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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • 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
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • 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
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
  • C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • 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
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

• the present invention relates to a polymer, a method for producing the same, a photosensitive resin composition, a cured product, a monomer compound, and a method for producing the same.
• the present invention provides a polymer that can provide a cured product with excellent solvent resistance even under low temperature curing conditions and has excellent storage stability, a method for producing the same, a photosensitive resin composition, a cured product, and This invention relates to monomeric compounds and methods for producing the same.
• Photosensitive resin compositions can be used in various applications such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, and organic protective films used in liquid crystal display devices, solid-state image sensors, etc.
• Applications to various applications such as optical components and electrical/electronic equipment have been studied, and resins and resin compositions with excellent properties required for each application have been developed.
• optical components, electrical machinery, electronic devices, and the like have become smaller, thinner, and more energy-saving, and as a result, the various components used are required to have higher quality performance.
• research is being conducted on resins and photosensitive resin compositions that can be used as materials for various parts and the like.
• Patent Document 1 describes a composition with (meth)acryloyl groups and acetal groups as having sufficient photocurability, allowing a high-resolution pattern to be obtained by photolithography, and having excellent thermal decomposition properties during firing. or a photocurable composition containing a photopolymerization initiator and a compound having a specific group having a hemiacetal group.
• Patent Document 2 describes a photosensitive resin composition that produces a cured film having high sensitivity, high transparency, and excellent ITO sputtering resistance, and describes a photosensitive resin composition that produces a carboxyl group or a phenolic hydroxyl group with an acid. a monomer unit having a group, and a monomer unit having a group having 3 to 16 carbon atoms having an ethylenically unsaturated bond at the terminal, a polymer having a weight average molecular weight of more than 1000, a photoacid generator, and a solvent.
• a photosensitive resin composition is described.
• Patent Document 3 describes a resin composition containing an alkali-soluble resin having a structure derived from a vinyl ether compound and a basic compound as a resin composition with excellent storage stability; describes a negative resist composition containing at least a component having a vinyl ether structure protected by acetal in its molecule.
• Patent Documents 5 to 7 describe polyfunctional (meth)acrylic acid esters having an acetal structure.
• the present invention was made in view of the above-mentioned current situation, and provides a polymer that can provide a cured product with excellent solvent resistance even under low-temperature curing conditions and also has excellent storage stability.
• the object of the present invention is to provide a photosensitive resin composition containing the same, and a cured product thereof.
• Another object of the present invention is to provide monomeric compounds that can be used for producing the above polymers, and methods for producing the above polymers and monomeric compounds.
• the present inventor conducted various studies on polymers that can be used in photosensitive resin compositions, and found that by using a polymer with a specific structure, the crosslinking reaction progresses well even under low-temperature curing conditions of 160°C or less. As a result, it was discovered that a cured product with excellent solvent resistance and a resin with excellent storage stability could be obtained, and the present invention was completed.
• X represents a hydrogen atom or a methyl group.
• R 1 represents a linear or branched divalent organic group.
• R 2 represents an organic group having 1 to 20 carbon atoms.
• [3] The polymer according to [1] or [2] above, further comprising an acid group-containing structural unit (B).
• [4] The polymer according to any one of [1] to [3] above, further comprising a structural unit (C) having a ring structure in the main chain.
• a polymer solution comprising the polymer according to any one of [1] to [4] above and a polar solvent.
• a step (Q-1) of polymerizing a monomer containing a group containing a hydroxyl group and a monomer component containing a hydroxyl group-containing monomer, and the polymer obtained in the above step (Q-1) are added with an acid.
• (meth)acrylate means “acrylate and/or methacrylate”
• (meth)acrylic acid means “acrylic acid and/or methacrylic acid”.
• X represents a hydrogen atom or a methyl group.
• L represents a linear or branched divalent organic group.
• Y represents a vinyl ether group that can be decomposed by acid or heat and attached to the side chain of the polymer.
• Examples of the divalent saturated aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a t-butylene group, a pentylene group, a neopentylene group, a hexamethylene group, and a heptylene group.
• Examples include alkylene groups such as octylene group, 2-ethylhexylene group, nonylene group, decylene group, undecylene group, and dodecylene group.
• the number of carbon atoms in the saturated aliphatic hydrocarbon group is preferably 1 to 10, more preferably 2 to 4.
• the divalent organic group represented by L above is a group represented by -COO-R 1 - (R 1 represents a linear or branched divalent organic group). It is preferable that there be.
