the basic compound used. It is preferably 70 to 150 mol%, more preferably 80 to 120 mol%, and even more preferably 80 to 120 mol%.
- the content of the acid compound and the phosphoric acid derivative is the range of 0.5 to 2.0 molar equivalents with respect to the basic compound, the storage stability of the copolymer is further improved and the cured product is cured. Coloring can be further suppressed.
- the content is the total amount of the acid compound and the phosphoric acid derivative when the acid compound and the phosphoric acid derivative are used in combination.
- the copolymer solution may further contain a basic compound.
- the basic compound By containing the basic compound, the cross-linking reaction proceeds satisfactorily even under low temperature curing conditions of 160 ° C. or lower when the copolymer is cured, and a cured product having further excellent solvent resistance can be provided.
- Examples of the basic compound include the above-mentioned basic compounds. Of these, amine compounds are preferable. Further, as the basic compound, secondary amines, tertiary amines, heterocyclic amines, and phosphorus compounds are more preferable in terms of ease of evaporation and handling, side reactions can be suppressed, and the weight after addition is heavy. A tertiary amine or triphenylphosphine is more preferable because it can suppress an increase in the molecular weight of the coalescence.
- the content of the basic compound is not particularly limited and may be appropriately set according to the intended use, blending of other components, etc., but is 0.01 with respect to 100% by mass of the total solid content of the copolymer solution. It is preferably from 10% by mass, more preferably 0.01 to 6% by mass, and even more preferably 0.02 to 4% by mass.
- the content of the basic compound is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and 0 with respect to 100 parts by mass of the copolymer. .1 to 6 parts by mass is more preferable.
- the basic compound used as a catalyst during the synthesis of the above-mentioned copolymer remains in the copolymer solution after the synthesis of the copolymer, it depends on the residual amount.
- the content in the copolymer solution may be adjusted by adding a basic compound.
- a method for producing the copolymer solution for example, a monomer containing an epoxy group-containing monomer represented by the above formula (a) and a hydroxyl group-containing monomer represented by the above formula (b1).
- a step of polymerizing the components (polymerization step) and a step of reacting the polymer obtained in the above polymerization step with the acid group-containing compound represented by the above formula (b2) or the above formula (b3) in the presence of a basic compound.
- a method including (reaction step) and a step of adding an acid compound having a pKa of 4.2 or less and a protonic polar solvent (addition step) is preferably mentioned.
- a step of reacting the polymer with an acid group-containing compound represented by the formula (b2) or the formula (b3) in the presence of a basic compound, and an acid compound having a pKa of 4.2 or less and a protonic polar solvent are added.
- a method for producing a copolymer solution which comprises a step of making a polymer solution, is also one of the present inventions.
- Examples of the polymerization step include the same steps as in the step (1) in the above-mentioned method for producing a copolymer.
- reaction step examples include the same method as the method in which the step (2) in the above-mentioned method for producing a copolymer is carried out in the presence of a basic compound.
- acid group-containing compound represented by the above formula (b2) or the above formula (b3) and the basic compound include the above-mentioned acid group-containing compound and the same as the basic compound.
- the acid compounds having a pKa of 4.2 or less and the protic and aprotic solvents used in the addition step are as described above.
- the copolymer of the present invention and the copolymer solution can be combined with other components to form a curable resin composition. Since the curable resin composition contains the copolymer of the present invention, it is possible to provide a cured product having excellent solvent resistance even under low temperature curing conditions. Further, when the curable resin composition contains the copolymer solution, the storage stability is further improved. Such a curable resin composition containing the above-mentioned copolymer or copolymer solution is also one of the preferred embodiments of the present invention.
- the content of the copolymer is not particularly limited and may be appropriately set according to the intended use, blending of other components, etc., for example, the total solid content of the curable resin composition. It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 80% by mass or less with respect to 100% by mass. , 75% by mass or less, more preferably 70% by mass or less.
- the total amount of solids means the total amount of the component which forms a cured product (excluding the solvent which volatilizes at the time of forming a cured product).
- the curable resin composition preferably contains the above-mentioned protonic polar solvent in terms of good stability as a composition.
- the content of the protonic polar solvent in the curable resin composition is 10% by mass or more with respect to 100% by mass of the solid content of the copolymer in terms of ensuring the stability of the curable resin composition. It is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 3000% by mass or less, and further preferably 1000% by mass or less.
- the content of the protonic polar solvent in the curable resin composition is 1% by mass or more with respect to 100% by mass of the solid content of the curable resin composition in terms of ensuring the stability of the curable resin composition. It is preferably 5% by mass or more, further preferably 10% by mass or more, preferably 400% by mass or less, and more preferably 300% by mass or less. It is more preferably 200% by mass or less.
- the curable resin composition may also contain various components such as a polymerizable compound and a polymerization initiator.
- various components such as the polymerizable compound and the polymerization initiator include the same components as those of the photosensitive resin composition described later.
- a photosensitive resin composition As an example of a preferable form of the curable resin composition, a photosensitive resin composition will be described.
- the copolymer or copolymer solution of the present invention can be further made into a photosensitive resin composition by further combining a polymerizable compound and a photopolymerization initiator. Since the photosensitive resin composition contains the above-mentioned copolymer, it is possible to provide a cured product having excellent solvent resistance even under low-temperature curing conditions of 160 ° C. or lower, for example, about 90 ° C. Further, since it further contains a polymerizable compound, it is possible to provide a cured product having various physical properties such as curability, adhesion to a substrate, surface hardness, and heat resistance. Such a photosensitive resin composition containing the above-mentioned copolymer or copolymer solution, a polymerizable compound, and a photopolymerization initiator is also one of the present inventions.
- the content of the copolymer is not particularly limited and may be appropriately set according to the intended use, blending of other components, etc., but for example, the solid of the photosensitive resin composition. It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and 80% by mass or less with respect to 100% by mass of the total amount. Is more preferable, and it is more preferably 75% by mass or less, and further preferably 70% by mass or less.
- the polymerizable compound is a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams.
- active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.) and electron beams.
- Examples thereof include a monofunctional compound having one polymerizable unsaturated group in the molecule and a polyfunctional compound having two or more polymerizable unsaturated groups.
- Examples of the monofunctional compound include N-substituted maleimide-based monomers; (meth) acrylic acid esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids; unsaturated groups and carboxyls. Unsaturated monocarboxylic acids with extended chains between groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc. Can be mentioned. Examples of these include the same compounds as those mentioned as the monomer component of the above-mentioned copolymer. Further, a monomer 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 Falkylene oxide di (meth) acrylate;
- a trifunctional or higher functional (meth) acrylate compound such as a modified product of dipentaerythritol hexaacrylate represented by.
- 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, trimetylol propanetrivinyl ether, ditri Methylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylol propanetrivinyl ether, ethylene oxide-added ditrimethylol propanetetravinyl ether, ethylene oxide-added pentaerythritol tetra
- 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 Falkylene oxide diallyl ether, trimethyl propanetriallyl ether, Ditrimethylol propanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol propanetriallyl ether, ethylene oxide-added ditrimethylol propanetetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide
- Allyl group-containing (meth) acrylic acid esters such as allyl (meth) acrylate; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene Polyfunctional (meth) acryloyl group-containing isocyanurates such as oxide-added tri (methacryloyloxyethyl) isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.
- Polyfunctional urethane (meth) acrylates obtained by reacting the polyfunctional isocyanate of (meth) with hydroxylated (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.
- the polymer having a vinyl ether group in the side chain improves the curability of the resin composition, but may lower the storage stability. Therefore, in terms of storage stability, the photosensitive resin composition is not recommended. It is preferable not to contain a polymer having a vinyl ether group in the side chain.
- the functional number of the polyfunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more.
- the functional number is preferably 10 or less, more preferably 8 or less.
- the molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less from the viewpoint of handling.
- the polyfunctional polymerizable compound is preferably a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, or a (meth) acryloyl group from the viewpoints of reactivity, economy, availability, and the like.
- examples thereof include compounds having a (meth) acryloyl group, such as a contained isocyanurate compound, and more preferably, a polyfunctional (meth) acrylate compound.
- the photosensitive resin composition becomes more excellent in photosensitive and curability, and a cured product having higher hardness and higher transparency can be obtained.
- the polyfunctional polymerizable compound it is more preferable to use a trifunctional or higher functional (meth) acrylate compound.
- the above polymerizable compound may be used alone or in combination of two or more.
- the content of the polymerizable compound is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately set, but a photosensitive resin composition is suitable. From the viewpoint of 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 preferably includes a radically polymerizable photopolymerization initiator.
- the radically polymerizable photoinitiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam.
- the photopolymerization initiator examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-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-morpho) Aminoketone compounds such as phosphorus-4-yl-phenyl) -butane-1-one (“IRGACURE379”, manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one (“IRGACURE651”, “IRGACURE651”, Benzyl ketal compounds such as BASF), phenylglycylic acid methyl ester (“DAROCUR MBF”, BASF); 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE90
- alkylphenone-based compounds exemplified in paragraphs [0084] to [0086] of No. 227485; 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime).
- the content of the photopolymerization initiator is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately set.
- 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 with respect to the mass%.
- the photosensitive resin composition of the present invention preferably further contains a photoacid generator.
- a photoacid generator is a compound that generates an acid when exposed to active energy rays such as radiation, and is, for example, a strong acid such as toluene sulfonic acid or boron tetrafluoride, a sulfonium salt, an ammonium salt, or a phosphonium salt.
- Onium salts such as iodonium salt or selenium salt; iron-allene complexes; silanol-metal chelate complexes; disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidesulfonates, benzoinsulfonates, etc. Examples thereof include sulfonic 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 may contain other components in addition to the above-mentioned components, if necessary.
- examples of the above other components include solvents; coloring materials (pigments, dyes); dispersants; heat resistant improvers; leveling agents; developing aids; inorganic fine particles such as silica fine particles; silane-based, aluminum-based, titanium-based, and the like.
- thermosetting resin such as filler, epoxy resin, phenol resin, polyvinylphenol
- curing aid such as polyfunctional thiol compound
- plasticizer polymerization inhibitor
- ultraviolet absorber antioxidant
- matting agent Antifoaming agents
- antistatic agents slip agents
- surface modifiers rocking agents
- rocking aids quinonediazide compounds
- polyhydric phenol compounds cationically polymerizable compounds
- acid generators etc.
- thermosetting resin such as filler, epoxy resin, phenol resin, polyvinylphenol
- curing aid such as polyfunctional thiol compound
- plasticizer polymerization inhibitor
- ultraviolet absorber antioxidant
- slip agents surface modifiers
- rocking agents rocking aids
- quinonediazide compounds polyhydric phenol compounds
- cationically polymerizable compounds acid generators; etc.
- these may be used individually by 1 type, or may be used in combination of 2 or more type.
- these other components may be
- the method for preparing the photosensitive resin composition of the present invention is not particularly limited, and a known method may be used.
- each of the above-mentioned contained components is mixed and dispersed using various mixers and dispersers.
- the method can be mentioned.
- the mixing / dispersing step is not particularly limited and may be carried out by a known method. It may also further include other steps that are normally performed.
- the photosensitive resin composition contains a coloring material, it is preferably prepared through a known step such as a dispersion treatment step of the coloring material.
- the copolymer, the copolymer solution, or the cured product obtained by curing the photosensitive resin composition (curable resin composition) of the present invention has excellent solvent resistance.
- a cured product of such a copolymer, a copolymer solution, or a photosensitive resin composition is also one of the present inventions.
