WO2024018984A1 - Copolymère, composition de résine durcissable et article durci - Google Patents

Copolymère, composition de résine durcissable et article durci Download PDF

Info

Publication number
WO2024018984A1
WO2024018984A1 PCT/JP2023/025849 JP2023025849W WO2024018984A1 WO 2024018984 A1 WO2024018984 A1 WO 2024018984A1 JP 2023025849 W JP2023025849 W JP 2023025849W WO 2024018984 A1 WO2024018984 A1 WO 2024018984A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
copolymer
compound
epoxy group
polymerizable unsaturated
Prior art date
Application number
PCT/JP2023/025849
Other languages
English (en)
Japanese (ja)
Inventor
瑠美 永井
Original Assignee
株式会社ダイセル
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Publication of WO2024018984A1 publication Critical patent/WO2024018984A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment

Definitions

  • the present disclosure relates to a copolymer, a curable resin composition, and a cured product. Additionally, this application claims priority to Japanese Patent Application No. 2022-116755 filed in Japan on July 21, 2022, the contents of which are incorporated herein.
  • a polarizing plate is provided on a glass substrate, a transparent conductive circuit layer such as ITO and a thin film transistor (TFT) are formed, and then covered with an interlayer insulating film.
  • a polarizing plate is provided on the glass plate, patterns of a black matrix layer and a color filter layer are formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed to form a top plate.
  • the device is manufactured by making the back plate and the top plate face each other with a spacer interposed therebetween, and filling liquid crystal between the two plates.
  • a chemically amplified resist that utilizes a photoacid generator, which is a photosensitizer, is known as a method for increasing the sensitivity of a radiation-sensitive resin composition (resist), which is one method for forming fine patterns.
  • a resin composition containing a copolymer containing a structural unit having an epoxy group and a photoacid generator a protonic acid is generated from the photoacid generator by exposure, and the epoxy group is cleaved to cause a crosslinking reaction. .
  • the copolymer becomes insoluble in the developer and a pattern is formed.
  • dramatically higher sensitivity has been achieved compared to conventional resists, which have a photoreaction efficiency (reaction per photon) of less than 1.
  • most of the resists developed are of the chemically amplified type, which are used to develop highly sensitive materials compatible with shorter wavelength exposure light sources.
  • a radiation-sensitive resin composition is generally used as a material for forming an insulating film.
  • Such radiation-sensitive resin compositions are required to have high radiation sensitivity in order to improve productivity. If the insulating film has low solvent resistance, the insulating film will swell, deform, and peel from the substrate due to organic solvents, resulting in serious problems in the production of liquid crystal display elements and integrated circuit elements. obtain. Therefore, the insulating film is required to have excellent solvent resistance.
  • Patent Document 1 describes a copolymer having a polymerizable unsaturated group in the side chain (a copolymer obtained by adding acrylic acid and tetrahydrophthalic anhydride to a copolymer containing glycidyl methacrylate). Disclosed.
  • Patent Document 2 describes epoxy group-containing monomers (3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-9-yl acrylate and 3,4 - A mixture of epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate) and a carboxyl group-containing monomer, to which a highly reactive epoxy group-containing monomer is added. Polymers are disclosed.
  • the copolymer of Patent Document 2 has excellent storage stability and solvent resistance in that it contains an epoxy group-containing monomer that has low reactivity with carboxyl groups, but it requires curing at a high temperature of 230 ° C. or higher. There were problems with poor curability, such as a tendency to leave residue during development. Additionally, if the epoxy group-containing monomer is changed to relatively highly reactive 3,4-epoxycyclohexylmethyl methacrylate for the purpose of improving curability, it will react with the epoxy group-containing monomer used in the addition reaction, reducing production stability. There was a tendency to
  • “poor storage stability” means that the weight average molecular weight of the copolymer increases over time, and “excellent storage stability” means that the copolymer remains stable even after long-term storage. It means that the weight average molecular weight of the polymer does not increase or is difficult to increase. Furthermore, “poor production stability” means that a uniform copolymer cannot be obtained or gelation occurs during the production of the copolymer; “high production stability” means that , means that a uniform copolymer can be obtained during the production of the copolymer and that gelation is less likely to occur. Note that whether or not the resulting copolymer is uniform can be evaluated based on molecular weight distribution.
  • an object of the present disclosure is to provide a copolymer that has excellent curability, production stability, and storage stability, and that can impart excellent solvent resistance to a cured product. There is a particular thing.
  • Another object of the present invention is to provide a curable resin composition containing the copolymer and a cured product thereof.
  • a copolymer containing a specific structural unit has excellent curability, manufacturing stability, and storage stability, and further provides excellent solvent resistance to a cured product. and completed the invention according to the present disclosure.
  • R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • R 2a represents a divalent organic group.
  • X a represents a heteroatom.
  • a copolymer having an epoxy group derived from the epoxy group-containing polymerizable unsaturated compound (b) and a polymerizable unsaturated group derived from the epoxy group-containing polymerizable unsaturated compound (c) is provided.
  • the epoxy group of the compound (b) is preferably an alicyclic epoxy group.
  • the epoxy group of the compound (b) is preferably a monocyclic or bicyclic alicyclic epoxy group.
  • the epoxy group is preferably bonded to an aliphatic hydrocarbon group.
  • R 2a in formula (1) preferably represents a divalent organic group containing an ester bond.
  • the copolymer of the present disclosure preferably further includes a structural unit (D) derived from at least one compound selected from the group consisting of (d1) to (d4) below.
  • the present disclosure also provides a curable resin composition containing the copolymer.
  • the curable resin composition further contains a photopolymerization initiator.
  • the curable resin composition further contains a coloring material.
  • the present disclosure also provides a cured product of the curable resin composition.
  • the cured product of the curable resin composition is preferably a color filter.
  • R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • R 2a represents a divalent organic group.
  • X a represents a heteroatom.
  • a method for producing a copolymer is provided.
  • the copolymer of the present disclosure has excellent curability, production stability, and storage stability, and further provides excellent solvent resistance to the cured product. Further, the curable resin composition containing the above copolymer has excellent curability. Moreover, the cured product has excellent solvent resistance.
  • the copolymer of the present disclosure has the following formula (1) (In the formula, R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 2a represents a divalent organic group. X a represents a heteroatom.) A structural unit (A) derived from the compound (a) represented by Addition reaction between the structural unit (B) derived from the epoxy group-containing polymerizable unsaturated compound (b) and the compound (a) represented by the above formula (1) and the epoxy group-containing polymerizable unsaturated compound (c) A copolymer containing a structural unit (C) derived from a substance, A carboxyl group derived from the compound (a) represented by the formula (1), It is characterized by having an epoxy group derived from the epoxy group-containing polymerizable unsaturated compound (b), and a polymerizable unsaturated group derived from the epoxy group-containing polymerizable unsaturated compound (c).
  • the copolymer of the present disclosure can be obtained by copolymerizing compounds corresponding to the structural units (A) to (C).
  • the copolymer of the present disclosure also includes a structural unit (A) derived from the compound (a) represented by the formula (1) and a structural unit (B) derived from the epoxy group-containing polymerizable unsaturated compound (b). ) can also be obtained by subjecting it to an addition reaction with an epoxy group-containing polymerizable unsaturated compound (c).
  • the carboxyl group derived from the compound (a) represented by formula (1) in the copolymer is added to the epoxy group of the epoxy group-containing polymerizable unsaturated compound (c), and the structural unit (C) becomes.
  • the structural unit (A) that did not undergo an addition reaction with the epoxy group-containing polymerizable unsaturated compound (c) has a carboxyl group derived from the compound (a) represented by formula (1), and the structural unit (C) has a polymerizable unsaturated group derived from the epoxy group-containing polymerizable unsaturated compound (c).
  • the copolymer of the present disclosure may further contain a structural unit (D) derived from at least one compound selected from the group consisting of (d1) to (d4). That is, the copolymer of the present disclosure can be obtained by copolymerization of compounds corresponding to the structural units (A) to (C) and, if necessary, a compound corresponding to the structural unit (D). Further, it can also be obtained by subjecting a copolymer containing the structural unit (A), the structural unit (B), and the structural unit (D) to an addition reaction with the compound (c).