• the linear or branched divalent organic group represented by R 1 above is preferably the linear or branched divalent hydrocarbon group, or the linear or branched divalent hydrocarbon group described above; Examples include groups containing a chain divalent hydrocarbon group and a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, -SO 2 -, etc.
• -R 3 -(O-R 4 ) n - (wherein R 3 and R 4 are the same or different and represent a divalent saturated aliphatic hydrocarbon group. n is an integer of 0 or more ) is more preferable.
• the divalent saturated aliphatic hydrocarbon group represented by R 3 and R 4 is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms.
• the above n is preferably an integer of 0 to 10, and more preferably 1.
• organic groups include groups obtained by acetal-protecting vinyl ether groups.
• the group in which the vinyl ether group is acetal-protected include groups containing a bonding group of -O-CH(CH 3 )-O-, preferably represented by -O-CH(CH 3 )-O-R 2 . The following groups are mentioned.
• R 2 preferably represents an organic group having 1 to 20 carbon atoms.
• hydrocarbon group containing a cyclic structure examples include a hydrocarbon group having a cyclic structure, or a hydrocarbon group having a cyclic structure and a chain structure.
• Examples of the hydrocarbon group having a cyclic structure include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
• the alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group.
• Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group and naphthyl group.
• the monovalent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms.
• the organic group represented by R 2 is preferably -R 5 (excluding a group containing a carbonyl group) or -CO-R 6 in terms of good low-temperature curability. , -CO-R 6 are more preferred.
• R 5 and R 6 in the formula are the same or different and represent an organic group, preferably a hydrocarbon group, or at least one selected from the group consisting of a hydrocarbon group and -O- and -COO-. represents a group containing one type of bond, more preferably an aliphatic hydrocarbon group, or an aliphatic hydrocarbon group and at least one type of bond selected from the group consisting of -O- and -COO-. It represents a group including, more preferably an alkyl group.
• the number of carbon atoms in the organic group represented by R 6 is preferably 1 to 19, more preferably 1 to 10, even more preferably 1 to 5, and most preferably 3. By controlling the carbon number within the above range, it is possible to achieve both storage stability and low temperature curability.
• X represents a hydrogen atom or a methyl group.
• R 1 represents a linear or branched divalent organic group.
• R 2 represents an organic group having 1 to 20 carbon atoms.
• R 1 and R 2 in the above formula (1-1) are the same as R 1 and R 2 described above, respectively.
• the polymer having the above-mentioned structural unit (A) can be obtained, for example, by polymerizing a monomer component containing a monomer into which the above-mentioned structural unit (A) can be introduced.
• the monomer into which the above structural unit (A) can be introduced is not particularly limited as long as a polymer having the above structural unit (A) can be obtained by polymerization, but for example, in the following formula (2), The monomers represented are mentioned.
• CH 2 CXL-Y (2) (In the formula, X, L, and Y are the same as X, L, and Y in formula (1), respectively.)
• R 7 represents a hydrogen atom or a methyl group.
• R 8 represents a linear or branched divalent organic group.
• R 9 represents an organic group having 1 to 20 carbon atoms. .
• the linear or branched divalent organic group represented by R 8 is the linear or branched divalent organic group represented by R 1 in the above formula (1-1).
• Preferred examples include groups similar to divalent organic groups such as .
• the organic group having 1 to 20 carbon atoms represented by R 9 the same groups as the organic group having 1 to 20 carbon atoms represented by R 2 in the above formula (1-1) are preferably mentioned.
• the organic group represented by R 9 is preferably -CO-R 6 .
• R 6 in the formula is preferably a hydrocarbon group, more preferably a chain saturated hydrocarbon group.
• the number of carbon atoms in the organic group represented by R 6 is preferably 1 to 19, more preferably 1 to 10, even more preferably 1 to 5, and most preferably 3.
• the monomer compound represented by the above formula (a) include (meth)acrylic acid 2-(2-(1-acetoxyethoxy)ethoxy)ethyl (meth)acrylic acid 2-(2- (1-isopropoxyethoxy)ethoxy)ethyl, 2-(2-(1-ethoxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-propionyloxyethoxy)ethoxy)(meth)acrylate ) ethyl, 2-(2-(1-butyloxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-formyloxyethoxy)ethoxy)ethyl (meth)acrylate, and the like.
• 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl (meth)acrylate and 2-(2-(1-butyloxyethoxy)ethoxy)ethyl (meth)acrylate are preferred.
• 2-(2-(1-butyloxyethoxy)ethoxy)ethyl (meth)acrylate is most preferred.