- the film thickness is preferably 0.1 ⁇ m or more. When the film thickness is 0.1 ⁇ m or more, even better solvent resistance can be exhibited.
- the film thickness is more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more.
- the upper limit of the film thickness is not particularly limited and may be appropriately set according to the purpose and application 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 more preferable to have.
- the method for obtaining the cured product is not particularly limited, and a known method may be used.
- the above-mentioned copolymer, copolymer solution, or photosensitive resin composition may be applied or applied onto a substrate.
- a method of obtaining a cured product by drying, heating, irradiating an energy ray such as ultraviolet rays, or a combination thereof to cure the molded product.
- the copolymer, the copolymer solution, or the photosensitive resin composition of the present invention it is possible to provide a cured product having excellent solvent resistance even under low temperature curing conditions.
- the method for producing such a cured product include a step of applying the photosensitive resin composition on a substrate to form a coating film, a step of irradiating the formed coating film with light, and light irradiation.
- a method including a step of heating the coated coating film at 160 ° C. or lower is preferable.
- the base material is not particularly limited and may be appropriately selected depending on the purpose and application. Examples thereof include base materials made of various materials such as a glass plate and a plastic plate.
- the method of applying the photosensitive resin composition to form a coating film is not particularly limited, and known methods such as spin coating, slit coating, roll coating, and cast coating can be used.
- the above-mentioned drying can be carried out by a known method, and specifically, can be carried out by the same method as the drying method described in the "arrangement step" of the " ⁇ color filter manufacturing method>" described later.
- the manufacturing method includes a step of irradiating the coating film with light after forming the coating film.
- the method of irradiating the formed coating film with light is not particularly limited and can be performed by a known method. Specifically, the "light irradiation step" of " ⁇ Manufacturing method of color filter>” described later. It can be carried out by the same method as described in 1.
- light irradiation When irradiating the coating film with light, light irradiation may be performed via a photomask.
- the photomask it is preferable to use a mask in which a light-shielding portion is formed according to a target pattern.
- a development step By performing the developing step, a desired pattern can be formed on the coating film.
- the developing method is not particularly limited and can be carried out by a known method. Specifically, the developing method is the same as the method described in "Development step" of " ⁇ Color filter manufacturing method>" described later. be able to.
- the manufacturing method also includes a step of heating the light-irradiated coating film at 160 ° C. or lower. Since the above-mentioned photosensitive resin composition is used in the above-mentioned production method, the heating step (post-curing step) after light irradiation 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, and more preferably 90 ° C. or higher in terms of maintaining curability.
- the heating method other than the temperature is not particularly limited and can be performed by a known method. For example, the same method as described in the “heating step” of “ ⁇ Color filter manufacturing method>” described later can be used. It can be carried out.
- the copolymer, the copolymer solution, and the photosensitive resin composition (curable resin composition) containing the copolymer of the present invention sufficiently proceed with the curing reaction even under low temperature curing conditions of 160 ° C or lower, for example, about 90 ° C.
- the copolymer, copolymer solution, and photosensitive resin composition of the present invention may be, for example, a liquid crystal display, an organic EL, a quantum dot, a micro LED liquid crystal display device, a solid-state image pickup device, a touch panel display device, or the like.
- Various optical members such as color filters, black matrices, photo spacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, insulating films, films, organic protective films, etc. It can be suitably used for applications of constituent members such as devices. Among them, it is preferably used for color filter applications.
- the photosensitive resin composition of the present invention is suitably used for optical materials, and is also preferably used for negative molds.
- a color filter having a cured product of the above-mentioned photosensitive resin composition on a color filter substrate is also one of the preferred embodiments of the present invention.
- the cured product formed by the above-mentioned photosensitive resin composition is particularly suitable as a black matrix or a segment requiring coloring such as each pixel of red, green, blue, yellow and the like.
- it is also suitable as a segment that does not necessarily require coloring, such as a photo spacer, a protective layer, and an orientation control rib.
- the substrate used for the color filter examples include glass substrates such as white plate glass, blue plate glass, alkali-reinforced glass, and silica-coated blue plate glass; a ring-opening polymer of polyester, polycarbonate, polyolefin, polysulfone, and cyclic olefin, and hydrogen thereof.
- a step of arranging the above-mentioned photosensitive resin composition on a substrate also referred to as an arranging step for each pixel color (that is, for each pixel of one color) and on the substrate.
- a step of irradiating the arranged photosensitive resin composition with light also referred to as a light irradiation step
- a step of developing with a developing solution also referred to as a developing step
- a step of heat treating also referred to as a heating step
- the order of forming the pixels of each color is not particularly limited.
- Arrangement step (preferably coating step) It is preferable that the arrangement step is performed by coating.
- the method for applying the photosensitive resin composition on the substrate include spin coating, slit coating, roll coating, cast coating, and the like, and any of these methods can be preferably used.
- the arrangement step it is also preferable to apply the photosensitive resin composition on the substrate and then dry the coating film.
- the coating film can be dried by using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but usually, the drying is performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. Suitable.
- Light irradiation step As the light source of the active light used in the above light irradiation step, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and the like.
- 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 excima laser, a nitrogen laser, a helium cadmium laser, or a semiconductor laser is used.
- examples of the exposure machine method include a proximity method, a mirror projection method, and a stepper method, and the proximity method is preferably used.
- the active energy ray may be irradiated through a predetermined mask pattern depending on the application.
- the exposed portion is cured, and the cured portion is insoluble or sparingly soluble in the developing solution.
- the development step is a step of developing with a developer after the light irradiation step described above to remove an unexposed portion and form a pattern. This makes it possible to obtain a patterned cured film.
- the development process can usually be performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, and ultrasonic development.
- the developer used in the developing step is not particularly limited as long as it dissolves the photosensitive resin composition, but an organic solvent or an alkaline aqueous solution is usually used, and a mixture thereof may be used.
- an alkaline aqueous solution is used as the developing solution, it is preferable to wash it with water after developing.
- the organic solvent and the alkaline aqueous solution include the same as those described in JP-A-2015-157909.
- the heating step is a step of further curing the exposed portion (cured portion) by firing after the above-mentioned developing step (also referred to as “post-curing step”).
- post-curing step a step of post-exposure with a light amount of 0.5 to 5 J / cm 2 using a light source such as a high-pressure mercury lamp, a step of post-heating at a temperature of 60 to 200 ° C. for 10 seconds to 120 minutes, and the like can be mentioned. Be done.
- a post-curing step it becomes possible to further strengthen the hardness and adhesion of the patterned cured film.
- the heating step is generally performed at a temperature of about 200 to 260 ° C., but if the photosensitive resin composition is used, the heating step is performed under relatively low temperature conditions of 200 ° C. or lower, preferably 160 ° C. or lower. Sufficient curing can be performed. Therefore, it is possible to obtain a product having excellent solvent resistance without impairing the characteristics retained by the substrate and 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 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 for example, it can be performed by using a heating device such as a hot plate, a convection oven, or a high frequency heater.
- the film 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, still more preferably 1 to 10 ⁇ m.
- Display device A display device including the above-mentioned color filter is also one of the preferred embodiments of the present invention.
- Display device members and display devices having a cured product of the photosensitive resin composition are also included in a preferred embodiment of the present invention.
- the cured product (cured film) formed by the photosensitive resin composition is stable, has excellent adhesion to a substrate or the like, has high hardness, exhibits high smoothness, and has 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, or the like is suitable.
- the cured product cured film
- the member may be a film-shaped single-layer or multilayer member composed of the cured film, or the single-layer or multilayer member. It may be a member in which another layer is further combined with the member of the above, or it may be a member including the cured film in the composition.
- the copolymer, the copolymer solution, and the photosensitive resin composition (curable resin composition) of the present invention provide a cured product having excellent solvent resistance even under low-temperature curing conditions. be able to.
- the copolymer, copolymer solution, and photosensitive resin composition of the present invention are various optical members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image pickup devices, touch panel display devices, and the like. And as a constituent member, it can be suitably used for various applications such as electric and electronic devices.
- part means “part by mass”
- % means “% by mass”.
- Weight average molecular weight The weight average molecular weight was measured by the GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.
- Epoxy equivalent (g / equivalent) It was determined by dividing the mass (g) of the solid content of the copolymer by the number of moles (mol) of the epoxy groups contained in the copolymer.
- Double bond equivalent (g / equivalent) It was determined by dividing the mass (g) of the solid content of the copolymer by the double bond amount (mol) of the copolymer.
- the solvent-resistant photosensitive resin composition is spin-coated on a 5 cm square glass substrate, dried at 100 ° C. for 3 minutes, exposed at 200 mJ using a high-pressure mercury lamp, and at 90 ° C. or 110 ° C. Each was heat-treated (post-cured) for 40 minutes to obtain a cured film having a film thickness of 2 ⁇ m. Then, the cured film was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 40 ° C. for 10 minutes and then taken out, and the immersion liquid (NMP) after the cured film was taken out was measured with a spectrophotometer UV3100 (Shimadzu Corporation).
- NMP 1-methyl-2-pyrrolidone
- the absorbance was measured by (manufactured by) and evaluated according to the following criteria. The larger the absorbance value, the more the coloring material is eluted in the immersion liquid, and it is evaluated that the solvent resistance of the photosensitive resin composition is low. (Evaluation criteria) ⁇ : Absorbance value is less than 0.2 ⁇ : Absorbance value is 0.2 or more and less than 0.3 ⁇ : Absorbance value is 0.3 or more and less than 0.4 ⁇ : Absorbance value is 0.4 or more XX : Film peeling
- Viscosity The viscosity of the copolymer solution was measured at 25 ° C. using a viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.).
- the residual film ratio was calculated by measuring the weight of the film before and after the evaluation of the solvent resistance in (7) above. Specifically, the film weight before the solvent resistance evaluation was calculated by using the glass substrate as the tare weight. After that, the residual film ratio was calculated by dividing the film weight after the solvent resistance evaluation by the film weight before the evaluation.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 43.6 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 43.6 parts of vinyl toluene, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol monomethyl ether were placed in a beaker.
- a mixture of 2.0 parts of n-dodecyl mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction vessel reached 90 ° C., the dropping was started from the dropping tank over 3 hours while maintaining the same temperature, and the polymerization was carried out. After the dropping was completed, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride, 0.33 parts of triethylamine as a catalyst, 29.0 parts of propylene glycol monomethyl ether acetate were reacted at 60 ° C. for 10 hours to prepare the copolymer solution A-3. Obtained. Table 1 shows various physical properties of the obtained copolymer.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 43.6 parts of 2-ethylhexyl acrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol were placed in a beaker.
- a mixture of 2.0 parts of n-dodecyl mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction vessel reached 90 ° C., the dropping was started from the dropping tank over 3 hours while maintaining the same temperature, and the polymerization was carried out. After the dropping was completed, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride, 0.33 parts of triethylamine as a catalyst, 29.0 parts of propylene glycol monomethyl ether acetate were reacted at 60 ° C. for 10 hours to prepare the copolymer solution A-4. Obtained. Table 1 shows various physical properties of the obtained copolymer.
- copolymer solution A-5 SAH adduct solution of BzMI-CHMA-HEAA-GMA copolymer
- a reaction vessel equipped with a thermometer, agitator, gas introduction tube, cooling tube and dropping tank introduction port After charging 85.6 parts of ethyl methyl ether and substituting with nitrogen, the mixture was heated and heated to 90 ° C.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 46.65 parts of cyclohexyl methacrylate, 26.8 parts of N-hydroxyethyl acrylamide, 16.55 parts of glycidyl methacrylate, and diethylene glycol ethyl methyl ether were placed in a beaker.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 46.65 parts of cyclohexyl methacrylate, 30.0 parts of glycerin monomethacrylate (“Blemmer GL” manufactured by Nippon Yushi Co., Ltd.), glycidyl methacrylate 13 in a beaker.