  • a structural unit (D) derived from at least one compound selected from the group consisting of (d1) to (d4). That is, the copolymer of the present disclosure can be obtained by copolymerization of compounds corresponding to the structural units (A) to (C) and, if necessary, a compound corresponding to the structural unit (D). Further, it can also be obtained by subjecting a copolymer containing the structural unit (A), the structural unit
  • the structural unit (A) is a structural unit derived from the compound (a) represented by the formula (1), and for example, the compound (a) represented by the formula (1) is subjected to the epoxy group-containing polymerization. It can be introduced into a copolymer by subjecting it to a copolymerization reaction with a sexually unsaturated compound (b) or the like.
  • the compound (a) represented by the formula (1) can be used alone or in combination of two or more.
  • the copolymer of the present disclosure has excellent production stability and storage stability due to the presence of the structural unit (A).
  • the copolymer of the present disclosure has excellent manufacturing stability and storage stability by having the structural unit (A). The reason for this will be explained below using a copolymer of the present disclosure that is a structural unit derived from (meth)acrylic acid instead of the structural unit (A) as a comparison target.
  • the copolymer of the present disclosure has a structure derived from a structural unit (A) derived from the compound (a) represented by the formula (1) and an epoxy group-containing polymerizable unsaturated compound (b).
  • A structural unit derived from the compound (a) represented by the formula (1)
  • an epoxy group-containing polymerizable unsaturated compound (b) By subjecting the copolymer containing the unit (B) to an addition reaction with the epoxy group-containing polymerizable unsaturated compound (c), the epoxy group of the compound (c) is added to some of the carboxyl groups of the copolymer. Obtained by adding a group.
  • the reactivity of the epoxy group derived from the compound (b) contained in the combination becomes low.
  • priority is given to the reaction between the carboxyl group derived from the compound (a) represented by the formula (1) in the copolymer and the epoxy group of the compound (c)
  • the desired uniformity can be achieved. It is easy to obtain a copolymer and gelation tends to be difficult to occur. Thus, it can be said that the copolymer of the present disclosure has excellent production stability.
  • the copolymer of the present disclosure includes a structural unit (A) derived from the compound (a) and a structural unit (B) derived from the compound (b).
  • A structural unit derived from the compound (a)
  • B structural unit derived from the compound (b)
  • carboxyl group derived from the compound (a) and the epoxy group derived from the compound (b) have high reactivity, these groups react within the molecule (within the copolymer), resulting in co-reactivity over time.
  • the weight average molecular weight of the polymer increases.
  • the acidity of the copolymer as a whole becomes relatively high.
  • the reactivity of the epoxy group derived from (meth)acrylic acid increases, and the reaction between the carboxyl group derived from (meth)acrylic acid and the epoxy group proceeds.
  • the weight average molecular weight of the copolymer increases over time during storage of the curable resin composition.
  • the acidity of the entire copolymer is moderately low due to the structure of the compound (a) represented by formula (1).
  • the reactivity of the epoxy group derived from b) is reduced. Therefore, the carboxyl group derived from the compound (a) and the epoxy group derived from the compound (b) become difficult to react, and the weight average molecular weight of the copolymer tends to be difficult to increase even after long-term storage. There is.
  • R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • R 2a represents a divalent organic group.
  • X a represents a heteroatom.
  • alkyl group having 1 to 7 carbon atoms in R 1a examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, etc. It will be done.
  • the divalent organic group in R 2a is, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group (alkylene groups having 1 to 20 carbon atoms are preferable, and alkylene groups having 1 to 12 carbon atoms are more preferable).
  • an alkylene group having 1 to 6 carbon atoms more preferably an alkylene group having 1 to 3 carbon atoms, an alkenylene group (preferably an alkenylene group having 2 to 20 carbon atoms, and an alkenylene group having 2 to 12 carbon atoms) (more preferably an alkenylene group having 2 to 6 carbon atoms), a cycloalkylene group, an arylene group, and a group in which a plurality of these are linked directly or via a linking group.
  • the linking group include an ether bond, a carbonyl group, an ester bond, a sulfide bond, and an amide group, and an ester bond is preferable from the viewpoint of production stability and storage stability.
  • the divalent organic group contains an ester bond, the acidity of the copolymer containing the structural unit (A) becomes appropriately low, so that production stability and storage stability tend to be improved.
  • the number of carbon atoms (total number) in the divalent organic group is not particularly limited, but is preferably 1 to 15, more preferably 2 to 10, and still more preferably 3 to 6.
  • the acidity of the carboxyl group derived from the compound (a) represented by formula (1) becomes appropriately low. There is a tendency for the curing properties, manufacturing stability, and storage stability of the combination to be improved.
  • the heteroatom in X a is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom, with an oxygen atom being preferred.
  • the proportion of the structural unit (A) in the copolymer is not particularly limited, but, for example, it is preferably 10 to 50 mol% with respect to all the structural units constituting the copolymer, and the lower limit thereof is 20 mol%. is more preferable, and its upper limit is more preferably 40 mol%.
  • the proportion of the structural unit (A) is at least the above lower limit, there is a tendency for excellent developability.
  • the proportion of the structural unit (A) is at most the above upper limit, excessive development is suppressed, and thus there is a tendency for excellent solvent resistance.
  • the proportion of the structural unit in the copolymer is based on the molar amount of the compound (monomer) used in the copolymerization.
  • the ratio of the structural unit (A) in the copolymer refers to the ratio of the amount of compound (a) represented by formula (1) to the total amount (100 mol%) of the compounds used in copolymerization. means.
  • the one to which the epoxy group of the epoxy group-containing polymerizable unsaturated compound (c) is added becomes the structural unit (C), and the structural unit Not included in (A). Therefore, the proportion of the structural unit (A) in the copolymer is determined by subtracting the amount of the epoxy group-containing polymerizable unsaturated compound (c) from the amount of the compound (a) represented by formula (1) used. It is calculated as
  • the structural unit (B) is a structural unit derived from the epoxy group-containing polymerizable unsaturated compound (b), and for example, the epoxy group-containing polymerizable unsaturated compound (b) is represented by the above formula (1). It can be introduced into a copolymer by subjecting it to a copolymerization reaction with compound (a) or the like.
  • the epoxy group-containing polymerizable unsaturated compound (b) can be used alone or in combination of two or more.
  • the compound (b) is not particularly limited as long as it contains an epoxy group and a polymerizable unsaturated group, but it is preferable that the epoxy group is an alicyclic epoxy group. That is, the compound (b) is preferably a compound containing an alicyclic epoxy group and a polymerizable unsaturated group (an alicyclic epoxy group-containing polymerizable unsaturated compound). Note that the alicyclic ring in the alicyclic epoxy group may have a substituent other than the epoxy group. Moreover, in this specification, "alicyclic epoxy group” means an epoxy group composed of two adjacent carbon atoms and an oxygen atom that constitute an alicyclic ring.
  • the production stability and curability of the copolymer of the present disclosure tend to improve. This is thought to be because the reactivity of the alicyclic epoxy group in the above compound is moderately low, making it difficult to react with the epoxy group derived from the epoxy group-containing polymerizable unsaturated compound (c). .
  • Examples of the alicyclic epoxy group include epoxycyclohexyl group, 2,3-epoxybicyclo[2.2.1]heptanyl group, and 2,3-epoxy-7-oxabicyclo[2.2.1]heptanyl group. , 3,4-epoxytricyclo[5.2.1.0 2,6 ]decanyl group (3,4-epoxydicyclopentanyl group), a substituent on one or more carbon atoms constituting these groups Examples include groups having the following.
  • the epoxy group in the compound (b) is a monocyclic or bicyclic (however, the ring formed by the epoxy group is not included) polymer from the viewpoint of curability, production stability, and storage stability of the copolymer.
  • a cyclic epoxy group is preferred.
  • the alicyclic epoxy group has an epoxycyclohexyl skeleton.
  • the compound (b) is preferably bonded to the polymerizable unsaturated group via the carbon atom at the 3rd or 4th position of the skeleton.
  • Examples of the alicyclic epoxy group-containing polymerizable unsaturated compound include a compound represented by the following formula (2).
  • R 1b represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • R 2b is the same or different and represents an alkyl group having 1 to 7 carbon atoms.