• the above monomer compounds may be used alone or in combination of two or more.
• R 7 represents a hydrogen atom or a methyl group
• R 8 represents a linear or branched chain
• Those which represent a divalent organic group and R 9 represents an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group) are new compounds.
• Such novel monomeric compounds are also part of the present invention.
• the above polymer may have only one type of the above structural unit (A), or may have two or more types.
• the content of the structural unit (A) is preferably 1 to 100% by mass, and preferably 5 to 50% by mass, based on 100% by mass of the total structural units of the polymer, in terms of good low-temperature curability. %, and even more preferably 10 to 40% by mass.
• Examples of the above-mentioned acid groups 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. or two or more types. Among these, a carboxyl group or a carboxylic acid anhydride group is preferred, and a carboxyl group is more preferred, since the developability becomes even better.
• a structural unit derived from an acid group-containing monomer is obtained as the structural unit (B).
• the acid group-containing monomer include compounds having the above-mentioned acid group and a polymerizable double bond (carbon-carbon double bond) in the molecule.
• the polymerizable double bond include a (meth)acryloyl group, a vinyl group, an allyl group, and a methallyl group. Among these, a (meth)acryloyl group is preferred.
• carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, long-chain unsaturated monocarboxylic acids, unsaturated acid anhydrides) are preferred from the viewpoint of versatility and availability. preferable.
• the acid group-containing monomer is more preferably an unsaturated monocarboxylic acid, and even more preferably (meth)acrylic acid.
• a polymer having an acid group-containing structural unit (B) After preparing a precursor polymer (prepolymer) having hydroxyl groups in advance, the hydroxyl groups are reacted with a polybasic acid or a polybasic acid anhydride to introduce acid groups (carboxyl groups). , a polymer having an acid group-containing structural unit (B).
• a polymer having an acid group-containing structural unit is produced by such a method, the acid group will be located relatively far from the main chain of the polymer, making it easier for the crosslinking reaction to proceed when the polymer is cured. Therefore, the curability can be further improved.
• a structural unit containing a carboxyl group produced by reacting a structural unit derived from a hydroxyl group-containing monomer with a polybasic acid or polybasic acid anhydride is obtained as the structural unit (B).
• Examples of the hydroxyl group-containing monomer include the same monomer compounds as the hydroxyl group-containing monomer described below as a monomer providing the structural unit (D).
• Examples of the polybasic acid or polybasic acid anhydride include the same compounds as the acid group-containing compounds described below. A specific reaction method will be explained in the polymer manufacturing method described later.
• an epoxy group can also be used instead of the hydroxyl group. That is, after preparing a polymer having epoxy groups in advance, the epoxy groups are subjected to an addition reaction with the acid groups of an acid group-containing monomer to open the epoxy groups, and the hydroxyl groups generated at that time are treated with a polybasic acid. Alternatively, a method of reacting a polybasic acid anhydride to produce a carboxyl group may also be mentioned.
• the content of the structural unit (B) is preferably 0 to 80% by mass based on 100% by mass of the total structural units of the polymer.
• the amount is more preferably 3 to 80% by weight, even more preferably 5 to 45% by weight, and even more preferably 10 to 30% by weight based on 100% by weight of the structural unit.
• dialkyl-2,2'-(oxydimethylene) diacrylate monomer examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 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- Propenoate, di(stearyl)-2,
• ( ⁇ -allyloxymethyl) acrylate monomer ⁇ -allyloxymethyl acrylate methoxyethyl, ⁇ -allyloxymethyl acrylate methoxyethoxyethyl, ⁇ -allyloxymethyl acrylate methoxyethoxyethoxyethyl, ⁇ -allyloxy 3-methoxybutyl methyl acrylate, ethoxyethyl ⁇ -allyloxymethyl acrylate, ethoxyethoxyethyl ⁇ -allyloxymethyl acrylate, phenoxyethyl ⁇ -allyloxymethyl acrylate, phenoxyethoxyethyl ⁇ -allyloxymethyl acrylate, etc.
• the above polymer may have a structural unit (D) other than the above-mentioned structural units (A), (B), and (C).
• Examples of the above-mentioned other structural unit (D) include structural units derived from the following monomers.
• the structural unit (D) is a structural unit derived from at least one monomer selected from the group consisting of a hydroxyl group-containing monomer, a (meth)acrylic acid ester monomer, and a styrene derivative. It is preferable that there be.
• the above polymer may have only one type of the above structural unit (D), or may have two or more types.