- a mixture of 4.0 parts of n-dodecyl mercaptan and 67.4 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a dropping tank (B). After the temperature of the reaction vessel reached 90 ° C., the dropping was started from the dropping tank over 3 hours while maintaining the same temperature, and the polymerization was carried out. After the dropping was completed, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and aging was performed for 90 minutes. Then, after cooling to room temperature, 11.5 parts of succinic anhydride and 4.7 parts of propylene glycol monomethyl ether acetate were reacted at 60 ° C. for 10 hours to obtain a copolymer solution A-7. Table 1 shows various physical properties of the obtained copolymer.
- the dropping tank (A) 10.0 parts of N-benzylmaleimide, 19.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 41.0 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 14.3 parts of cyclohexyl methacrylate, 55.0 parts of 2-hydroxyethyl methacrylate, 20.7 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- the dropping tank (A) in a beaker, 10.0 parts of methyl ⁇ - (allyloxymethyl) acrylate, 43.6 parts of tertiary butyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, and glycidyl methacrylate 16.4 parts, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl (registered trademark) O” manufactured by Nippon Oil & Fats Co., Ltd.) are stirred and mixed.
- the dropping tank (A) 10.0 parts of N-cyclohexylmaleimide, 43.6 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 27.5 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 32.5 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 29.0 parts of 2-ethylhexyl acrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 31.0 parts of glycidyl methacrylate, and propylene glycol were placed in a beaker.
- a mixture of 2.0 parts of n-dodecyl mercaptan and 31.33 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction vessel reached 90 ° C., the dropping was started from the dropping tank over 3 hours while maintaining the same temperature, and the polymerization was carried out. After the dropping was completed, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the mixture was aged for 90 minutes.
- the dropping tank (A) 20.0 parts of N-benzylmaleimide, 25.0 parts of cyclohexyl methacrylate, 50.0 parts of 2-hydroxyethyl methacrylate, 5.0 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- a dropping tank (A) 30.0 parts of N-benzylmaleimide, 10.0 parts of cyclohexyl methacrylate, 10.0 parts of 2-hydroxyethyl methacrylate, 50.0 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- a mixture of 6.0 parts of n-dodecyl mercaptan and 82.24 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction vessel reached 90 ° C., the dropping was started from the dropping tank over 3 hours while maintaining the same temperature, and the polymerization was carried out. After the dropping was completed, the temperature was maintained at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C., and the mixture was aged for 90 minutes. Then, after cooling to room temperature, 22.8 parts of acrylic acid, 0.37 parts of triphenylphosphine and 0.18 parts of Antage W-400 as a catalyst were reacted at 85 ° C. for 12 hours.
- a dropping tank (A) 10.0 parts of N-benzylmaleimide, 29.3 parts of cyclohexyl methacrylate, 40.0 parts of 2-hydroxyethyl methacrylate, 20.7 parts of glycidyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
- Pigment Dispersion 1 (Preparation of Pigment Dispersion 1) 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparon DA-7301 as a dispersant, and C.I. I. Pigment Green 58, 2.25 copies, and C.I. I. Pigment Yellow 138 was mixed in 1.5 parts and dispersed in a paint shaker for 3 hours to obtain Pigment Dispersion 1 (solid content 22% by mass).
- Example 1 In terms of solid content, 35.0 parts of the copolymer solution A-1, 30.0 parts of dipentaerythritol hexaacrylate as the radically polymerizable compound, and Irgacure OXE-02 (manufactured by BASF Japan) as the radically polymerizable photopolymerization initiator. ), 30.0 parts of the pigment dispersion 1, and a diluting solvent (propylene glycol monomethyl ether acetate) so as to have a solid content concentration of 20%, and stirring to make the photosensitive resin composition 1 Got
- a diluting solvent propylene glycol monomethyl ether acetate
- Photosensitive resin compositions 2 to 20 were obtained in the same manner as in Example 1 except that the formulations shown in Table 2 were used. The solvent resistance of the obtained photosensitive resin compositions 1 to 20 was evaluated. The results are shown in Table 2.
- the photosensitive resin composition containing a copolymer having an epoxy group-containing structural unit and a long-chain acid group-containing structural unit and having an epoxy equivalent of 20000 or less is cured at a low temperature of 90 ° C. or 110 ° C. It was found that even under the conditions, a cured product having good curability and excellent solvent resistance was given.
- Example 19 Comparative Example 3 (Confirmation of storage stability) The following operation was performed to investigate the effect of storage stability with the diluting solvent.
- this product changes in the physical properties (weight average molecular weight and viscosity) of the copolymer before and after storage at 40 ° C. for 2 weeks were confirmed.
- the ratio (%) of the difference between the weight average molecular weight before and after storage with respect to the weight average molecular weight before storage was shown.
- the viscosity the ratio (%) of the difference in viscosity before and after storage to the viscosity before storage was shown.
- Copolymer solution A-20 is obtained by the same preparation method as in copolymer solution A-19 except that propylene glycol monomethyl ether acetate is added instead of propylene glycol monomethyl ether. rice field. Table 4 shows various physical properties of the obtained copolymer.
- Example 20 In terms of solid content, 35.0 parts of the copolymer solution A-19, 30.0 parts of dipentaerythritol hexaacrylate as the radically polymerizable compound, and Irgacure OXE-02 (manufactured by BASF Japan) as the radically polymerizable photopolymerization initiator. ), 30.0 parts of the pigment dispersion 1, 1.0 part of P-2M (light ester P-2M, pKa: 1.29, manufactured by Kyoeisha Chemical Co., Ltd.), and a diluting solvent (propylene glycol monomethyl). Ether acetate) was added so as to have a solid content concentration of 20%, and the mixture was stirred to obtain a photosensitive resin composition 21.
- P-2M light ester P-2M, pKa: 1.29, manufactured by Kyoeisha Chemical Co., Ltd.
- a diluting solvent propylene glycol monomethyl