  • X b represents a single bond or a divalent organic group. Note that R 2b represents a substituent on the cyclohexane ring represented by formula (2), and is not included in the substituents that Y b has.
  • Y b is a non-bonding (meaning that there is no group corresponding to Y b ), a methylene group or ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or oxygen Indicates a sulfur atom that may be bonded to another atom.
  • n represents an integer of 0 or more (preferably an integer of 0 to 7).
  • R 1b examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, etc. It will be done. From the viewpoint of copolymerizability and reactivity, R 1b is preferably a hydrogen atom, a methyl group, or an ethyl group.
  • R 2b examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, etc. It will be done.
  • n is 2 or more, n R 2b 's may be the same or different.
  • R 2b is preferably a methyl group or an ethyl group.
  • the divalent organic group in X b is, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a trimethylene group (an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 12 carbon atoms is more preferable).
  • an alkylene group having 1 to 6 carbon atoms more preferably an alkylene group having 1 to 3 carbon atoms, an alkenylene group (preferably an alkenylene group having 2 to 20 carbon atoms, and an alkenylene group having 2 to 12 carbon atoms) (more preferably an alkenylene group having 2 to 6 carbon atoms), a cycloalkylene group, an arylene group, and a group in which a plurality of these are linked directly or via a linking group.
  • the linking group include an ether bond, a carbonyl group, an ester bond, a sulfide bond, and an amide group.
  • X b is preferably bonded to the carbon atom at the 3rd or 4th position of the epoxycyclohexyl skeleton represented by formula (2).
  • the methylene group or ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent for Y b is not particularly limited, but a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
  • Examples of the sulfur atom that may be bonded to the oxygen atom of Y b include a sulfur atom and a sulfonyl group.
  • Examples of the compound represented by the formula (2) include a compound represented by the following formula (2').
  • R 1b , R 2b , X b , Y b , and n in formula (2') are the same as those explained in formula (2).
  • the proportion of the structural unit (B) in the copolymer is not particularly limited, but it is preferably 5 to 40 mol% with respect to all the structural units constituting the copolymer, and the lower limit is 10 mol%. More preferably, it is 15 mol%. Further, the upper limit thereof is more preferably 35 mol%, and even more preferably 30 mol%.
  • the ratio of the structural unit (B) is within the above range, the amount of epoxy groups contained in the copolymer is suitable for curing, so it can be cured even at a relatively low temperature, and the crosslinked structure of the cured product is dense. Therefore, it tends to have excellent solvent resistance.
  • the structural unit (C) is a structural unit derived from an addition reaction product of the compound (a) represented by the formula (1) and the epoxy group-containing polymerizable unsaturated compound (c). Specifically, it is a structural unit derived from a compound obtained by adding the epoxy group of the epoxy group-containing polymerizable unsaturated compound (c) to the carboxyl group of the compound (a) represented by the formula (1) above. be.
  • the epoxy group-containing polymerizable unsaturated compound (c) is not particularly limited as long as it is a compound containing an epoxy group and a polymerizable unsaturated group, and may be the same as the compound (b), but manufacturing stability From this point of view, it is preferable that the compound is different from the epoxy group-containing polymerizable unsaturated compound (b).
  • the epoxy group is preferably a group bonded to an aliphatic hydrocarbon group (aliphatic epoxy group), and particularly preferably a glycidyl group.
  • the epoxy group-containing polymerizable unsaturated compound (c) can be used alone or in combination of two or more.
  • Examples of the compound (c) include allyl glycidyl ether, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyl Examples include oxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, and 4-hydroxybutyl (meth)acrylate glycidyl ether, among which glycidyl (meth)acrylate is It is preferable from the viewpoint of improving production stability and curability.
  • the compound (b) is an alicyclic epoxy group-containing polymerizable unsaturated compound
  • the compound (c) is an aliphatic epoxy group-containing polymerizable unsaturated compound (particularly a glycidyl group-containing polymerizable unsaturated compound).
  • (containing polymerizable unsaturated compounds) not only have excellent production stability and storage stability, but also cure at relatively low temperatures, and the cured product has excellent solvent resistance. The reason for this remarkable effect is that [1] the epoxy group of the aliphatic epoxy group-containing polymerizable unsaturated compound has high reactivity with respect to the alicyclic epoxy group-containing polymerizable unsaturated compound.
  • the proportion (content) of the structural unit (C) in the copolymer is not particularly limited, but, for example, it is preferably 10 to 60 mol% with respect to all the structural units constituting the copolymer, and the lower limit is 15 mol. % is more preferable. Further, the upper limit thereof is more preferably 50 mol%, and even more preferably 35 mol%. When the proportion of the structural unit (C) is at least the above lower limit, there is a tendency to cure even at a relatively low temperature due to the presence of the polymerizable unsaturated group derived from the epoxy group-containing polymerizable unsaturated compound (c).
  • the proportion of the structural unit (C) in the copolymer means that all of the epoxy group-containing polymerizable unsaturated compound (c) used is the compound (a) represented by formula (1). It is calculated based on the molar amount of the epoxy group-containing polymerizable unsaturated compound (c), assuming that it has reacted with a carboxyl group.
  • the structural unit (D) is styrene (d1) which may be substituted with an alkyl group, N-substituted maleimide (d2), N-vinyl compound (d3), and an unsaturated carboxyl group represented by the above formula (2). It is a structural unit derived from at least one compound selected from the group consisting of acid derivatives (d4).
  • the structural unit (D) has the function of imparting hardness to the cured product (cured film), the function of smoothing the copolymerization reaction, the function of increasing solubility in solvents, the function of increasing adhesion to substrates, etc. .
  • the structural unit (D) comprises at least one compound selected from the group consisting of the above (d1) to (d4), the compound (a) represented by the above formula (1) and the epoxy group-containing polymerizable unsaturated It can be introduced into a copolymer by subjecting it to a copolymerization reaction with compound (b) and the like.
  • the alkyl group in styrene (d1) which may be substituted with an alkyl group is not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, etc. Examples include alkyl groups having 1 to 7 carbon atoms. Among these, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group is preferred, and a methyl group is more preferred.
  • the alkyl group may be bonded to either the vinyl group or the benzene ring of styrene.
  • N-substituted maleimide (d2) examples include a compound represented by the following formula (3).
  • R 1 represents a monovalent organic group.
  • Examples of the monovalent organic group include a hydrocarbon group and a heterocyclic group.
  • Examples of the hydrocarbon group include alkyl groups (e.g., alkyl groups having 1 to 6 carbon atoms) such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl; cyclopentyl, cyclohexyl, Examples include cycloalkyl groups such as cyclooctyl, adamantyl, and norbornyl; aryl groups such as phenyl; aralkyl groups such as benzyl; and groups in which two or more of these are bonded.
  • Examples of the heterocyclic group include 5- to 10-membered heterocycloalkyl groups and heteroaryl groups containing at least one heteroatom selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms. .
  • the N-substituted maleimide (d2) is not particularly limited, but includes, for example, N-alkylmaleimide such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide; N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclo Examples include N-cycloalkylmaleimides such as octylmaleimide, N-adamantylmaleimide, and N-norbornylmaleimide; N-arylmaleimides such as N-phenylmaleimide; and N-aralkylmaleimides such as N-benzylmaleimide. Among them, N-cyclohexylmaleimide is preferred.
  • the N-substituted maleimide (d2) can be used alone or in combination of two or more.
  • the N-vinyl compound (d3) is not particularly limited, but includes, for example, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, and N-vinylcarbazole. , N-vinylpiperidone, N-vinylcaprolactam and the like.
  • the N-vinyl compound (d3) can be used alone or in combination of two or more.
  • the unsaturated carboxylic acid derivative (d4) is represented by the following formula (4).
  • R 1d represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • R 2d represents a monovalent organic group.
  • X d represents a heteroatom.
  • Examples of the alkyl group having 1 to 7 carbon atoms for R 1d include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, and the like.
  • R 1d a hydrogen atom or a methyl group is particularly preferable.
  • Examples of the monovalent organic group in R 2d include a carboxyl group, an alkyl group, a heteroalkyl group, an alkenyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, and a group in which two or more of these are linked. . Note that the carbon atom in the monovalent organic group of R 2d is bonded to X d .