• the content ratio of the structural unit (D) is preferably 0 to 99% by mass, more preferably 1 to 99% by mass, and 2 to 99% by mass, based on 100% by mass of the total structural units of the polymer. It is more preferably 80% by weight, and even more preferably from 10 to 70% by weight.
• the content ratio of each structural unit (D) can be appropriately set depending on the use and purpose of the polymer of the present invention.
• the acid value of the above polymer is preferably 10 to 200 mgKOH/g.
• the acid value of the above polymer is preferably 20 to 150 mgKOH/g, and even more preferably 50 to 130 mgKOH/g, from the viewpoint of good developability.
• the above acid value is a value obtained by measurement by a neutralization titration method using a potassium hydroxide (KOH) solution, and is an acid value per 1 g of resin solid content.
• the weight average molecular weight of the above polymer is preferably 1,000 to 100,000.
• the weight average molecular weight of the above polymer is preferably from 3,000 to 50,000, and even more preferably from 5,000 to 20,000, from the standpoint of good low-temperature curability.
• the above weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) according to the method described in Examples.
• the vinyl ether equivalent of the above polymer is preferably 200 to 50,000 g/mol.
• the vinyl ether equivalent is more preferably from 300 to 10,000 g/mol, and even more preferably from 400 to 2,000 g/mol, from the viewpoint of improving curability and storage stability.
• the vinyl ether group here refers to a vinyl ether group generated when all acetal bonds in a polymer are deprotected, and refers to a vinyl ether group potentially existing in the polymer.
• the vinyl ether equivalent is the mass of the solid content of the polymer solution per 1 mol of vinyl ether groups of the polymer.
• the mass of the solid content of the polymer solution is the mass of the monomer components constituting the polymer.
• the vinyl ether equivalent can be determined by dividing the mass (g) of the solid content of the polymer in the polymer solution by the vinyl ether group (mol) of the polymer. Moreover, it can also be measured using various analyzes such as titration, elemental analysis, NMR, and IR, and differential scanning calorimetry.
• the above polymer may have a polymerizable double bond in the side chain.
• the curability of the above polymer can be improved.
• the polymerizable double bond include the above-mentioned polymerizable double bonds.
• a (meth)acryloyl group is preferred from the viewpoint of reactivity.
• the double bond equivalent of the above polymer is preferably 400 to 50,000 g/mol.
• the double bond equivalent is preferably 500 to 10,000 g/mol, and even more preferably 600 to 2,000 g/mol, from the viewpoint of improving curability.
• the double bond here refers to a double bond that is radically polymerizable. In other words, it is a polymerizable double bond typified by a (meth)acryloyl group.
• a double bond such as that produced by adding tetrahydrophthalic anhydride to a hydroxyl group is not a double bond because it has no reactivity. It is not included in the calculation as an equivalent amount.
• the double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of double bonds in the polymer.
• the mass of the solid content of the polymer solution is the mass of the monomer components constituting the polymer.
• the double bond equivalent can be determined by dividing the mass (g) of the solid content of the polymer in the polymer solution by the amount (mol) of double bonds in the polymer. Moreover, it can also be measured using various analyzes such as titration, elemental analysis, NMR, and IR, and differential scanning calorimetry.
• Method for producing polymer The method for producing the polymer of the present invention is not particularly limited as long as the above-mentioned polymer can be obtained. ), (C), and (D) can be introduced using a known method. The amount of each monomer can be adjusted as appropriate so that the content of each structural unit in the polymer falls within a desired range.
• the method for polymerizing the monomer components is not particularly limited, and commonly used methods such as bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used. Among these, solution polymerization is preferred because it is industrially advantageous and allows easy structural adjustment such as molecular weight. Furthermore, as the polymerization mechanism of the above monomer components, polymerization methods based on mechanisms such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization can be used. Polymerization methods based on are preferred. Furthermore, the molecular weight of the polymer obtained by polymerizing the above monomer components can be controlled by adjusting the amount and type of polymerization initiator, the polymerization temperature, the type and amount of chain transfer agent, and the like.
• Examples of the polymerization initiator include known peroxides and azo compounds that are commonly used as polymerization initiators.
• Examples of the chain transfer agent include compounds having a mercapto group, such as alkylmercaptans, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, which are commonly used as chain transfer agents. These may be used alone or in combination of two or more. Moreover, the amount of these additions can be appropriately set using a known method.
• solvent used in the above polymerization examples include aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane; and acetone, methyl ethyl ketone, and methyl isobutyl ketone.