- Photosensitive resin compositions 22 to 24 were obtained in the same manner as in Example 20 except that the formulations shown in Table 5 were used. The solvent resistance of the obtained photosensitive resin compositions 21 to 24 was evaluated. The results are shown in Table 5.
- the photosensitive resin composition containing a copolymer having an epoxy group-containing structural unit and an acid group-containing structural unit and having an epoxy equivalent of 20000 or less can be obtained even under low-temperature curing conditions at 90 ° C. It can be seen that the curability is good and the solvent resistance is excellent.
- Examples 24-40 (Confirmation of storage stability) To 100 parts (as-is) of the copolymer solution, add the diluting solvent (propylene glycol monomethyl ether) and P-1M, P-2M, MSA, or ACA in the amounts shown in Table 6 or Table 7. A copolymer solution was prepared.
- the amount of the diluting solvent corresponds to 129.6% by mass with respect to 100% by mass of the copolymer solid content in Table 6 (35 parts), and corresponds to 129.6% by mass with respect to 100% by mass of the copolymer solid content in Table 7 (8 parts). It corresponds to 29.6% by mass.
- P-1M Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.) 2-Metachloroxyethyl Acid Phosphate, pKa: 1.78, Molecular Weight: 210.12
- P-2M Light Ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.) 2-Metacloyloxyethyl acid phosphate, pKa: 1.29, molecular weight: 322.25
- MSA Methanesulfonic acid, pKa: -2.6, Molecular weight: 96.1 ACA: acetic acid, pKa: 4.76, molecular weight: 60.05
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Abstract
Description
近年では、光学部材や電機・電子機器等の小型化・薄型化・省エネルギー化が進みつつあり、それに伴って、使用される各種部材等にはより高品位な性能が要望されている。そのような要望に応えるため、各種部材等の材料となる硬化性樹脂について研究が行われている。
例えば、特許文献1には、側鎖にカルボキシル基及び光反応性不飽和基を有し、アルカリ水溶液に可溶性であるオリゴマーと、エポキシ基を有する化合物と、増感剤と、ジシアンジアミド変性物を含む感光性樹脂組成物が記載されている。
また例えば、特許文献2には、エポキシ基またはオキセタニル基を有するラジカル重合性モノマー、カルボキシル基を有するラジカル重合性モノマー等を重合させて得られるアルカリ可溶性重合体を含む感光性組成物が記載されている。
また例えば、特許文献3には、単独重合体としたときにガラス転移温度が10℃以下となる(メタ)アクリレートモノマー、エポキシ基またはカルボキシル基を有する(メタ)アクリレートモノマー等の付加共重合体に、特定の変性反応を行うことによって得られる側鎖に酸基、ヒドロキシ基及び重合性不飽和結合をする硬化性ポリマー、上記硬化性ポリマーを含む感光性重合体組成物が記載されている。
特許文献1に記載の従来の感光性樹脂組成物では、樹脂の合成において高い温度が必要とされていた。また、樹脂の硬化性において改善の余地があった。
なお、以下において記載する本発明の個々の好ましい形態を2つ以上組み合わせたものもまた、本発明の好ましい形態である。
また、本明細書において、「(メタ)アクリル酸」は、「アクリル酸及び/又はメタクリル酸」を意味し、「(メタ)アクリレート」は、「アクリレート及び/又はメタクリレート」を意味する。
本発明の共重合体は、下記一般式(1)で表されるエポキシ基含有構造単位(A)と、下記一般式(2)で表される酸基含有構造単位(B)とを有し、エポキシ当量が20000以下であることを特徴とする。
上記エポキシ当量は、共重合体固形分量を共重合体中に含まれるエポキシ基のモル数で除すことで求めることができる。また、上記エポキシ当量は、JIS K7236:2001に準拠した方法でも求めることができる。
本発明の共重合体は、上記一般式(1)で表されるエポキシ基含有構造単位(A)を有する。
上記一般式(1)中、R1は、水素原子又はメチル基を表す。
R2は、直接結合、又は、2価の有機基を表す。上記有機基としては、鎖状もしくは環状の飽和又は不飽和の炭化水素基、-O-、-CO-、-COO-、-NH-、-S-、-SO-、-SO2-、及び、これらの組み合わせからなる2価の基等が挙げられる。
上記炭化水素基としては、2価の脂肪族炭化水素基、脂環族炭化水素基、芳香族炭化水素基が挙げられる。
上記脂肪族炭化水素基としては、直鎖状又は分岐状であってもよく、例えばメチレン基、エチレン基、トリメチレン基、プロピレン基、エチリデン基、プロピリデン基、イソプロピリデン基等のアルキレン基や、ビニレン基、プロペニレン基、ビニリデン基等が挙げられる。
上記脂環族炭化水素基としては、例えば1,2-シクロペンチレン基、1,2-シクロへキシレン基、シクロペンチリデン基、シクロヘキシリデン基等のシクロアルキレン基等が挙げられる。
上記芳香族炭化水素基としては、例えば1,2-フェニレン基、1,2-ナフチレン基、2,3-ナフチレン基、ベンジリデン基、シンナミリデン基、ビフェニリレン基等が挙げられる。
上記エポキシ基含有基としては、例えば、下記式(x1)~(x4)で表される基が好ましく挙げられる。
mは、1~10の整数であり、好ましくは2~8の整数であり、より好ましくは3~6の整数である。
なかでも、Xとしては、反応性の点で、(x1)が好ましく、n=1である(x1)がより好ましい。
R6で表される2価の有機基としては、例えば、上述したR2で表される2価の有機基と同様の基を挙げることができる。
R6で表される2価の有機基の炭素数は、0~10であることが好ましく、1~4であることがより好ましく、1~2であることが更に好ましい。
上記構造単位(A)を導入しうる単量体としては、例えば、下記式(a)で表される化合物が挙げられる。
本発明の共重合体は、更に、上記一般式(2)で表される酸基含有構造単位(B)を有する。
R4は、直接結合、又は有機基を表す。R4で表される有機基としては、上述したR2で表される有機基と同様の基等が挙げられる。
R4で表される有機基の原子数は、1~10であることが好ましく、1~8であることがより好ましく、2~5であることが更に好ましい。
R4で表される有機基としては、置換基を有してもよい2価の有機基が好ましく、エステル結合を含む2価の有機基が好ましく、-CO-O-R-(Rは、炭素数1~3の2価の脂肪族炭化水素基を表す。)、-CO-O-R(-O-CO-R’)-(Rは、炭素数1~3の直鎖状又は分岐鎖状の2価の脂肪族炭化水素基を表す。R’は、炭素数1~3の1価の脂肪族炭化水素基を表す。)がより好ましく、-CO-O-R-(Rは、炭素数1~3の2価の脂肪族炭化水素基を表す。)が更に好ましい。
なかでも、上記有機基は、-R-、-O-R-、-O-R-O-、-CO-R-、-O-R-O-CO-R’-(R及びR’は、同一又は異なって、置換基を有してもよい2価の炭化水素基を表す。)であることが好ましく、-R-、-O-R-、-O-R-O-CO-R’-(R及びR’は、同一又は異なって、置換基を有してもよい2価の脂肪族炭化水素基を表す。)であることがより好ましく、エチレン基であることが更に好ましい。
また、2つ以上の酸基を有していてもよい。
R7及びR8で表される有機基としては、上述した2価の有機基等が好ましく挙げられるが、なかでも、R7としては、置換基を有してもよい2価の炭化水素基が好ましく、置換基を有してもよい2価の脂肪族炭化水素基がより好ましく、アルキレン基が更に好ましい。
R8としては、置換基を有してもよい2価の炭化水素基が好ましく、置換基を有してもよい2価の脂肪族炭化水素基がより好ましく、アルキレン基が更に好ましい。
本発明の共重合体は、更に、主鎖に環構造を有する共重合体であることが好ましい。すなわち、上記共重合体は、主鎖に環構造を有する構造単位(C)を更に有することが好ましい。上記共重合体が主鎖に環構造を有する重合体であると、耐熱性にも優れた硬化物を与えることができる。
上記環構造としては、イミド環、テトラヒドロピラン環、テトラヒドロフラン環、ラクトン環等が挙げられる。
主鎖に環構造を導入しうる単量体を含む単量体成分を重合することにより、上記構造単位(C)を有する共重合体を得ることができる。
上記α-(アリルオキシメチル)アクリレート系単量体の具体例としては、例えば、α-アリルオキシメチルアクリル酸;α-アリルオキシメチルアクリル酸メチル、α-アリルオキシメチルアクリル酸エチル、α-アリルオキシメチルアクリル酸n-プロピル、α-アリルオキシメチルアクリル酸i-プロピル、α-アリルオキシメチルアクリル酸n-ブチル、α-アリルオキシメチルアクリル酸s-ブチル、α-アリルオキシメチルアクリル酸t-ブチル、α-アリルオキシメチルアクリル酸n-アミル、α-アリルオキシメチルアクリル酸s-アミル、α-アリルオキシメチルアクリル酸t-アミル、α-アリルオキシメチルアクリル酸n-ヘキシル、α-アリルオキシメチルアクリル酸s-ヘキシル、α-アリルオキシメチルアクリル酸n-ヘプチル、α-アリルオキシメチルアクリル酸n-オクチル、α-アリルオキシメチルアクリル酸s-オクチル、α-アリルオキシメチルアクリル酸t-オクチル、α-アリルオキシメチルアクリル酸2-エチルヘキシル、α-アリルオキシメチルアクリル酸カプリル、α-アリルオキシメチルアクリル酸ノニル、α-アリルオキシメチルアクリル酸デシル、α-アリルオキシメチルアクリル酸ウンデシル、α-アリルオキシメチルアクリル酸ラウリル、α-アリルオキシメチルアクリル酸トリデシル、α-アリルオキシメチルアクリル酸ミリスチル、α-アリルオキシメチルアクリル酸ペンタデシル、α-アリルオキシメチルアクリル酸セチル、α-アリルオキシメチルアクリル酸ヘプタデシル、α-アリルオキシメチルアクリル酸ステアリル、α-アリルオキシメチルアクリル酸ノナデシル、α-アリルオキシメチルアクリル酸エイコシル、α-アリルオキシメチルアクリル酸セリル、α-アリルオキシメチルアクリル酸メリシル等のアルキル-(α-アリルオキシメチル)アクリレート系単量体;α-アリルオキシメチルアクリル酸メトキシエチル、α-アリルオキシメチルアクリル酸メトキシエトキシエチル、α-アリルオキシメチルアクリル酸メトキシエトキシエトキシエチル、α-アリルオキシメチルアクリル酸3-メトキシブチル、α-アリルオキシメチルアクリル酸エトキシエチル、α-アリルオキシメチルアクリル酸エトキシエトキシエチル、α-アリルオキシメチルアクリル酸フェノキシエチル、α-アリルオキシメチルアクリル酸フェノキシエトキシエチル等のアルコキシアルキル-(α-アリルオキシメチル)アクリレート系単量体;α-アリルオキシメチルアクリル酸ヒドロキシエチル、α-アリルオキシメチルアクリル酸ヒドロキシプロピル、α-アリルオキシメチルアクリル酸ヒドロキシブチル、α-アリルオキシメチルアクリル酸フルオロエチル、α-アリルオキシメチルアクリル酸ジフルオロエチル、α-アリルオキシメチルアクリル酸クロロエチル、α-アリルオキシメチルアクリル酸ジクロロエチル、α-アリルオキシメチルアクリル酸ブロモエチル、α-アリルオキシメチルアクリル酸ジブロモエチル、α-アリルオキシメチルアクリル酸ビニル、α-アリルオキシメチルアクリル酸アリル、α-アリルオキシメチルアクリル酸メタリル、α-アリルオキシメチルアクリル酸クロチル、α-アリルオキシメチルアクリル酸プロパギル、α-アリルオキシメチルアクリル酸シクロペンチル、α-アリルオキシメチルアクリル酸シクロヘキシル、α-アリルオキシメチルアクリル酸4-メチルシクロヘキシル、α-アリルオキシメチルアクリル酸4-t-ブチルシクロヘキシル、α-アリルオキシメチルアクリル酸トリシクロデカニル、α-アリルオキシメチルアクリル酸イソボルニル、α-アリルオキシメチルアクリル酸アダマンチル、α-アリルオキシメチルアクリル酸ジシクロペンタジエニル、α-アリルオキシメチルアクリル酸フェニル、α-アリルオキシメチルアクリル酸メチルフェニル、α-アリルオキシメチルアクリル酸ジメチルフェニル、α-アリルオキシメチルアクリル酸トリメチルフェニル、α-アリルオキシメチルアクリル酸4-t-ブチルフェニル、α-アリルオキシメチルアクリル酸ベンジル、α-アリルオキシメチルアクリル酸ジフェニルメチル、α-アリルオキシメチルアクリル酸ジフェニルエチル、α-アリルオキシメチルアクリル酸トリフェニルメチル、α-アリルオキシメチルアクリル酸シンナミル、α-アリルオキシメチルアクリル酸ナフチル、α-アリルオキシメチルアクリル酸アントラニル;等が挙げられる。なかでも、アルキル-(α-アリルオキシメチル)アクリレート系単量体が好適である。上記アルキル-(α-アリルオキシメチル)アクリレート系単量体としては、透明性や分散性、工業的入手の容易さ等の観点から、α-アリルオキシメチルアクリル酸メチル(メチル-(α-アリルオキシメチル)アクリレートとも称する)が特に好適である。
上記共重合体は、上述した構造単位(A)、(B)及び(C)以外に、他の構造単位(D)を更に有していてもよい。上記構造単位(D)としては、例えば、上述した水酸基含有単量体の他、上述した長鎖不飽和モノカルボン酸類以外の酸基含有単量体、(メタ)アクリル酸エステル系単量体、酸基を生成する基を有する単量体、他の共重合可能な単量体等に由来する構造単位が挙げられる。
上記熱もしくは酸により酸基を生成する基としては、例えば、3級炭素含有基、ビニルエーテル化合物により酸基がブロック化された基、t-ブチル基やアセチル基等の保護基によりフェノール性水酸基が保護された基、等が挙げられる。
Raの炭素数は、より好ましくは炭素数1~50であり、更に好ましくは炭素数1~35であり、更により好ましくは炭素数1~20であり、特に好ましくは炭素数1~12であり、最も好ましくは炭素数1~9である。