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, hexyl group, octyl group, decyl group, dodecyl group, isodecyl group, lauryl group, and stearyl group.
  • alkyl groups having 1 to 23 carbon atoms examples include alkyl groups having 1 to 23 carbon atoms.
  • the heteroalkyl group is, for example, a -(R 2d1 -O)p-R 2d2 group (wherein R 2d1 represents an alkylene group having 1 to 12 carbon atoms.
  • R 2d2 is a hydrogen atom or a C 1 to 12 p is an integer of 1 or more)
  • -R 2d3 -NR 2d4 R 2d5 group wherein, R 2d3 is an alkylene group having 1 to 12 carbon atoms.
  • R 2d4 and R 2d5 are , each of which is the same or different and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
  • alkenyl group examples include alkenyl groups having 2 to 23 carbon atoms such as allyl group, 3-butenyl group, and 5-hexenyl group.
  • cycloalkyl group examples include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, and norbornyl group.
  • heterocycloalkyl group examples include groups containing a cyclic ether structure such as an oxetane ring, an oxolane ring, an oxane ring, and an oxepane ring (for example, a cyclic ether-containing group having three or more members).
  • aryl group examples include aryl groups having 6 to 12 carbon atoms such as phenyl group and naphthyl group.
  • Examples of the heteroatom in X include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the unsaturated carboxylic acid derivative (d4) represented by formula (4) is not particularly limited, but includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (Meth)acrylates with alkyl groups such as (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylamino (Meth)acrylates with alkylamino groups such as ethyl (meth)acrylate, N,N-diisopropylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy Hydroxyl group-containing (meth)acrylates such as buty
  • phenyl examples include (meth)acrylates having an aryl group such as (meth)acrylate and benzyl (meth)acrylate.
  • the unsaturated carboxylic acid derivative (d4) represented by formula (2) can be used alone or in combination of two or more. Among these, (meth)acrylates having an alkyl group and (meth)acrylates having an aryl group are preferred, and methyl (meth)acrylate, butyl (meth)acrylate, and benzyl (meth)acrylate are more preferred.
  • the proportion (content) of the structural unit (D) in the copolymer is not particularly limited, but it is preferably 0 to 50 mol% with respect to all the structural units constituting the copolymer, and the lower limit is 1. It is more preferably mol%, and its upper limit is more preferably 35 mol%.
  • the proportion of the structural unit (D) is 1 mol% or more (particularly 5 mol% or more), it has the function of imparting hardness to the cured product (cured film), the function of smoothing the copolymerization reaction, and the ability to be used as a solvent. There is a tendency for the function of increasing the solubility of the substance, the function of increasing the adhesion to the substrate, etc. to be effectively expressed.
  • the proportion of the structural unit (D) is below the above upper limit, the proportion of the structural units (A) to (C) becomes relatively large, so the functions of these structural units tend to be effectively expressed. be.
  • the total amount of the structural units (A) to (C) is: It is preferably 90 mol% or more, more preferably 95 mol% or more, even more preferably 99 mol% or more, and even if it is substantially 100 mol%, based on all the structural units constituting the copolymer. good.
  • the total amount of the structural units (A) to (D) is: It is preferably 90 mol% or more, more preferably 95 mol% or more, even more preferably 99 mol% or more, and even if it is substantially 100 mol%, based on all the structural units constituting the copolymer. good.
  • the weight average molecular weight (Mw) of the copolymer of the present disclosure is not particularly limited, but is preferably, for example, 5,000 to 70,000, more preferably 7,000 to 20,000.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight: Mw/Mn) of the copolymer of the present disclosure is not particularly limited, but is, for example, 3.5 or less (for example, 1.1 to 3.5). It is preferably 2.5 or less (1.1 to 2.5).
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured, for example, by GPC using polystyrene as a standard substance, and are preferably measured by the method used in the Examples.
  • the acid value of the copolymer of the present disclosure is, for example, about 30 to 120 mgKOH/g, preferably about 40 to 100 mgKOH/g. When the acid value is within the above range, developability tends to be excellent. Note that the method for measuring the acid value of the copolymer is not particularly limited, but it may be measured, for example, by the method described in the Examples.
  • the copolymer of the present disclosure has excellent production stability and storage stability, and also has excellent curability. That is, it cures even at relatively low temperatures, and the cured product has excellent solvent resistance. Further, the curable resin composition containing the copolymer has excellent storage stability, is cured even at a relatively low temperature, and the cured product has excellent solvent resistance. Furthermore, since the cured product has excellent solvent resistance and high insulation properties, it is useful as a material for forming a protective film or an insulating film. Further, the copolymer of the present disclosure is useful as a binder resin or a pigment dispersion resin because its cured product has excellent storage stability.
  • the copolymer of the present disclosure can be obtained by subjecting a compound corresponding to the structural units (A) to (C) and, if necessary, a compound corresponding to the structural unit (D) to a copolymerization reaction. Can be done.
  • the copolymer of the present disclosure comprises the compound (a) represented by the formula (1), the epoxy group-containing polymerizable unsaturated compound (b), and (d1) to (d4) as necessary. ) is subjected to a copolymerization reaction with at least one compound selected from the group consisting of It can be manufactured by adding.
  • compounds that can be introduced into a copolymer such as compound (a) represented by formula (1) may be collectively referred to as "monomers".
  • the copolymerization reaction of monomers may be carried out in the presence of a polymerization initiator.
  • a polymerization initiator conventional or known radical polymerization initiators can be used, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2 , 2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), diethyl-2,2'-azobis(2-methylpropionate) azo compounds such as dibutyl-2,2'-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, etc.
  • Examples include organic peroxides, hydrogen peroxide, and the like.
  • a peroxide When a peroxide is used as a radical polymerization initiator, it may be used in combination with a reducing agent to form a redox type initiator.
  • azo compounds are preferred, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate) ) is more preferable.
  • the amount of the polymerization initiator used is not particularly limited as long as it does not interfere with smooth copolymerization reaction, but for example, it is preferably 1 to 20 parts by weight, more preferably 1 to 20 parts by weight based on the total amount of monomers (100 parts by weight). is 3 to 15 parts by weight.
  • the copolymerization reaction can be carried out by conventional methods used in producing acrylic polymers and styrenic polymers, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization.
  • the monomer and the polymerization initiator may be supplied to the reaction system all at once, or part or all of them may be added dropwise to the reaction system.
  • a method in which a solution of a polymerization initiator dissolved in a polymerization solvent is dropped into a monomer or a mixture of a monomer and a polymerization solvent held at a constant temperature or a method in which monomers are
  • a method in which a solution of the agent dissolved in a polymerization solvent is dropped into a polymerization solvent maintained at a constant temperature for polymerization dropping polymerization method, etc.
  • the polymerization solvent can be selected as appropriate depending on the monomer composition, and examples include ether (diethyl ether; ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether, propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl ether, Propylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono , chain ethers such as glycol ethers such as di- or trialkyl ethers; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, eth
  • glycol acetates or glycol ether acetates examples include aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, and mixed solvents thereof.
  • the reaction temperature in the polymerization reaction can be appropriately selected depending on the type and composition of the monomer, and is not particularly limited, but is preferably, for example, 30 to 150°C.
  • the copolymer of the present disclosure will be combined with the compound (a) represented by the above formula (1), the epoxy group-containing polymerizable unsaturated compound (b), and the above (d1) to (d4) as necessary. ) is subjected to a copolymerization reaction with at least one compound selected from the group consisting of A case of manufacturing by adding will be explained.
  • the addition reaction of the compound (C) may be carried out in the presence of a catalyst.
  • a catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU); Quaternary ammonium salts such as methylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide; Alkylureas such as tetramethylurea; Alkylguanidines such as tetramethylguanidine; Metal compounds (metal salts, etc.) such as cobalt naphthenate; Organic Metal complexes include phosphine compounds (especially tertiary phosphine) such as triphenylphosphine. These catalysts can be used alone or in combination of two or more.