• Ketone solvents such as chlorobenzene, dichloromethane, chloroform, and 1,2-dichloroethane
• nitrile solvents such as acetonitrile, propionitrile, and valeronitrile
• Ester solvents such as dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF) , tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), cyclopentyl methyl ether (CPME), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and other ether solvents; perfluorohexane, perfluoro Fluorine-based solvents such as cyclohexane, pentafluorobenzene, and octafluorotoluene; DMSO, nitromethane, and the like. Only one type of these may be used, or
• the polymerization temperature may be appropriately set depending on the type and amount of the monomer used, the type and amount of the polymerization initiator, etc., but for example, 40 to 130°C is preferable, and 50 to 120°C is more preferred. Further, the polymerization time can be similarly set appropriately, and for example, 1 to 15 hours is preferable, and 2 to 11 hours is more preferable.
• the method for producing the above polymer includes, among others, a monomer component containing a monomer (a) containing a group that generates a vinyl ether group by acid or heat, and a monomer component containing an acid group-containing monomer (b). It is preferable to include a step of polymerizing.
• This is a method for producing a polymer having a structural unit (A) represented by the above formula (1) and an acid group-containing structural unit (B), in which the vinyl ether group is removed by acid or heat.
• a method for producing a polymer (polymer production method 1) comprising a step (P-1) of polymerizing a monomer containing a group to be produced and a monomer unit containing an acid group-containing monomer , is one of the inventions.
• Examples of the monomer having a group capable of producing a vinyl ether group by acid or heat include monomers into which the above-mentioned structural unit (A) can be introduced, preferably those represented by the above formula (a). Examples include monomeric compounds. Examples of the acid group-containing monomer include those mentioned above.
• step (P-1) above can be carried out in the same manner as the polymerization method described above.
• additives such as the above-mentioned polymerization initiator and chain transfer agent, solvents, and the like may be used as appropriate.
• the polymerization in step (P-1) above is preferably carried out in the presence of a basic compound.
• a basic compound By polymerizing the monomer components in the presence of a basic compound, the production of vinyl ether groups of the monomer (a) by the acid groups of the acid group-containing monomer units is suppressed, The desired polymerization reaction can proceed favorably. Furthermore, since the acidity of the reaction system is neutralized and the generation of vinyl ether groups is suppressed, gelation can be suppressed and a polymer with excellent storage stability can be obtained. Furthermore, a basic compound may be added after polymerization in order to improve the storage stability of the resulting polymer.
• Examples of the basic compounds include ammonia; primary amines such as methylamine; secondary amines such as dimethylamine; tertiary amines such as triethylamine and diethylmethylamine; aliphatic compounds such as dimethylethanolamine, n-butylamine, and diethylamine.
• Tetraalkylammonium halides such as tetramethylammonium chloride and tetraethylammonium chloride
• Tetraalkylammonium organic acid salts such as tetramethylammonium acetate
• Tetraalkylammonium inorganic acid salts such as tetramethylammonium hydrogen sulfate and tetraethylammonium hydrogen sulfate
• Tetra (Hydroxy)alkylammonium hydroxides such as methylammonium hydroxide, tetraethylammonium hydroxide, monohydroxyethyltrimethylammonium hydroxide
• hydroxides of alkali metals such as sodium and potassium
• transition metals such as barium, strontium, calcium, and lanthanum hydroxides
• free salts of complex salts such as [Pt(NH 3 ) 6 ](OH) 4 ; and the like.
• the acid group-containing compound is preferably a polybasic acid or a polybasic acid anhydride, such as carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimellitic acid; succinic anhydride, maleic anhydride, etc. , carboxylic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, trimellitic anhydride, and the like. Among these, carboxylic acid anhydrides are preferred, and succinic anhydride is more preferred, since they have higher addition reactivity.
• the amount of the acid group-containing compound used may be appropriately determined depending on the use, purpose, desired acid value, etc. of the resulting polymer.
• the reaction between the polymer and the acid group-containing compound in step (Q-2) is preferably carried out in the presence of a basic compound.
• the addition reaction of the acid group-containing compound described above produces acid groups at the ends of the polymer, which are immediately neutralized by the basic compound. Therefore, vinyl ether groups are easily protected in groups that generate vinyl ether groups by acid or heat in the resulting polymer, and reactions between polymers are suppressed, resulting in better synthesis and storage stability of the polymer. Become.
• Examples of the basic compound include the same compounds as the above-mentioned basic compounds.