上記Rb、Rc及びRdは、同一又は異なって、炭素数1~15の飽和炭化水素基であることが好ましく、より好ましくは炭素数1~10の飽和炭化水素基、更に好ましくは炭素数1~5の飽和炭化水素基、特に好ましくは炭素数1~3の飽和炭化水素基である。
上記Raは、好ましくはt-ブチル基、t-アミル基である。
上記ビニルエーテル化合物としては、例えば、メチルビニルエーテル、エチルビニルエーテル、i-プロピルビニルエーテル、n-プロピルビニルエーテル、n-ブチルビニルエーテル、i-ブチルビニルエーテル、t-ブチルビニルエーテル、2-エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル等の脂肪族ビニルエーテル化合物や、ジヒドロピラン等の、開環してビニルエーテルを生じうる環状エーテル化合物等が挙げられる。
上記ビニルエーテル化合物のなかでも、より低温で保護基が脱離しやすい点で、ジヒドロピランが好ましい。
N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-イソプロピルアクリルアミド等の(メタ)アクリルアミド類;ポリスチレン、ポリメチル(メタ)アクリレート、ポリエチレンオキシド、ポリプロピレンオキシド、ポリシロキサン、ポリカプロラクトン、ポリカプロラクタム等の重合体分子鎖の片末端に(メタ)アクリロイル基を有するマクロモノマー類;1,3-ブタジエン、イソプレン、クロロプレン等の共役ジエン類;酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル類;スチレン、ビニルトルエン、α-メチルスチレン、キシレン、メトキシスチレン、エトキシスチレン等の芳香族ビニル類;メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、2-エチルヘキシルビニルエーテル、n-ノニルビニルエーテル、ラウリルビニルエーテル、シクロヘキシルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、メトキシエトキシエチルビニルエーテル、メトキシポリエチレングリコールビニルエーテル、2-ヒドロキシエチルビニルエーテル、4-ヒドロキシブチルビニルエーテル等のビニルエーテル類;N-ビニルピロリドン、N-ビニルカプロラクタム、N-ビニルイミダゾール、N-ビニルモルフォリン、N-ビニルアセトアミド等のN-ビニル化合物類;(メタ)アクリル酸イソシアナトエチル、アリルイソシアネート等の不飽和イソシアネート類;等が挙げられる。
また、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸N,N-ジエチルアミノエチル等のアミン基を有するモノマーを使用する場合も、触媒を使用することなく付加反応を行うことができ、共重合体の保存安定性を向上させることができる。
上記側鎖の長い単量体としては、単量体の最も長い側鎖の原子数が5~20であるものが好ましく、6~20であるものがより好ましく、7~10であるものが更に好ましい。上記側鎖は、直鎖状であっても分岐状であってもよい。上記側鎖の長い単量体の具体例としては、(メタ)アクリル酸2-エチルヘキシルが好ましく挙げられる。
上記酸価は、水酸化カリウム(KOH)溶液を用いた中和滴定法により測定して得られる値であり、重合体固形分1gあたりの酸価である。
上記共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定することができ、具体的には実施例に記載の方法で測定することができる。
本発明の共重合体を製造する方法としては、少なくとも上述の構造単位(A)と構造単位(B)とを有し、所定範囲のエポキシ当量を有する共重合体を得ることができる方法であれば、特に制限されず、例えば、上述した各構造単位を導入しうる単量体を含む単量体成分を重合する方法や、単量体成分を重合してベースポリマーを得て、上記ベースポリマーが有する基に他の化合物を付加反応させ、所定の構造単位を有する重合体を得る方法等が挙げられる。
また上記単量体成分を重合して得られる重合体の分子量は、重合開始剤の量や種類、重合温度、連鎖移動剤の種類や量を適宜調整することにより制御することができる。
このような方法で上記共重合体を製造することにより、共重合体の製造時にゲル化が生じるのを抑制することができ、上記構造単位(A)と構造単位(B)を有する共重合体を効率良く得ることができる。
すなわち、本発明はまた、式(a)で表されるエポキシ基含有単量体、及び、式(b1)で表される水酸基含有単量体を含む単量体成分を重合する工程(1)と、上記重合工程(1)で得られた重合体と、上記式(b2)又は式(b3)で表される酸基含有化合物を反応させる工程(2)を含むことを特徴とする共重合体の製造方法である。
工程(1)
本発明の共重合体の製造方法において、上記式(a)で表されるエポキシ基含有単量体、及び、上記式(b1)で表される水酸基含有単量体を含む単量体成分を重合する。
上記式(a)で表されるエポキシ基含有単量体としては、例えば、上述した共重合体の構造単位(A)を導入しうる単量体として記載した単量体等が挙げられる。上記式(b1)で表される上記水酸基含有単量体としては、上述したものが挙げられる。
次いで、上記工程(1)で得られた重合体と、上記式(b2)又は式(b3)で表される酸基含有化合物を反応させる工程を含む。
上記工程(1)で得られた重合体(ベースポリマー)と、上記式(b2)又は式(b3)で表される酸基含有化合物を反応させることにより、工程(1)で得られた重合体(ベースポリマー)の水酸基に、上記酸基含有化合物が付加されて長鎖の酸基を形成することができる。
反応温度としては、例えば、25~100℃が好ましく、30~90℃がより好ましい。
反応時間としては、特に限定されないが、例えば、1~20時間が挙げられる。
上記塩基性化合物としては、例えば、アンモニア;メチルアミン等の一級アミン;ジメチルアミン等の二級アミン;トリエチルアミン、ジエチルメチルアミン等の三級アミン;ジメチルエタノールアミン、n-ブチルアミン、ジエチルアミン等の脂肪族アミン;シクロヘキシルアミン等の環状脂肪族アミン;ピペリジン、モルホリン、N-エチルピペリジン、N-エチルモルホリン、ピリジン等のヘテロ環状アミン;ベンジルアミン、N-メチルアニリン、N,N-ジメチルアニリン等の芳香族アミン;テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド等のテトラアルキルアンモニウムハライド;酢酸テトラメチルアンモニウム等のテトラアルキルアンモニウム有機酸塩;硫酸水素テトラメチルアンモニウム、硫酸水素テトラエチルアンモニウム等のテトラアルキルアンモニウム無機酸塩;テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、モノヒドロキシエチルトリメチルアンモニウムヒドロキシド等の(ヒドロキシ)アルキルアンモニウムヒドロキシド;ナトリウム、カリウム等のアルカリ金属の水酸化物;バリウム、ストロンチウム、カルシウム、ランタン等の遷移金属の水酸化物;[Pt(NH3)6](OH)4等の錯塩の遊離塩;トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリメチルホスフィン等のリン化合物等が挙げられる。なかでも、蒸散のしやすさ、取り扱いやすさの点で、二級アミン、三級アミン、ヘテロ環状アミン、リン化合物であることが好ましく、副反応を抑制でき、付加後の重合体の分子量の上昇を抑制することができる点で、三級アミン、トリフェニルホスフィンであることがより好ましい。
上記酸基含有単量体としては、上述したものが挙げられ、好ましくは(メタ)アクリル酸が挙げられる。
上記イソシアネート基含有重合性単量体としては、上述した不飽和イソシアネート類等が挙げられ、低温で付加反応することができ、共重合体の保存安定性が良好となり得る点で、好ましくは(メタ)アクリル酸イソシアナトエチルが挙げられる。
上記付加反応は、特に制限されず、公知の方法で行うことができる。
また上記付加反応では、通常使用される化合物、触媒、溶媒等を使用してもよい。
本発明はまた、上述した共重合体、及び、プロトン性極性溶媒を含むことを特徴とする共重合体溶液でもある。本発明の共重合体溶液は、保存安定性に優れる。
上記共重合体は、上述のとおり、酸基とエポキシ基を有し、これらの基は反応性が高いため、低温での上記共重合体の硬化が容易となる一方、保存安定性を担保することは難しかった。本発明者は、プロトン性極性溶媒を添加することにより、上記共重合体の保存安定性を向上でき、高い耐溶剤性と保存安定性を両立し得ることを見いだした。
プロトン性極性溶媒の添加により上記共重合体の保存安定性が向上する理由については定かではないが、上記共重合体において、カルボキシル基等の酸基が主鎖から離間した位置に存在することで、プロトン性極性溶媒が上記酸基と比較的容易に水素結合して、酸基のアニオン性が低下し、当該酸基とエポキシ基との反応性が抑制されるためと推測される。
上記プロトン性極性溶媒としては、例えば、水、アルコール系溶媒、アミン系溶媒、及び、フェノール系溶媒が挙げられる。なかでも、上記プロトン性極性溶媒は、アルコール系溶媒であることが好ましい。
上記アルコール系溶媒の具体例としては、メタノール、エタノール、1-プロパノール、1-ブタノール、1-ペンタノール、1-ヘキサノール、エチレングリコール、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-n-プロピルエーテル、エチレングリコールモノ-n-ブチルエーテル、エチレングリコールモノフェニルエーテル、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-プロピルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノ-n-ブチルエーテル、トリプロピレングリコール、トリプロピレングリコールモノ-n-ブチルエーテル等の第一級アルコール;
イソプロパノール、2-ブタノール、2-ペンタノール、3-ペンタノール、2-ヘキサノール、シクロヘキサノール、2-ヘプタノール、3-ヘプタノール、プロピレングリコール、プロピ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エチルエーテル、プロピレングリコールモノ-n-プロピルエーテル、プロピレングリコールモノ-n-ブチルエーテル、プロピレングリコールモノフェニルエーテル、ジプロピレングリコール、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モノエチルエーテル、ジプロピレングリコールモノ-n-プロピルエーテル、ジプロピレングリコールモノ-n-ブチルエーテル、又は、トリプロピレングリコールモノメチルエーテル等の第二級アルコール;
tert-ブタノール、tert-ペンタノール、tert-ヘキサノール等の第三級アルコール等が挙げられる。
なかでも、上記アルコール系溶媒は、エポキシ基との反応性抑制と、共重合体溶液を低粘度化できる点で、第二級アルコール、又は、第三級アルコールであることが好ましい。
また、濃度調製する溶媒として、例えば、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル類;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類;酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、3-メトキシブチルアセテート等のエステル類;トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類;クロロホルム;ジメチルスルホキシド;等を含んでいてもよい。
上記共重合体溶液は、更に、pKaが4.2以下である酸化合物を含んでもよい。
上記共重合体溶液が、pKaが4.2以下である酸化合物を含むことにより、上記共重合体の酸基とエポキシ基の反応が抑制され、上記共重合体の保存安定性をより一層向上させることができる。pKaが4.2以下である酸化合物を含むことで、上記共重合体の保存安定性が向上しうるのは、上記共重合体の酸基含有構造単位(B)を形成しうる酸基よりも酸強度の強い酸化合物が存在することで、共重合体中の酸基のアニオン性が低下して、当該酸基とエポキシ基の反応性が抑制されるためと考えられる。また、上記共重合体溶液中に塩基性化合物が存在すると、カルボキシル基と塩を形成していた塩基性化合物を、pKaが4.2以下である酸化合物が補足し、共重合体中のカルボキシル基の求核力が低下して、当該酸基とエポキシ基の反応性を抑制することができると考えられる。
上記酸化合物のpKaは、3以下であることが好ましく、2以下であることがより好ましい。上記酸化合物のpKaの下限は、特に限定されないが、-3以上であることが好ましく、0以上であることがより好ましい。
pKaの値は、例えば、化学便覧、基礎編II(改訂5版、丸善株式会社)等の文献を参照することができ、当該文献に掲載されてない数値は、当該文献に記載の方法で算出することができる。
上記共重合体溶液は、リン酸誘導体を含んでもよい。上記共重合体溶液がリン酸誘導体を更に含むことにより、上記共重合体の保存安定性を向上することができる。
上記リン酸エステル又は亜リン酸エステルのエステル基としては、アルキルエステル基、アリールエステル基、アラルキルエステル基、重合性二重結合を有するエステル基等が挙げられる。上記アルキルエステル基のアルキルとしては、メチル、エチル、オクチル、2-エチルヘキシル等が挙げられる。上記アリールエステル基のアリールとしては、フェニル、トリル、ナフチル等が挙げられる。上記アラルキルエステル基のアラルキルとしては、ベンジル等が挙げられる。上記重合性二重結合を有するエステル基としては、2-アクリロイロキシエチルエステル基、2-メタクリロイロキシエチルエステル基等が挙げられる。
上記ホスホン酸の具体例としては、メチルホスホン酸等のアルキルホスホン酸、フェニルホスホン酸等のアリールホスホン酸等が挙げられる。
上記ホスフィン酸の具体例としては、メチルホスフィン酸等のアルキルホスフィン酸、フェニルホスフィン酸等のアリールホスフィン酸等が挙げられる。
上記リン酸エステルは、重合性二重結合を2個又は3個以上含むことが好ましい。
上記共重合体溶液は、更に、塩基性化合物を含んでもよい。塩基性化合物を含むことにより、共重合体の硬化時に160℃以下の低温硬化条件でも架橋反応が良好に進行し、耐溶剤性により一層優れた硬化物を与えることができる。
上記共重合体溶液を製造する方法として、例えば、上記式(a)で表されるエポキシ基含有単量体、及び、上記式(b1)で表される水酸基含有単量体を含む単量体成分を重合する工程(重合工程)と、上記重合工程で得られた重合体と、上記式(b2)又は式(b3)で表される酸基含有化合物を塩基性化合物存在下に反応させる工程(反応工程)と、pKaが4.2以下の酸化合物及びプロトン性極性溶媒を添加する工程(添加工程)とを含む方法が好ましく挙げられる。
すなわち、式(a)で表されるエポキシ基含有単量体、及び、式(b1)で表される水酸基含有単量体を含む単量体成分を重合する工程と、上記重合工程で得られた重合体と、式(b2)又は式(b3)で表される酸基含有化合物を塩基性化合物存在下に反応させる工程と、pKaが4.2以下の酸化合物及びプロトン性極性溶媒を添加する工程とを含むことを特徴とする共重合体溶液の製造方法も本発明の一つである。