  • the amount of the catalyst used is not particularly limited, but for example, it is preferably 0.01 to 30% by weight, and the lower limit is 0.1% by weight, based on the epoxy group-containing polymerizable unsaturated compound (c). More preferably, it is 1% by weight. Further, the upper limit thereof is more preferably 25% by weight, and even more preferably 20% by weight.
  • the addition reaction is usually performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it dissolves the raw materials, and for example, the solvents exemplified as the polymerization solvents above can be used.
  • the reaction temperature during the addition reaction is not particularly limited, but is preferably, for example, 10 to 150°C, more preferably 60 to 100°C.
  • a polymerization inhibitor may be added to the reaction system in order to suppress gelation due to polymerization of the polymerizable unsaturated group.
  • the polymerization inhibitor include methquinone, hydroquinone, hydroquinone monomethyl ether, and phenothiazine.
  • the obtained reaction product can be purified by precipitation or reprecipitation, if necessary.
  • the solvent used for precipitation or reprecipitation may be either an organic solvent or water, or a mixed solvent thereof.
  • organic solvents examples include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated Hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc.), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.) ), ethers (chain ethers such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ethers such as tetrahydrofuran and dioxane),
  • the curable resin composition of the present disclosure is characterized by containing the copolymer of the present disclosure. Further, the composition may contain a curable compound other than the copolymer of the present disclosure, a photopolymerization initiator, and a solvent.
  • Curable compounds other than the copolymer of the present disclosure are not particularly limited, and include, for example, polyfunctional vinyl compounds, polyfunctional thiol compounds, and polyfunctional epoxy compounds.
  • the polyfunctional vinyl compound is not particularly limited as long as it has two or more vinyl groups, but examples include di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; polyalkylenes such as polyethylene glycol and polypropylene glycol; Di(meth)acrylate of glycol; di(meth)acrylate of polymer with hydroxylation at both ends such as both-terminal hydroxy polybutadiene, both-terminal hydroxy polyisoprene, and both-terminal hydroxy polycaprylactone; glycerin, 1,2,4,-butane Poly(meth)acrylates of trihydric or higher polyhydric alcohols such as triol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol (e.g.
  • polyalkylenes of trihydric or higher polyhydric alcohols Poly(meth)acrylates of glycol adducts; Poly(meth)acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; Polyester(meth)acrylates, epoxy(meth)acrylates, urethane(meth)acrylates; ) acrylate, oligo(meth)acrylate such as silicone resin (meth)acrylate, and the like.
  • Polyfunctional vinyl compounds can be used alone or in combination of two or more.
  • the polyfunctional thiol compound is not particularly limited as long as it has two or more thiol groups, but examples include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, and 1,4-butanediol bisthiopropionate.
  • Thioglycolate ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol Tetrakis thioglycolate, pentaerythritol tetrakis thiopropionate, trimercaptopropionate tris(2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N,N-dibutylamino)-4,6-dimercapto-s-triazine, tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tris-3-mercaptopropionate, tris(3-mercaptopropynyloxy
  • the polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups, but examples include glycidyl ether type epoxy compounds [polyhydroxy compounds (bisphenols, polyhydric phenols, alicyclic polyhydric alcohols)] , aliphatic polyhydric alcohols, etc.) and epichlorohydrin (e.g., (poly)C 2-4 alkylene glycols such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc.) diglycidyl ether; diglycidyl ether of polyhydric phenols such as resorcinol and hydroquinone; diglycidyl ether of alicyclic polyhydric alcohols such as cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenols; bisphenols (4,4' - dihydroxybiphenyl, bis(hydroxyphen
  • the photopolymerization initiator is not particularly limited, but examples thereof include radical photopolymerization initiators and cationic photopolymerization initiators.
  • a photoradical polymerization initiator is a compound that generates radicals upon irradiation with light and initiates a curing reaction (radical polymerization) of a photopolymerizable compound contained in a curable resin composition.
  • the photoradical polymerization initiators can be used alone or in combination of two or more.
  • Examples of the photoradical polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -diketone compounds, Examples include polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, and anthracene compounds.
  • thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropyl.
  • Examples include thioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
  • acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl ]-2-Methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethyl Amino-1-(4-morpholinophenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-ethylbenzyl
  • biimidazole compound examples include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole -chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-t
  • triazine compounds examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4 -methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino) -2-methylphenyl)
  • Examples of the oxime compound include O-ethoxycarbonyl- ⁇ -oximino-1-phenylpropan-1-one.
  • benzoin compounds examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.
  • benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(tert-butyl peroxide). (oxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.
  • anthracene-based compounds examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. .
  • the photocationic polymerization initiator is a compound that generates acid upon irradiation with light to initiate a curing reaction (cationic polymerization) of the photopolymerizable compound contained in the curable resin composition, and has a cationic moiety that absorbs light. and an anion part that is a source of acid generation.
  • the photocationic polymerization initiators can be used alone or in combination of two or more.
  • photocationic polymerization initiators examples include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds, etc. can be mentioned.
  • the anion moiety of the photocationic polymerization initiator is, for example, [(Y) s B(Phf) 4-s ] - (wherein, Y represents a phenyl group or a biphenylyl group.
  • Phf represents a hydrogen atom in which at least one hydrogen atom is represents a phenyl group substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom (s is an integer of 0 to 3), BF 4 - , [(Rf) k PF 6-k ] - (Rf: an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms, k: an integer from 0 to 5), AsF 6 - , SbF 6 - , SbF 5 OH - , etc. can.
  • photocationic polymerization initiators examples include (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl) Borate, 4-(phenylthio)phenyldiphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4 -(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)pheny
  • the trade names are "Cylacure UVI-6970”, “Cylacure UVI-6974”, “Cylacure UVI-6990”, “Cylacure UVI-950” (all manufactured by Union Carbide, USA), and "Irgacure 250”.
  • the content of the photopolymerization initiator (if two or more types are included, the total amount) is, for example, 0.1 to 100 parts by weight based on 100 parts by weight of the photopolymerizable compound (total amount) contained in the curable resin composition.
  • the lower limit is preferably 0.5 parts by weight, and even more preferably 3 parts by weight.
  • the upper limit thereof is more preferably 50 parts by weight, and even more preferably 20 parts by weight.
  • solvent examples include ether (diethyl ether; ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether, propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl ether, dipropylene glycol mono- or dialkyl ether, tripropylene glycol mono- or dialkyl ether).
  • ether diethyl ether; ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether, propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl ether, dipropylene glycol mono- or dialkyl ether, tripropylene glycol mono- or dialkyl ether).
  • glycol ethers such as dialkyl ether, 1,3-propanediol mono- or dialkyl ether, 1,3-butanediol mono- or dialkyl ether, 1,4-butanediol mono- or dialkyl ether, glycerin mono-, di- or trialkyl ether; chain ethers such as tetrahydrofuran, cyclic ethers such as dioxane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C 5- Carboxylic acid esters such as 6 cycloalkanediol mono or diacetate, C 5-6 cycloalkanedimethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, di
  • the curable resin composition of the present disclosure also includes resins such as novolac resins, phenolic resins, imide resins, and carboxyl group-containing resins, curing agents, curing accelerators, and additives (fillers, antifoaming agents, etc.). additives, flame retardants, antioxidants, ultraviolet absorbers, coloring agents, stress-lowering agents, flexibility imparting agents, waxes, crosslinking agents, halogen trapping agents, leveling agents, wetting improvers, etc.) May contain.
  • resins such as novolac resins, phenolic resins, imide resins, and carboxyl group-containing resins
  • curing agents curing accelerators
  • additives fillers, antifoaming agents, etc.
  • additives flame retardants, antioxidants, ultraviolet absorbers, coloring agents, stress-lowering agents, flexibility imparting agents, waxes, crosslinking agents, halogen trapping agents, leveling agents, wetting improvers, etc.