• the amount of the basic compound used is not particularly limited as long as it can suppress the generation of vinyl ether groups, but for example, the amount of the basic compound used in the above step (Q-1) may be The amount is preferably 0.5 to 10 equivalents, more preferably 0.8 to 2 equivalents, and even more preferably 0.9 to 1.2 equivalents, relative to 1 equivalent of the structural unit containing .
• a polymerizable double bond can be introduced into the side chain of the polymer by subjecting the acid group to an addition reaction with an epoxy group-containing compound.
• an epoxy group-containing compound For example, after preparing a polymer having an acid group (base polymer), the acid group is reacted with the above-mentioned epoxy group-containing monomer, and the epoxy group is cleaved, resulting in an addition reaction to form a polymerizable double bond. can be introduced.
• the basic compound may remain (exist) after producing the polymer, and the basic compound A polymer solution containing the compound is also one of the preferred embodiments of the present invention.
• a polymer solution has good storage stability.
• the polymer solution may further contain a polar solvent described below.
• Examples of the vinyl ether group-containing (meth)acrylate compound include a compound represented by the following formula (3).
• R 11 represents a hydrogen atom or a methyl group.
• R 12 represents a linear or branched divalent organic group.
• Examples of the organic group represented by R 12 in the above formula (3) include the same groups as the organic group represented by R 8 in the above formula (a).
• vinyl ether group-containing (meth)acrylate compound examples include 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, and the like.
• carboxylic acid compounds include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, heptylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; Monocarboxylic acid compounds such as formic acid, benzoic acid, ⁇ -carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate; oxalic acid, malonic acid, succinic acid , tartaric acid, malic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, dicarboxylic acid compounds such as 5-norbornenedicarboxylic acid, and the like.
• Monocarboxylic acid compounds such as formic acid,
• ketones such as methyl ethyl ketone
• polar solvents such as dimethylformamide and dimethyl sulfoxide
• halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, and chlorobenzene
• esters such as ethyl acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethers such as ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether
• examples include one or two of ether acetates such as acetate, ethylene glycol monophenyl ether acetate, and propylene glycol monomethyl
• catalysts and polymerization inhibitors may be added.
• known additives such as catalysts and polymerization inhibitors may be added.
• the above catalyst include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, and glycolic acid; oxalic acid, maleic acid, oxaloacetic acid, malonic acid, and fumaric acid.
• Aromatic sulfonic acids or salts thereof sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; hydrogen sulfates such as sodium hydrogen sulfate, potassium hydrogen sulfate; sulfuric acid , mineral acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, polyphosphoric acid; heteropolyacids such as phosphovanazide molybdic
• polymerization inhibitor examples include quinone polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; 2,2'-methylene-bis(4-methyl-tert-butylphenol), 2, 6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl 4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6 - Alkylphenol polymerization inhibitors such as tri-tert-butylphenol; amine polymerization inhibitors such as alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, and phenothiazine; 4-hydroxy-2,2,6,6 N-oxyls such as -tetramethylpiperidine-N-oxyl; copper dithiocarbamate polymerization inhibitors such as copper dimethyldithioc
• the amount of the polymerization inhibitor used is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, based on 100 parts by mass of the vinyl ether group-containing (meth)acrylate compound.
• the amount is preferably 0.01 to 0.5 parts by mass, and more preferably 0.01 to 0.5 parts by mass.
• the reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C, and even more preferably 20 to 60°C.
• the reaction time is, for example, preferably 0.1 to 20 hours, more preferably 1 to 15 hours, and even more preferably 2 to 12 hours.
• a basic compound may be added to the monomeric compound in order to improve the storage stability of the monomeric compound.
• Examples of the basic compound include the same basic compounds as mentioned above.
• the above-mentioned monomer compounds can be produced by the above-mentioned production method, but among the above-mentioned monomer compounds, the monomer compound represented by the following formula (a-1) is a vinyl ether group-containing (meth) It includes a step of reacting an acrylate compound and a carboxylic acid compound, and in the reaction step, the amount of the carboxylic acid compound used is 1 equivalent or more with respect to 1 equivalent of the vinyl ether group of the vinyl ether group-containing (meth)acrylate compound. Preferably, it is produced by a method. This method of manufacturing the above formula (a-1) is a new manufacturing method and is one of the aspects of the present invention.
• R 7 represents a hydrogen atom or a methyl group.
• R 8 represents a linear or branched divalent organic group.
• R 10 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Represents a group (excluding groups containing a (meth)acryloyl group) Examples of the organic group having 1 to 20 carbon atoms represented by R 10 include the same groups as the organic group represented by R 6 described above, except that groups containing a (meth)acryloyl group are excluded.