本発明の共重合体、及び、共重合体溶液は、他の成分と組み合わせて硬化性樹脂組成物とすることができる。上記硬化性樹脂組成物は、本発明の共重合体を含むので、低温硬化条件でも耐溶剤性に優れた硬化物を与えることができる。また、上記硬化性樹脂組成物が、上記共重合体溶液を含む場合は、更に保存安定性にも優れるものとなる。このような、上記共重合体又は共重合体溶液を含む硬化性樹脂組成物もまた、本発明の好ましい形態の一つである。
なお、本明細書において、「固形分総量」とは、硬化物を形成する成分(硬化物の形成時に揮発する溶媒等を除く)の総量を意味する。
上記硬化性樹脂組成物における上記プロトン性極性溶媒の含有量は、硬化性樹脂組成物の安定性を担保する点で、上記共重合体の固形分100質量%に対して、10質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、また3000質量%以下であることが好ましく、1000質量%以下であることがより好ましい。
上記硬化性樹脂組成物の好ましい形態の一例として、感光性樹脂組成物について説明する。
本発明の共重合体、又は、共重合体溶液は、更に、重合性化合物、及び、光重合開始剤を組み合わせることにより、感光性樹脂組成物とすることができる。
上記感光性樹脂組成物は、上述した共重合体を含むので、160℃以下、例えば90℃程度の低温硬化条件下でも耐溶剤性に優れた硬化物を与えることができる。また、重合性化合物を更に含むので、硬化性や、基材への密着性、表面硬度、耐熱性等の各種物性にも優れた硬化物を与えることができる。このような、上述した共重合体又は共重合体溶液と、重合性化合物と、光重合開始剤を含む感光性樹脂組成物もまた、本発明の一つである。
上記重合性化合物は、フリーラジカル、電磁波(例えば赤外線、紫外線、X線等)、電子線等の活性エネルギー線の照射等により重合し得る、重合性不飽和結合(重合性不飽和基とも称す)を有する低分子化合物であり、例えば、重合性不飽和基を分子中に1つ有する単官能の化合物と、2個以上有する多官能の化合物が挙げられる。
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、シクロヘキサンジメタノールジ(メタ)アクリレート、ビスフェノールAアルキレンオキシドジ(メタ)アクリレート、ビスフェノールFアルキレンオキシドジ(メタ)アクリレート等の2官能(メタ)アクリレート化合物;
ただし、ビニルエーテル基を側鎖に有する重合体は、樹脂組成物の硬化性を向上させるが、保存安定性を低下させることがあるので、保存安定性の点では、上記感光性樹脂組成物は、ビニルエーテル基を側鎖に有する重合体を含まないことが好ましい。
また上記重合性化合物の分子量としては特に限定されないが、取り扱いの観点から、例えば、2000以下が好ましい。
光重合開始剤としては、好ましくはラジカル重合性の光重合開始剤が挙げられる。ラジカル重合性の光重合開始剤とは、電磁波や電子線等の活性エネルギー線の照射により重合開始ラジカルを発生させるものである。
上記光重合開始剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本発明の感光性樹脂組成物は、更に、光酸発生剤を含むことが好ましい。光酸発生剤を更に含むことにより、感光性樹脂組成物の硬化性がより一層向上しうる。
上記光酸発生剤は、放射線等の活性エネルギー線に暴露されることにより酸を発生する化合物であり、例えば、トルエンスルホン酸または四フッ化ホウ素などの強酸、スルホニウム塩、アンモニウム塩、ホスホニウム塩、ヨードニウム塩またはセレニウム塩などのオニウム塩類;鉄-アレン錯体類;シラノール-金属キレート錯体類;ジスルホン類、ジスルホニルジアゾメタン類、ジスルホニルメタン類、スルホニルベンゾイルメタン類、イミドスルホネート類、ベンゾインスルホネート類などのスルホン酸誘導体;有機ハロゲン化合物類;等が挙げられる。
本発明の感光性樹脂組成物は、上述した成分以外に、必要に応じて他の成分を含んでいてもよい。上記他の成分としては、例えば、溶剤;色材(顔料、染料);分散剤;耐熱向上剤;レベリング剤;現像助剤;シリカ微粒子等の無機微粒子;シラン系、アルミニウム系、チタン系等のカップリング剤;フィラー、エポキシ樹脂、フェノール樹脂、ポリビニルフェノール等の熱硬化性樹脂;多官能チオール化合物等の硬化助剤;可塑剤;重合禁止剤;紫外線吸収剤;酸化防止剤;艶消し剤;消泡剤;帯電防止剤;スリップ剤;表面改質剤;揺変化剤;揺変助剤;キノンジアジド化合物;多価フェノール化合物;カチオン重合性化合物;酸発生剤;等が挙げられる。これらは、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。これらの他の成分は、公知のものから適宜選択して使用するとよく、その使用量も適宜設定することができる。
例えば、上記感光性樹脂組成物をカラーフィルター用途に使用する場合には、上記感光性樹脂組成物は色材を含むことが好ましい。
本発明の感光性樹脂組成物を調製する方法としては、特に制限されず公知の方法を用いればよく、例えば、上述した各含有成分を、各種の混合機や分散機を用いて混合・分散する方法が挙げられる。混合・分散工程は特に制限されず、公知の方法により行えばよい。また、通常行われる他の工程を更に含んでいてもよい。上記感光性樹脂組成物が色材を含む場合は、色材の分散処理工程等の公知の工程を経て調製することが好ましい。
本発明の共重合体、共重合体溶液、又は、感光性樹脂組成物(硬化性樹脂組成物)を硬化して得られる硬化物は、優れた耐溶剤性を有する。そのような共重合体、共重合体溶液、又は感光性樹脂組成物の硬化物も本発明の一つである。
上記製造方法においては、上記感光性樹脂組成物を基材上に塗布した後、塗布物を乾燥させて塗布膜を形成することが好ましい。上記乾燥は、公知の方法で行うことができ、具体的には、後述する「<カラーフィルターの製造方法>」の「配置工程」に記載の乾燥方法と同様の方法で行うことができる。
上記形成された塗布膜に光照射する方法としては、特に制限されず、公知の方法で行うことができ、具体的には、後述する「<カラーフィルターの製造方法>」の「光照射工程」に記載の方法と同様の方法で行うことができる。
加熱温度は、155℃以下であることが好ましく、150℃以下であることがより好ましい。加熱温度の下限としては、硬化性が維持できる点で、70℃以上であることが好ましく、90℃以上であることがより好ましい。
温度以外の上記加熱方法については、特に制限されず、公知の方法で行うことができ、例えば、後述する「<カラーフィルターの製造方法>」の「加熱工程」に記載の方法と同様の方法で行うことができる。
本発明の共重合体、共重合体溶液、及びこれを含む感光性樹脂組成物(硬化性樹脂組成物)は、160℃以下、例えば90℃程度の低温硬化条件でも、硬化反応が十分に進行し、耐溶剤性に優れた硬化物を与えることができる。そのため、低温条件で充分に硬化させる必要がある用途や、耐溶剤性が必要とされる用途に好適に使用することができる。
本発明の感光性樹脂組成物は、光学材料用として好適に使用され、また、ネガ型用として好適に使用される。
基板上に、上述の感光性樹脂組成物の硬化物を有するカラーフィルターも、本発明の好ましい形態の一つである。
上記カラーフィルターにおいて、上述の感光性樹脂組成物により形成される硬化物は、例えば、ブラックマトリクスや、赤色、緑色、青色、黄色等の各画素のような着色が必要なセグメントとして特に好適であるが、フォトスペーサー、保護層、配向制御用リブ等の着色を必ずしも必要としないセグメントとしても好適である。
また上記基板には、必要に応じて、コロナ放電処理、オゾン処理、シランカップリング剤等による薬品処理等を行ってもよい。
上記カラーフィルターを得るには、例えば、画素一色につき(すなわち、一色の画素ごとに)、基板上に、上述の感光性樹脂組成物を配置する工程(配置工程とも称す)と、当該基板上に配置された感光性樹脂組成物に光を照射する工程(光照射工程とも称す)と、現像液により現像処理する工程(現像工程とも称す)と、加熱処理する工程(加熱工程とも称す)とを含む手法を採用し、これと同じ手法を各色で繰り返す製造方法を採用することが好適である。なお、各色の画素の形成順序は、特に限定されるものではない。
上記配置工程は、塗布により行うことが好適である。基板上に上記感光性樹脂組成物を塗布する方法としては、例えば、スピン塗布、スリット塗布、ロール塗布、流延塗布等が挙げられ、いずれの方法も好ましく用いることができる。
上記配置工程ではまた、上記感光性樹脂組成物を基板上に塗布した後、塗膜を乾燥することが好適である。塗膜の乾燥は、例えば、ホットプレート、IRオーブン、コンベクションオーブン等を用いて行うことができる。乾燥条件は、含まれる溶媒成分の沸点、硬化成分の種類、膜厚、乾燥機の性能等に応じて適宜選択されるが、通常、50~160℃の温度で10秒~300秒間行うことが好適である。
上記光照射工程において、使用される活性光線の光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアーク、蛍光ランプ等のランプ光源、アルゴンイオンレーザー、YAGレーザー、エキシマレーザー、窒素レーザー、ヘリウムカドミニウムレーザー、半導体レーザー等のレーザー光源等が使用される。また、露光機の方式としては、プロキシミティー方式、ミラープロジェクション方式、ステッパー方式が挙げられるが、プロキシミティー方式が好ましく用いられる。
なお、活性エネルギー光線の照射工程では、用途によっては、所定のマスクパターンを介して活性エネルギー光線を照射することとしてもよい。この場合、露光部が硬化し、硬化部が現像液に対して不溶化又は難溶化されることになる。
上記現像工程は、上述した光照射工程の後、現像液によって現像処理し、未露光部を除去しパターンを形成する工程である。これにより、パターン化された硬化膜を得ることができる。現像処理は、通常、10~50℃の現像温度で、浸漬現像、スプレー現像、ブラシ現像、超音波現像等の方法で行うことができる。
上記加熱工程は、上述した現像工程の後、焼成によって露光部(硬化部)を更に硬化させる工程(「後硬化工程」とも称す)である。例えば、高圧水銀灯等の光源を使用して、0.5~5J/cm2の光量で後露光する工程や、例えば60~200℃の温度で10秒~120分間にわたって後加熱する工程等が挙げられる。このような後硬化工程を行うことにより、パターン化された硬化膜の硬度及び密着性を更に強固なものとすることが可能になる。
上記加熱工程は、一般的には、200~260℃程度の温度で行われるが、上記感光性樹脂組成物を使用すれば、200℃以下、好ましくは160℃以下の比較的低温な条件下で十分な硬化を行うことができる。そのため、基板や硬化物が保持する特性を損なうことなく、耐溶剤性に優れたものを得ることができる。
上述したカラーフィルターを備える表示装置も本発明における好ましい形態の一つである。
上記感光性樹脂組成物の硬化物を有する表示装置用部材及び表示装置もまた、本発明の好適な実施形態に含まれる。上記感光性樹脂組成物により形成される硬化物(硬化膜)は、安定して、基材等に対する密着性に優れ、かつ高硬度であるうえ、高平滑性を示し、高い透過率を有するものであるから、透明部材として特に好適であり、また、各種表示装置における保護膜や絶縁膜としても有用である。
なお、上記硬化物(硬化膜)を表示装置用部材として用いる場合、当該部材は、上記硬化膜から構成されるフィルム状の単層又は多層の部材であってもよいし、上記単層又は多層の部材に更に他の層が組み合わされた部材であってもよいし、また、上記硬化膜を構成中に含む部材であってもよい。
(1)重量平均分子量(Mw)
ポリスチレンを標準物質とし、テトラヒドロフランを溶離液として、HLC-8220GPC(東ソー社製)、カラム:TSKgel SuperHZM-M(東ソー社製)によるGPC(ゲル浸透クロマトグラフィー)法にて重量平均分子量を測定した。
共重合体溶液をアルミカップに約1gはかり取り、アセトン約3gを加えて溶解させた後、常温で自然乾燥させた。そして、熱風乾燥機(商品名:PHH-101、エスペック社製)を用い、真空下140℃で1.5時間乾燥した後、デシケータ内で放冷し、質量を測定した。その質量減少量から、重合体溶液の固形分(質量%)を計算した。
共重合体溶液を3g精秤し、アセトン90gと水10gの混合溶媒に溶解させ、0.1NのKOH水溶液を滴定液として用いて滴定した。滴定は、自動滴定装置(商品名:COM-555、平沼産業社製)を用いて行い、溶液の酸価と溶液の固形分から固形分1g当たりの酸価(mgKOH/g)を求めた。
共重合体固形分の質量(g)を共重合体中に含まれるエポキシ基のモル数(mol)で除することにより求めた。
共重合体固形分の質量(g)を共重合体の二重結合量(mol)で除することにより求めた。
感光性樹脂組成物を5cm角のガラス基板上にスピンコートし、100℃で3分間乾燥後、高圧水銀灯を用いて200mJで露光を行い、90℃、又は、110℃でそれぞれ40分間熱処理(後硬化)を行い、膜厚2μmの硬化膜を得た。そして、その硬化膜を1-メチル-2-ピロリドン(NMP)20gに40℃で10分間浸漬した後取り出し、硬化膜を取り出した後の浸漬液(NMP)について、分光光度計UV3100(島津製作所社製)で吸光度を測定し、下記の基準にて評価した。吸光度の値が大きいほど、浸漬液中に色材が多く溶出したことを示し、感光性樹脂組成物の耐溶剤性が低いと評価する。
(評価基準)
◎:吸光度の値が0.2未満
〇:吸光度の値が0.2以上0.3未満
△:吸光度の値が0.3以上0.4未満
×:吸光度の値が0.4以上
××:膜剥がれ
感光性樹脂組成物を5cm角のガラス基板上にスピンコートし、90℃で2分間乾燥後、高圧水銀灯を用いて100mJで露光を行い、90℃で30分間熱処理(後硬化)を行い、膜厚2μmの硬化膜を得た。そして、その硬化膜を表5に記載の浸漬溶剤20gに30℃で5分間浸漬した後取り出し、硬化膜を取り出した後の浸漬溶剤について、分光光度計UV3100(島津製作所社製)で吸光度を測定した。
共重合体溶液の粘度を、粘度計(VISCOMETER TV-22、東機産業社製)を用いて、25℃で測定した。
上記(7)の耐溶剤性の評価前後の膜の重量を測定することで残膜率を計算した。具体的には、ガラス基板を風袋重量とすることで、耐溶剤性評価前の膜重量を算出した。その後に、耐溶剤性評価後の膜重量を、評価前の膜重量で除することで、残膜率を算出した。