  • the content of the copolymer in the curable resin composition of the present disclosure is not particularly limited, but is, for example, 3 to 40% by weight. Further, the content of the copolymer relative to the total amount of curable compounds contained in the curable resin composition is not particularly limited, but is preferably 20% by weight or more, more preferably 30% by weight or more, still more preferably 40% by weight. Above, particularly preferably 50% by weight or more.
  • the curable resin composition of the present disclosure contains a coloring material
  • a coloring material such as a pigment is dispersed in a solvent, optionally with a pigment dispersant, to prepare a coloring material dispersion, and separately
  • a method for preparing a photosensitive resin composition for example, a coloring material such as a pigment is dispersed in a solvent, optionally with a pigment dispersant, to prepare a coloring material dispersion, and separately, Examples include a method of dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives if necessary in a solvent, mixing this with the above-mentioned coloring material dispersion, and further adding a solvent if necessary. It will be done.
  • the photosensitive resin composition of the present disclosure is usually sealed in a container and distributed and stored.
  • the photosensitive resin composition of the present disclosure has excellent storage stability during distribution and storage.
  • the curable resin composition of the present disclosure By curing the curable resin composition of the present disclosure, a cured product with excellent physical properties can be obtained.
  • the curable resin composition is applied to various substrates or substrates to form a coating film using a conventional coating means such as a spin coater, dip coater, roller coater, or slit coater, and then the coating film is A cured product can be obtained by curing.
  • Curing is performed, for example, by subjecting the curable resin composition to light irradiation and/or heat treatment.
  • the light irradiation uses, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, an LED light source, etc., and the cumulative irradiation amount is, for example, 500 to 5000 mJ/cm 2 It is preferable to irradiate in a range where .
  • the heat treatment is preferably performed at a temperature of, for example, 60 to 300°C (preferably 100 to 250°C) for, for example, 1 to 120 minutes (preferably 1 to 60 minutes).
  • the base material or substrate examples include silicon wafers, metals, plastics, glass, and ceramics.
  • the thickness of the coating film after curing is, for example, preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m.
  • the cured product (coating film after curing) of the present disclosure has excellent solvent resistance and high insulation properties, so it is useful as a protective film or an insulating film. It is also useful as a color filter protective film, a forming material for microlenses, colored patterns, etc., a transparent film, and the like.
  • the cured product thereof can be used as a color filter.
  • the color filter may include a colored pattern formed from the photosensitive resin composition.
  • a color filter can be manufactured, for example, through a process of forming a colored pattern on a substrate using the photosensitive resin composition and a process of post-baking the colored pattern.
  • the acid value of the copolymer was measured by neutralization titration using a 0.1N-NaOH standard solution. 0.5 g of the resin solution was accurately weighed, and 70 mL of THF and 10 mL of distilled water were added. Add a few drops of phenolphthalein solution as an indicator and stir to make it homogeneous. This solution was titrated with a 0.1 mol/L NaOH aqueous solution while stirring, and the end point was the point at which the solution changed color from colorless to pink, and the acid value was calculated using the following formula.
  • Acid value (KOHmg/g) A x F x 5.6/S/nonvolatile content (%) x 100 (In the formula, A is the amount of 0.1 mol/L NaOH aqueous solution dropped until the end point (mL), F is the factor of 0.1N-NaOH aqueous solution, and S is the amount of sample collected (g))
  • the produced copolymer had a weight average molecular weight Mw of 8,100, a dispersity of 1.80, and an acid value of 200 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 5,500, a dispersity of 1.67, and an acid value of 175 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 8,300, a dispersity of 1.69, and an acid value of 165 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 17,100, a dispersity of 2.19, and an acid value of 108 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 9,900, a dispersity of 2.06, and an acid value of 173 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 11,000, a dispersity of 3.51, and an acid value of 276.4 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 9,800, a dispersity of 3.36, and an acid value of 242.2 KOHmg/g.
  • 131 g of methacrylic acid (MAA), 99 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100), and 91 g of cyclohexyl maleimide (CHMI) were added to 60 g of propylene glycol monomethyl ether acetate and 110 g of 1-methoxy 2-propanol.
  • the dissolved solution and a mixed solution of 42 g of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 250 g of propylene glycol monomethyl ether acetate were added dropwise over about 5 hours using a dropping pump.
  • the produced copolymer had a weight average molecular weight Mw of 7,500, a dispersity of 2.21, and an acid value of 266.3 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 8,400, a dispersity of 2.15, and an acid value of 193.9 KOHmg/g.
  • the produced copolymer had a weight average molecular weight Mw of 10,700, a dispersity of 3.20, and an acid value of 302.7 KOHmg/g.
  • Example 1 78 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-1) obtained in Production Example 1, and the copolymer solution was reacted at 90°C for 13 hours. A combined solution (P-1) was obtained. The reaction was carried out under a mixed atmosphere of 6% oxygen and 94% nitrogen by volume.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • Example 2 A copolymer was prepared in the same manner as in Example 1 except that 55 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-2) obtained in Production Example 2. A solution (P-2) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • P-2 methoquinone
  • Example 3 A copolymer was produced in the same manner as in Example 1 except that 69 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-3) obtained in Production Example 3. A solution (P-3) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • P-3 methoquinone
  • Example 4 A copolymer was prepared in the same manner as in Example 1 except that 43 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-4) obtained in Production Example 4. A solution (P-4) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • P-4 methoquinone
  • Example 5 A copolymer was prepared in the same manner as in Example 1 except that 72 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-5) obtained in Production Example 5. A solution (P-5) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • P-5 methoquinone
  • a copolymer was produced in the same manner as in Example 1 except that 112 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-6) obtained in Production Example 6. A solution (P-6) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • P-6 methoquinone
  • a copolymer was prepared in the same manner as in Example 1 except that 98 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-7) obtained in Production Example 7. A solution (P-7) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • a copolymer was prepared in the same manner as in Example 1 except that 108 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-8) obtained in Production Example 8. A solution (P-8) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • a copolymer was prepared in the same manner as in Example 1 except that 64 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-9) obtained in Production Example 9. A solution (P-9) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • P-9 methoquinone
  • a copolymer was produced in the same manner as in Example 1 except that 127 g of glycidyl methacrylate (GMA), 3 g of triphenylphosphine (TPP) and 2 g of methoquinone were added to the copolymer solution (C-10) obtained in Production Example 10. A solution (P-10) was obtained.
  • GMA glycidyl methacrylate
  • TPP triphenylphosphine
  • Table 1 shows the copolymer compositions of the copolymer solutions (P-1) to (P-10) obtained in Examples 1 to 5 and Comparative Examples 1 to 5.
  • the molar ratio (mol%) of a structural unit is described as a ratio of the usage amount of a corresponding compound.
  • structural units (A) and (C) were calculated as follows.
  • the molar ratio of the structural unit (A) is calculated by subtracting the amount of the epoxy group-containing polymerizable unsaturated compound (c) from the amount of the compound (a) represented by formula (1). . This is based on the assumption that all of the epoxy group-containing polymerizable unsaturated compound (c) used reacted with the carboxyl group of the compound (a) represented by formula (1).
  • the molar ratio of the structural unit (C) is the molar ratio of the epoxy group-containing polymerizable unsaturated compound (c) used.
  • the weight average molecular weight (polystyrene equivalent) and molecular weight distribution (weight average molecular weight Mw/number average molecular weight Mn) of the copolymer were measured using the following apparatus.
  • copolymers of Examples 1 to 5 had excellent production stability, and the weight average molecular weight did not easily increase even at 40°C, resulting in excellent storage stability.
  • the copolymers of Comparative Examples 1, 2, and 5 gelled during production, resulting in poor production stability.
  • the copolymers of Comparative Examples 3 and 4 showed an increase in weight average molecular weight over time at 40°C, resulting in poor storage stability. This means that the copolymers of Examples 1 to 5 have structural units derived from 2-acryloyloxyethyl-succinic acid, while the copolymers of Comparative Examples 1 to 5 do not have the structural units. is cited as one of the reasons.