• Polymer solution The above-mentioned polymer is preferably used together with a polar solvent to form a polymer solution.
• a polar solvent By adding a polar solvent to the above-mentioned polymer to form a polymer solution, the storage stability of the polymer is improved. It is not clear why the storage stability of the above polymer is improved by the addition of a polar solvent, but the interaction with the acetal structure suppresses the deprotection of the acetal group, so it maintains solvent resistance while maintaining solvent resistance. It is thought that storage stability can be improved.
• Such a polymer solution containing the above-mentioned polymer and a polar solvent is also part of the present invention.
• the alcoholic solvent is preferably saturated alcohol, and includes monofunctional alcohols (monoalcohols), polyhydric alcohols, glycol monoethers, and the like.
• Specific examples of the alcoholic solvents include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n -Propyl ether, 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
• the number of carbon atoms in the alcoholic solvent is preferably 1 to 10, more preferably 2 to 8, and 3 to 6, since the boiling point is relatively low and removal by heating is easy. is even more preferable.
• propylene glycol monomethyl ether is particularly preferred.
• amine solvent examples include diethyleneamine, dimethylamine, oleylamine, and the like.
• phenolic solvent examples include phenol, cresol, o-cresol, m-cresol, p-cresol, xylenol, and the like.
• aprotic solvent examples include ether solvents, ether acetate solvents, and amide solvents. Among these, it is more preferable that the aprotic solvent is an amide solvent.
• ether solvent examples include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and the like.
• ether acetate solvent examples include ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, etc.
• ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, etc.
• ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl
• amide solvent examples include N,N-diethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and tetramethylurea. From the viewpoint of compatibility with the copolymer, N,N-dimethylformamide is preferred.
• the polar solvent is preferably at least one solvent selected from the group consisting of alcohol solvents, ether solvents, and amide solvents, and preferably selected from the group consisting of alcohol solvents and amide solvents. More preferably, at least one solvent is used.
• the boiling point of the polar solvent is preferably 70 to 180°C, and preferably 100 to 170°C, since it can be easily removed by heating, has a certain boiling point, and can easily form a flat film. is more preferable, and even more preferably 110 to 160°C.
• the polymer solution may contain one or more polar solvents.
• the content of the polar solvent in the polymer solution is preferably 10% by mass or more, more preferably 30% by mass or more, and 40% by mass or more based on 100% by mass of the polymer solid content. It is even more preferable that there be. Further, the content of the polar solvent is preferably 1000% by mass or less, and preferably 300% by mass or less, based on 100% by mass of the polymer solid content, in order to facilitate concentration adjustment in the resin composition. is more preferable, and even more preferably 200% by mass or less.
• the above polymer solution may be prepared by mixing a polymer purified from a polymer solution containing the above polymer obtained during polymerization with the above polar solvent, or a polymer solution containing the above polymer may be mixed with the above polar solvent. It may be prepared by adding a solvent.
• the polymer solution may contain the polymerization solvent.
• the polymer solution may contain components other than the above-described polymer and polar solvent.
• Polymer solution The above-mentioned polymer or polymer solution can be used together with a basic dispersant and/or a basic compound to form a polymer solution.
• the above polymer solution has excellent storage stability.
• a polymer solution containing the above-mentioned polymer or polymer solution and a basic dispersant and/or a basic compound is also part of the present invention. Further, it is also one of the preferred embodiments of the present invention that the polymer or basic dispersant is neutralized with a basic compound.
• SOLSPERSE registered trademark
• Ajisper registered trademark
• PA111 PB711, PB821, PB822, PB824, etc.
• Disparon (registered trademark) 1831, 1850, 1860, DA-703-50, DA-7301, DA-325, DA234 (all manufactured by Kusumoto Kasei Co., Ltd.).
• the polymer in the polymer solution preferably has an epoxy equivalent of 1000 g/mol or more, more preferably 5000 g/mol or more, and has an epoxy group It is more preferable not to have.
• the epoxy equivalent can be determined by dividing the mass (g) of the solid content of the polymer by the number of moles (mol) of epoxy groups contained in the polymer.
• the content of the polymer and the basic dispersant in the coloring material dispersion is preferably within the same range as the content of the polymer and the basic dispersant in the polymer solution described above.
• the amount of the solvent in the coloring material dispersion is preferably 10 to 1000 parts by mass, more preferably 30 to 1000 parts by mass, based on 100 parts by mass of the total solid content of the coloring material dispersion, in terms of good storage stability.