共重合体溶液A-1(HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート185.3部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにメタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル70.0部、プロピレングリコールモノメチルエーテルアセテート30部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n―ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート18.0部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミンを0.33部、炭酸ジメチル189部、プロピレングリコールモノメチルエーテルアセテート29.6部を仕込み、40℃10時間反応させ、共重合体溶液A-1を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-2(BzMI-CHMA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート172.0部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル43.6部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル16.4部、プロピレングリコールモノメチルエーテルアセテート30部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート31.33部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミンを0.33部、プロピレングリコールモノメチルエーテルアセテート29.0部、60℃10時間反応させ、共重合体溶液A-2を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-3(BzMI-VT-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート172.0部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、ビニルトルエン43.6部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル16.4部、プロピレングリコールモノメチルエーテルアセテート30部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート31.33部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミンを0.33部、プロピレングリコールモノメチルエーテルアセテート29.0部、60℃10時間反応させ、共重合体溶液A-3を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-4(BzMI-2EHA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート172.0部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、2-エチルヘキシルアクリレート43.6部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル16.4部、プロピレングリコールモノメチルエーテルアセテート30部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート31.33部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミンを0.33部、プロピレングリコールモノメチルエーテルアセテート29.0部、60℃10時間反応させ、共重合体溶液A-4を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-5(BzMI-CHMA-HEAA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、ジエチレングリコールエチルメチルエーテル85.6部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル46.65部、N-ヒドロキシエチルアクリルアミド26.8部、メタクリル酸グリシジル16.55部、ジエチレングリコールエチルメチルエーテル49.8部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n―ドデシルメルカプタン2.0部、ジエチレングリコールエチルメチルエーテル98.0部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸13.0部、ジエチレングリコールエチルメチルエーテル32.5部を60℃10時間反応させ、共重合体溶液A-5を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-6(BzMI-CHMA-GLMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート50.1部、ジエチレングリコールエチルメチルエーテル50.1部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル46.65部、グリセリンモノメタクリレート(日本油脂社製「ブレンマーGL」)30.0部、メタクリル酸グリシジル13.35部、プロピレングリコールモノメチルエーテルアセテート24.1部、ジエチレングリコールエチルメチルエーテル24.1部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n―ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート42.5部、ジエチレングリコールエチルメチルエーテル42.5部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸9.4部、プロピレングリコールモノメチルエーテルアセテート12.0部、ジエチレングリコールエチルメチルエーテル12.0部を60℃10時間反応させ、共重合体溶液A-6を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-7(BzMI-CHMA-HEMA-GMA-NIPAM共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート30.9部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル23.6部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル16.4部、N-イソプロピルアクリルアミド20.0部、プロピレングリコールモノメチルエーテルアセテート10.0部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン4.0部、プロピレングリコールモノメチルエーテルアセテート67.4部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、プロピレングリコールモノメチルエーテルアセテート4.7部を60℃10時間反応させ、共重合体溶液A-7を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-8(BzMI-CHMA-HEMA-GMA共重合体のMAA付加体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート64.0部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル19.0部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル41.0部、プロピレングリコールモノメチルエーテルアセテート10.0部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン4.0部、プロピレングリコールモノメチルエーテルアセテート54.82部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、メタクリル酸13.5部、触媒として、トリフェニルホスフィン0.34部、アンテージW-400 0.17部を、85℃12時間反応させた。その後、室温まで冷却した後、無水コハク酸13.1部を60℃5時間反応させ、共重合体溶液A-8を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-9(BzMI-CHMA-HEMA-GMA共重合体のカレンズMOI付加体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート208.7部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル14.3部、メタクリル酸2-ヒドロキシエチル55.0部、メタクリル酸グリシジル20.7部、プロピレングリコールモノメチルエーテルアセテート10.0部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート98.00部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、2-イソシアナトエチルメタクリレート(昭和電工製「カレンズMOI(登録商標)」)26.2部と、トリエチルアミン0.13部と、0.19部のアンテージW-400を、90℃、4時間反応させた。その後、室温まで冷却した後、無水コハク酸14.7部、触媒として、トリエチルアミン0.28部を60℃7時間反応させ、更にプロピレングリコールモノメチルエーテルを69部加え、60℃1時間反応させることで、残存する無水コハク酸を消失させ、共重合体溶液A-9を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-10(AMA-TBMA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート172部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにα-(アリルオキシメチル)アクリル酸メチル10.0部、メタクリル酸ターシャリーブチル43.6部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル16.4部、プロピレングリコールモノメチルエーテルアセテート30.0部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート31.3部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミン0.33部、プロピレングリコールモノメチルエーテルアセテート29.04部を60℃10時間反応させ、共重合体溶液A-10を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-11(MD-CHMA-HEMA-GMA共重合体のAA付加体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート86.5部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにジメチル-2,2’-[オキシビス(メチレン)]ビス-2-プロペノエート10.0部、メタクリル酸シクロヘキシル43.6部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル16.4部、プロピレングリコールモノメチルエーテルアセテート48.8部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート98部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、アクリル酸5.0部、触媒として、トリエチルアミン0.32部、アンテージW-400を0.16部、プロピレングリコールモノメチルエーテルアセテート20部を115℃7時間反応させた。その後、室温まで冷却した後、無水コハク酸12.6部、プロピレングリコールモノメチルエーテルアセテート20部を60℃10時間反応させ、共重合体溶液A-11を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-12(CHMI-CHMA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート172部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-シクロヘキシルマレイミド10.0部、メタクリル酸シクロヘキシル43.6部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル16.4部、プロピレングリコールモノメチルエーテルアセテート30.0部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート31.3部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミン0.33部、プロピレングリコールモノメチルエーテルアセテート29.0部を60℃10時間反応させ、共重合体溶液A-12を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-13(BzMI-DCPMA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート53.4部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド5.0部、メタクリル酸ジシクロペンタニル25.0部、メタクリル酸2-ヒドロキシエチル40.0部、メタクリル酸グリシジル30.0部、プロピレングリコールモノメチルエーテルアセテート10部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン6.0部、プロピレングリコールモノメチルエーテルアセテート54.0部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸23.1部、プロピレングリコールモノメチルエーテルアセテート9.13部、60℃12時間反応させた後に、プロピレングリコールモノメチルエーテル172部で希釈を行った。共重合体溶液A-13を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-14(BzMI-CHMA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート165.3部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル27.5部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル32.5部、プロピレングリコールモノメチルエーテルアセテート30部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート38.0部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミンを0.33部、プロピレングリコールモノメチルエーテルアセテート29.0部、60℃10時間反応させた後に、プロピレングリコールモノメチルエーテル76部で希釈を行った。