  • the side chain of the structural unit derived from 2-acryloyloxyethyl-succinic acid contains an ester bond and has a certain length, so the acidity of the copolymer as a whole is low. moderately low. Therefore, during the production of a copolymer, the reactivity of the epoxy group of the copolymer, that is, the alicyclic epoxy group derived from Cyclomer M100, is reduced, so the epoxy group derived from glycidyl methacrylate (GMA) It is thought that gelation is unlikely to occur because the group preferentially reacts with the carboxyl group derived from 2-acryloyloxyethyl-succinic acid. Further, it is considered that after production, the reaction between the carboxyl group and the epoxy group within the molecule of the copolymer was difficult to occur, so that no increase in the weight average molecular weight was observed over time.
  • GMA glycidyl methacrylate
  • Example 6 to 10 and Comparative Examples 6 to 7 A curable resin composition was prepared by mixing predetermined components in the proportions shown in Table 2, and the following evaluations were performed. The results are shown in Table 2. Note that the units of the components of the curable resin composition in the table are parts by weight.
  • NMP N-methylpyrrolidone
  • ⁇ -BL ⁇ -butyrolactone
  • the curable resin compositions of Examples 6 to 10 exhibited good solvent resistance even when the curing temperature was 180°C as well as at 230°C. On the other hand, the curable resin compositions of Comparative Examples 6 and 7 were shown to have poor solvent resistance.
  • AES 2-acryloyloxyethyl-succinic acid (manufactured by Kyoeisha Chemical Co., Ltd.)
  • AA Acrylic acid (manufactured by Mitsubishi Chemical Corporation)
  • MAA Methacrylic acid (manufactured by Mitsubishi Chemical Corporation)
  • M100 3,4-epoxycyclohexylmethyl methacrylate (trade name "Cyclomer M100", manufactured by Daicel Corporation)
  • GMA Glycidyl methacrylate (manufactured by NOF Corporation) ST: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • CHMI N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.)
  • BzMA Benzyl methacrylate (manufactured by Mitsubishi Chemical Corporation)
  • BMA Butyl methacrylate (manufactured by Mitsubishi Chemical Corporation)
  • DPHA Dip
  • R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • R 2a represents a divalent organic group.
  • X a represents a heteroatom.
  • a structural unit (A) derived from the compound (a) represented by Addition reaction between the structural unit (B) derived from the epoxy group-containing polymerizable unsaturated compound (b) and the compound (a) represented by the above formula (1) and the epoxy group-containing polymerizable unsaturated compound (c) A copolymer containing a structural unit (C) derived from a substance, A carboxyl group derived from the compound (a) represented by the formula (1), A copolymer having an epoxy group derived from the epoxy group-containing polymerizable unsaturated compound (b), and a polymerizable unsaturated group derived from the epoxy group-containing polymerizable unsaturated compound (c).
  • the proportion of the structural unit (A) in the copolymer is 10 to 50 mol% with respect to all the structural units constituting the copolymer, and the lower limit is 20 mol% or the upper limit is 40 mol%. % of the copolymer according to any one of [1] to [6].
  • the compound (b) has the above formula (2) (wherein R 1b represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 2b is the same or different and has 1 to 7 carbon atoms. ⁇ 7 represents an alkyl group.
  • X b represents a single bond or a divalent organic group.
  • R 2b represents a substituent on the cyclohexane ring represented by formula (2), and Y b Y b is a non-bonded (meaning that there is no group corresponding to Y b ) methylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent. or represents an ethylene group, an oxygen atom, or a sulfur atom that may be bonded to an oxygen atom; n represents an integer of 0 or more (preferably an integer of 0 to 7) [1 ] to [9].
  • the copolymer according to any one of [9].
  • the compound (b) has the above formula (2') (wherein R 1b represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 2b is the same or different and has a carbon number of It represents an alkyl group of 1 to 7.
  • X b represents a single bond or a divalent organic group.
  • R 2b represents a substituent on the cyclohexane ring represented by formula (2'), and Y It is not included in the substituents that b has.
  • Y b is non-bonded (meaning that there is no group corresponding to Y b ), and may have an alkyl group having 1 to 3 carbon atoms as a substituent.
  • n is an integer of 0 or more (preferably an integer of 0 to 7).
  • X b of the above formula (2) or (2') represents a divalent organic group (preferably an alkylene group such as a methylene group), or Y b is non-bonded.
  • the proportion of the structural unit (B) in the copolymer is 5 to 40 mol% with respect to all the structural units constituting the copolymer, and the lower limit is 10 mol% or 15 mol%. , the copolymer according to any one of [1] to [12], wherein the upper limit is 35 mol% or 30 mol%.
  • the epoxy group is a group bonded to an aliphatic hydrocarbon group (aliphatic epoxy group), preferably a glycidyl group [1] to any one of [14] Copolymers as described.
  • the compound (c) is allyl glycidyl ether, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3- At least one selected from the group consisting of glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, and 4-hydroxybutyl (meth)acrylate glycidyl ether.
  • the copolymer according to any one of [1] to [15].
  • the proportion of the structural unit (C) in the copolymer is 10 to 60 mol% with respect to all the structural units constituting the copolymer, and the lower limit is 15 mol% or the upper limit is 10 to 60 mol%. is 50 mol% or 35 mol%, the copolymer according to any one of [1] to [16].
  • the compound according to any one of [1] to [17] which contains a structural unit (D) derived from at least one compound selected from the group consisting of the following (d1) to (d4). Polymer.
  • the proportion of the structural unit (D) in the copolymer is 0 to 50 mol% with respect to all the structural units constituting the copolymer, and the lower limit is 1 mol% or the upper limit is 35 mol%. % of the copolymer according to [18] or [19].
  • the total amount of structural units (A) to (C) is 90 mol% or more, 95 mol% or more, 99 mol% or more, or substantially 100 mol% of all the structural units constituting the copolymer, and the copolymer contains the structural unit (A) and the structural unit ( B), a structural unit (C), and a structural unit (D), the total amount of structural units (A) to (D) is 90 mol% or more based on the total structural units constituting the copolymer, 95
  • Weight average molecular weight (Mw) is 5,000 to 70,000 or 7,000 to 20,000, and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight: Mw/Mn) is 3.5 or less (for example, 1.1 to 3.5), or the copolymer according to any one of [1] to [21], which has a molecular weight of 2.5 or less (1.1 to 2.5).
  • Mw/Mn molecular weight distribution
  • the copolymer according to any one of [1] to [22] which has an acid value of 30 to 120 mgKOH/g or 40 to 100 mgKOH/g.
  • a curable resin composition comprising the copolymer according to any one of [1] to [23].
  • a curable resin composition comprising the copolymer according to [24], further comprising a polyfunctional vinyl compound, a polyfunctional thiol compound, or a polyfunctional epoxy compound.
  • the content of the copolymer in the curable resin composition is 3 to 40% by weight, and the content of the copolymer with respect to the total amount of curable compounds contained in the curable resin composition is 20% by weight or more, 30% by weight or more.
  • [29] A cured product of the curable resin composition according to any one of [24] to [28].
  • [30] A color filter that is a cured product of the curable resin composition according to any one of [24] to [28].
  • Formula (1) above (wherein, R 1a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • R 2a represents a divalent organic group.
  • X a represents a heteroatom.
  • a method for producing a copolymer the method comprising:
  • the copolymer of the present disclosure has excellent curability, production stability, and storage stability, and further provides excellent solvent resistance to the cured product. Further, the curable resin composition containing the above copolymer has excellent curability. Moreover, the cured product has excellent solvent resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne un copolymère ayant une excellente aptitude au durcissement, une excellente stabilité de production et une excellente stabilité au stockage et capable de conférer une excellente résistance aux solvants à un article durci.　Le copolymère comprend une unité constitutive (A) dérivée d'un composé (a) représenté par la formule (1) (dans laquelle R1a représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 7 atomes de carbone ; R2a représente un groupe organique bivalent ; et Xa représente un hétéroatome), une unité constitutive (B) dérivée d'un composé insaturé polymérisable contenant un groupe époxy (b), et une unité constitutive (C) dérivée d'un produit de réaction d'addition d'un composé (a) représenté par la formule (1) et un composé insaturé polymérisable contenant un groupe époxy (c), et le copolymère a un groupe carboxyle dérivé du composé (a) représenté par la formule (1), un groupe époxy dérivé du composé insaturé polymérisable contenant un groupe époxy (b), et un groupe insaturé polymérisable dérivé du composé insaturé polymérisable contenant un groupe époxy (c).
PCT/JP2023/025849 2022-07-21 2023-07-13 Copolymère, composition de résine durcissable et article durci WO2024018984A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022116755A JP2024014141A (ja) 2022-07-21 2022-07-21 共重合体、硬化性樹脂組成物、及び硬化物
JP2022-116755 2022-07-21