共重合体溶液A-14を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-15(BzMI-2EHA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート172.0部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、2-エチルヘキシルアクリレート29.0部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル31.0部、プロピレングリコールモノメチルエーテルアセテート30部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート31.33部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸6.2部、触媒としてトリエチルアミンを0.33部、プロピレングリコールモノメチルエーテルアセテート16.5部、60℃10時間反応させた後に、プロピレングリコールモノメチルエーテル40部で希釈を行い共重合体溶液A-15を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-16(BzMI-CHMA-HEMA-GMA共重合体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート83.6部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド20.0部、メタクリル酸シクロヘキシル25.0部、メタクリル酸2-ヒドロキシエチル50.0部、メタクリル酸グリシジル5.0部、プロピレングリコールモノメチルエーテルアセテート50部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン0.3部、プロピレングリコールモノメチルエーテルアセテート99.70部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸34.6部、触媒としてトリエチルアミンを0.40部、プロピレングリコールモノメチルエーテルアセテート78.9部、60℃10時間反応させ、共重合体溶液A-16を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-17(BzMI-CHMA-HEMA-GMA共重合体のAA付加体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート16.6部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド30.0部、メタクリル酸シクロヘキシル10.0部、メタクリル酸2-ヒドロキシエチル10.0部、メタクリル酸グリシジル50.0部、プロピレングリコールモノメチルエーテルアセテート30.0部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n―ドデシルメルカプタン6.0部、プロピレングリコールモノメチルエーテルアセテート82.24部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、アクリル酸22.8部、触媒として、トリフェニルホスフィン0.37部、アンテージW-400 0.18部を、85℃12時間反応させた。その後、室温まで冷却した後、無水コハク酸4.6部を60℃8時間反応させた後に、プロピレングリコールモノメチルエーテル118部で希釈を行い、共重合体溶液A-17を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液A-18(BzMI-CHMA-HEMA-GMA共重合体のカレンズMOI付加体のSAH付加体溶液)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート78.6部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル29.3部、メタクリル酸2-ヒドロキシエチル40.0部、メタクリル酸グリシジル20.7部、プロピレングリコールモノメチルエーテルアセテート10.0部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)6.0部を攪拌混合したものを準備し、滴下槽(B)に、n―ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート48.00部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、2-イソシアナトエチルメタクリレート(昭和電工製「カレンズMOI(登録商標)」)4.8部、0.16部のアンテージW-400を90℃8時間反応させた。その後、室温まで冷却した後、無水コハク酸14.6部、触媒として、トリエチルアミン0.36部を60℃10時間反応させ、共重合体溶液A-18を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液B-1(BzMI-CHMA-HEMA-サイクロマーM100-MAA共重合体)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート145.3部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル47.4部、メタクリル酸2-ヒドロキシエチル13.45部、3,4-エポキシシクロヘキシルメチルメタアクリレート(ダイセル社製「サイクロマーM100(登録商標)」)を20.25部、メタクリル酸8.9部、プロピレングリコールモノメチルエーテルアセテート10.0部、t-ブチルパーオキシピバレート(アルケマ吉富社製「ルペロックス11(登録商標)」)2.7部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート78部を攪拌混合したものを準備した。反応槽の温度が70℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間70℃を保った後、80℃まで昇温し、180分間熟成を行い、共重合体溶液B-1を得た。得られた共重合体の各種物性を表1に示す。
共重合体溶液B-2(BzMI-CHMA-HEMA-GMA-MAA共重合体)の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート145.3部仕込み、窒素置換した後、加熱して70℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル52.95部、メタクリル酸2-ヒドロキシエチル13.45部、メタクリル酸グリシジルを14.7部、メタクリル酸8.9部、プロピレングリコールモノメチルエーテルアセテート10.0部、t-ブチルパーオキシピバレート(アルケマ吉富社製「ルペロックス11(登録商標)」)2.7部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート78部を攪拌混合したものを準備した。反応槽の温度が70℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間70℃を保った後、80℃まで昇温し、180分間熟成を行い、共重合体溶液B-2を得た。得られた共重合体の各種物性を表1に示す。
BzMI:N-ベンジルマレイミド
AMA:α-(アリルオキシメチル)アクリル酸メチル
MD:ジメチル-2,2’-[オキシビス(メチレン)]ビス-2-プロペノエート
CHMI:N-シクロヘキシルマレイミド
CHMA:メタクリル酸シクロヘキシル
VT:ビニルトルエン
2EHA:アクリル酸2-エチルヘキヂル
DCPMA:メタクリル酸ジシクロペンタニル
TBMA:メタクリル酸ターシャリーブチル
HEMA:メタクリル酸-2-ヒドロキシエチル
HEAA:N-ヒドロキシエチルアクリルアミド
GLMA:グリセリンモノメタクリレート
M100:3,4-エポキシシクロヘキシルメチルメタアクリレート
GMA:メタクリル酸グリシジル
NIPAM:N-イソプロピルアクリルアミド
MAA:メタクリル酸
AA:アクリル酸
カレンズMOI:2-メタクリロイルオキシエチルイソシアネート
SAH:無水コハク酸
プロピレングリコールモノメチルエーテルアセテートを12.9部、分散剤としてディスパロンDA-7301を0.4部、色材としてC.I.ピグメントグリーン58を2.25部、及び、C.I.ピグメントイエロー138を1.5部混合し、ペイントシェーカーにて3時間分散することで顔料分散体1(固形分22質量%)を得た。
固形分で、共重合体溶液A-1を35.0部、ラジカル重合性化合物としてジペンタエリスリトールヘキサアクリレートを30.0部、ラジカル重合性光重合開始剤としてイルガキュアOXE-02(BASFジャパン社製)を5.0部、顔料分散体1を30.0部、更に希釈溶媒(プロピレングリコールモノメチルエーテルアセテート)を、固形分濃度20%となるように加え、攪拌することで感光性樹脂組成物1を得た。
表2に示す配合としたこと以外は実施例1と同様にして感光性樹脂組成物2~20を得た。
得られた感光性樹脂組成物1~20の耐溶剤性について評価した。結果を表2に示す。
(保存安定性確認)
希釈溶剤による保存安定性の効果を調べるために下記操作を行った。共重合体溶液A-2の100部(有姿)に対し、希釈溶剤を20部(共重合体固形分100質量%に対して、66.7質量%に相当)添加した共重合体溶液を用いて、40℃で2週間の保存前後における、共重合体の物性変化(重量平均分子量及び粘度)の確認を行った。希釈溶剤には、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルの2種類を使用した。得られた共重合体溶液の物性の変化を表3に示す。
変化量として、重量平均分子量については、保存前の重量平均分子量に対する、保存前後の重量平均分子量の差の割合(%)を表した。粘度については、保存前の粘度に対する保存前後の粘度の差の割合(%)を表した。
共重合体溶液A-19の調製
温度計、攪拌機、ガス導入管、冷却管及び滴下槽導入口を備えた反応槽に、プロピレングリコールモノメチルエーテルアセテート105.3部仕込み、窒素置換した後、加熱して90℃まで昇温した。他方、滴下槽(A)として、ビーカーにN-ベンジルマレイミド10.0部、メタクリル酸シクロヘキシル27.5部、メタクリル酸2-ヒドロキシエチル30.0部、メタクリル酸グリシジル32.5部、プロピレングリコールモノメチルエーテルアセテート30部、t-ブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製「パーブチル(登録商標)O」)2.0部を攪拌混合したものを準備し、滴下槽(B)に、n-ドデシルメルカプタン2.0部、プロピレングリコールモノメチルエーテルアセテート98.0部を攪拌混合したものを準備した。反応槽の温度が90℃になった後、同温度を保持しながら、滴下槽から3時間かけて滴下を開始し、重合を行った。滴下終了後30分間90℃を保った後、115℃まで昇温し、90分間熟成を行った。その後、室温まで冷却した後、無水コハク酸11.5部、触媒としてトリエチルアミンを0.33部、プロピレングリコールモノメチルエーテルアセテート29.0部を加えて60℃で7時間反応させた。その後、固形分が27%になるように、プロピレングリコールモノメチルエーテル42.0部を添加し共重合体溶液A-19を得た。得られた共重合体の各種物性を表4に示す。
共重合体溶液A-20の調製
プロピレングリコールモノメチルエーテルの代わりに、プロピレングリコールモノメチルエーテルアセテートを添加した以外は、共重合体溶液A-19と同様の調製方法で共重合体溶液A-20を得た。得られた共重合体の各種物性を表4に示す。
BzMI:N-ベンジルマレイミド
CHMA:メタクリル酸シクロヘキシル
HEMA:メタクリル酸-2-ヒドロキシエチル
GMA:メタクリル酸グリシジル
SAH:無水コハク酸
TEA:トリエチルアミン
固形分で、共重合体溶液A-19を35.0部、ラジカル重合性化合物としてジペンタエリスリトールヘキサアクリレートを30.0部、ラジカル重合性光重合開始剤としてイルガキュアOXE-02(BASFジャパン社製)を5.0部、顔料分散体1を30.0部、P-2M(ライトエステルP-2M、pKa:1.29、共栄社化学製)を1.0部、更に希釈溶媒(プロピレングリコールモノメチルエーテルアセテート)を、固形分濃度20%となるように加え、攪拌することで感光性樹脂組成物21を得た。
表5に示す配合としたこと以外は実施例20と同様にして感光性樹脂組成物22~24を得た。
得られた感光性樹脂組成物21~24の耐溶剤性について評価した。結果を表5に示す。
(保存安定性確認)
共重合体溶液100部(有姿)に対し、表6又は表7に記載した量で、希釈溶剤(プロピレングリコールモノメチルエーテル)と、P-1M、P-2M、MSA、又はACAを添加して共重合体溶液を調製した。希釈溶媒の量は、表6(35部)では共重合体固形分100質量%に対して129.6質量%に相当し、表7(8部)では共重合体固形分100質量%に対して29.6質量%に相当する。得られた共重合体溶液を用いて、40℃で1~2週間の保存前後における、共重合体溶液の物性変化(粘度)の確認を行った。得られた共重合体溶液の物性の変化を表6及び表7に示す。粘度の変化量(増粘率)として、保存前の粘度に対する保存前後の粘度の差の割合(%)を表した。また、共重合体溶液中の塩基性化合物(TEA)100モル%に対する酸化合物(P-1M、P-2M、MSA、ACA)の含有量を表中に示した。
P-1M:ライトエステルP-1M(共栄社化学製)2-メタクロイロキシエチルアシッドホスフェート、pKa:1.78、分子量:210.12
P-2M:ライトエステルP-2M(共栄社化学製)2-メタクロイロキシエチルアシッドホスフェート、pKa:1.29、分子量:322.25
MSA:メタンスルホン酸、pKa:-2.6、分子量:96.1
ACA:酢酸、pKa:4.76、分子量:60.05
Claims (14)
- 更に、主鎖に環構造を有する共重合体であることを特徴とする請求項1~3のいずれかに記載の共重合体。
- 請求項1~4のいずれかに記載の共重合体、及び、プロトン性極性溶媒を含むことを特徴とする共重合体溶液。
- 更に、pKaが4.2以下の酸化合物を含むことを特徴とする請求項5に記載の共重合体溶液。
- 更に、リン酸誘導体を含むことを特徴とする請求項5又は6に記載の共重合体溶液。
- 更に、塩基性化合物を含むことを特徴とする請求項5~7のいずれかに記載の共重合体溶液。
- 請求項1~4のいずれかに記載の共重合体、又は、請求項5~8のいずれかに記載の共重合体溶液と、重合性化合物と、光重合開始剤とを含むことを特徴とする感光性樹脂組成物。
- 更に、色材を含むことを特徴とする請求項9に記載の感光性樹脂組成物。
- ネガ型用であることを特徴とする請求項9又は10に記載の感光性樹脂組成物。
- 請求項1~4のいずれかに記載の共重合体、請求項5~8のいずれかに記載の共重合体溶液、又は、請求項9~11のいずれかに記載の感光性樹脂組成物の、硬化物。
- 下記式(a)で表されるエポキシ基含有単量体、及び、下記式(b1)で表される水酸基含有単量体を含む単量体成分を重合する工程と、
該重合工程で得られた重合体と、下記式(b2)又は式(b3)で表される酸基含有化合物を反応させる工程を含む
ことを特徴とする共重合体の製造方法。
- 下記式(a)で表されるエポキシ基含有単量体、及び、下記式(b1)で表される水酸基含有単量体を含む単量体成分を重合する工程と、
該重合工程で得られた重合体と、下記式(b2)又は式(b3)で表される酸基含有化合物とを塩基性化合物の存在下で反応させる工程と、
pKaが4.2以下である酸化合物、及び、プロトン性極性溶媒を添加する工程を含む
ことを特徴とする共重合体溶液の製造方法。
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