Publications (1)

Publication Number Publication Date
WO2024018984A1 true WO2024018984A1 (fr) 2024-01-25

Family

ID=89617928

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/025849 WO2024018984A1 (fr) 2022-07-21 2023-07-13 Copolymère, composition de résine durcissable et article durci

Country Status (3)

Country Link
JP (1) JP2024014141A (fr)
TW (1) TW202411281A (fr)
WO (1) WO2024018984A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008139679A1 (fr) * 2007-05-11 2008-11-20 Daicel Chemical Industries, Ltd. Copolymère photo- et/ou thermo-durcissable, compositions de résine durcissable, et articles durcis
JP2010044365A (ja) * 2008-07-17 2010-02-25 Jsr Corp 着色層形成用感放射線性組成物、カラーフィルタおよびカラー液晶表示素子
KR20180108217A (ko) * 2017-03-24 2018-10-04 동우 화인켐 주식회사 패턴의 형성방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008139679A1 (fr) * 2007-05-11 2008-11-20 Daicel Chemical Industries, Ltd. Copolymère photo- et/ou thermo-durcissable, compositions de résine durcissable, et articles durcis
JP2010044365A (ja) * 2008-07-17 2010-02-25 Jsr Corp 着色層形成用感放射線性組成物、カラーフィルタおよびカラー液晶表示素子
KR20180108217A (ko) * 2017-03-24 2018-10-04 동우 화인켐 주식회사 패턴의 형성방법

Also Published As

Publication number Publication date
JP2024014141A (ja) 2024-02-01
TW202411281A (zh) 2024-03-16

Similar Documents

Publication Publication Date Title
US8084545B2 (en) Photo- and/or thermo-curable copolymer, curable resin compositions, and cured articles
US20110112266A1 (en) Curable copolymer and curable resin composition
KR20200078476A (ko) 화합물, 조성물, 경화물 및 경화물의 제조 방법
JP7049067B2 (ja) 重合性組成物、ブラックマトリクス用感光性組成物及び硬化物
KR20120138678A (ko) 지환식 에폭시기 함유 경화성 수지 조성물, 그의 제조 방법 및 그의 경화물
WO2018235664A1 (fr) Composition polymérisable, composition photosensible pour matrices noires, et composition photosensible pour entretoises en colonne noire
TWI782107B (zh) 光酸產生劑、硬化性組成物、硬化體、光阻組成物以及抗蝕劑圖案的製作方法
KR102374939B1 (ko) 경화성 조성물, 경화물 및 경화물의 제조 방법
TW201922889A (zh) 組合物、硬化物及硬化物之製造方法
WO2024018984A1 (fr) Copolymère, composition de résine durcissable et article durci
JP2023150423A (ja) 感光性樹脂組成物、感光性樹脂組成物を硬化してなる硬化膜、硬化膜付き基板及び硬化膜付き基板の製造方法
JP7190294B2 (ja) 共重合体、該共重合体を含む硬化性樹脂組成物、及びその硬化物
JP7483417B2 (ja) 感光性樹脂組成物、及びその硬化物
CN114466874B (zh) 共聚物、固化性树脂组合物以及固化物
CN110794648A (zh) 感放射线性组合物、硬化膜、硬化膜的制造方法及显示元件
JP7483416B2 (ja) 着色感光性樹脂組成物、カラーフィルタ、及び表示装置用部材又は表示装置
KR20230165909A (ko) 감광성 수지 조성물, 경화물, 컬러 필터, 및 표시 장치용 부재 또는 표시 장치
KR20220152541A (ko) 감광성 수지 조성물, 경화물, 컬러 필터, 표시 장치용 부재 및 표시 장치
JP2022159105A (ja) 感光性樹脂組成物、及びその硬化物
WO2020012753A1 (fr) Composition durcissable, structure et procédé de formation associé
JP2022159104A (ja) 着色感光性樹脂組成物、カラーフィルタ、及び表示装置用部材又は表示装置
TW202319374A (zh) 組合物、硬化物及硬化物之製造方法
JP2022042418A (ja) 組成物、硬化物、硬化物の製造方法
JP2011162726A (ja) 硬化性樹脂組成物、硬化物、フィルム、および重合体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23842907

Country of ref document: EP

Kind code of ref document: A1