• the amount is 300 parts by weight, more preferably 40 to 200 parts by weight.
• the method for preparing the coloring material dispersion is not particularly limited, and it can be prepared by mixing and dispersing each component contained in the coloring material dispersion using a known mixing and dispersing means.
• the content of the polar solvent is preferably 10 to 1000 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition. , more preferably 30 to 300 parts by mass, and still more preferably 40 to 200 parts by mass.
• the content of the basic dispersant may be 1 to 50% by mass based on 100% by mass of the total solid content of the photosensitive resin composition.
• the amount is preferably 3 to 45% by weight, more preferably 5 to 35% by weight.
• 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, bisphenol F alkylene oxide di(meth)acrylate;
• Trifunctional or higher functional polyfunctional (meth)acrylate compounds such as modified dipentaerythritol hexaacrylate represented by;
• Ethylene glycol diallyl ether diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide added trimethylolpropane triallyl ether, ethylene oxide added ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol te
• Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide addition tri(acryloyloxyethyl)isocyanurate, alkylene Polyfunctional (meth)acryloyl group-containing isocyanurates such as oxidized 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 the reaction of polyfunctional isocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymerizable compounds may be used alone or in combination of two or more.
• polyfunctional polymerizable compounds it is preferable to use polyfunctional polymerizable compounds from the viewpoint of further enhancing the curability of the photosensitive resin composition.
• the functional number of the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more. Further, the functional number is preferably 10 or less, more preferably 8 or less.
• the molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, it is preferably, for example, 2000 or less.
• polyfunctional (meth)acrylate compounds from the viewpoint of reactivity, economy, availability, etc., preferred are polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and (meth)acryloyl groups.
• examples include compounds having a (meth)acryloyl group, such as isocyanurate compounds, and more preferably polyfunctional (meth)acrylate compounds.
• the photosensitive resin composition has better photosensitivity and curability, and a cured product with even higher hardness and transparency can be obtained.
• the polyfunctional polymerizable compound it is more preferable to use a trifunctional or more polyfunctional (meth)acrylate compound.
• the content of the polymerizable compound 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, and more preferably 15 to 50% by mass. More preferably, the amount is 40% by mass.
• Photopolymerization initiator Specific examples of the photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF), 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholinophenyl) Aminoketone compounds such as phosphorus-4-yl-phenyl)-butan-1-one ("IRGACURE379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE651", Benzyl ketal compounds such as phenylglyoxylic acid methyl ester (“DAROCUR MBF”, manufactured by BASF); 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”,
• the content of the photopolymerization initiator is preferably 0.3 to 20% by mass, and preferably 0.5 to 10% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. is more preferable, and even more preferably 1 to 8% by mass.
• the photoacid generator used in the present invention is a compound that generates radicals at the same time as an acid when irradiated with light.
• Examples of the above-mentioned photoacid generators include compounds that generate acids upon exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays, and specifically include onium salt compounds, sulfone compounds, and sulfone Known compounds such as acid ester compounds, quinonediazide compounds, sulfonimide compounds, and diazomethane compounds can be mentioned.
• the photoacid generator is preferably at least one selected from the group consisting of onium salt compounds, sulfonimide compounds, and diazomethane compounds, more preferably onium salt compounds, and triaryl More preferred are sulfonium salts.
• Specific examples of the photoacid generator include compounds described in paragraphs [0112] to [0117] of JP-A No. 2021-39186.
• the content of the photoacid generator is not particularly limited and may be set as appropriate as long as the effect of the present invention is exhibited, but for example, the total solid content of the photosensitive resin composition of the present invention 100 It is preferably 0.3 to 20% by weight, more preferably 0.5 to 10% by weight, and even more preferably 1 to 8% by weight.
• the photosensitive resin composition may also contain other components other than those mentioned above, if necessary.
• Other components mentioned above include, for example, solvents; coloring materials (pigments, dyes); dispersants; heat resistance improvers; leveling agents; development aids; inorganic particles such as silica particles; silane-based, aluminum-based, titanium-based, etc.
• Coupling agent filler, thermosetting resin such as phenol resin, polyvinylphenol; curing aid such as polyfunctional thiol compound; plasticizer; polymerization inhibitor; ultraviolet absorber; antioxidant; matting agent; antifoaming agent Antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinone diazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; thermal acid generators; and the like.
• thermosetting resin such as phenol resin, polyvinylphenol
• curing aid such as polyfunctional thiol compound
• plasticizer polymerization inhibitor
• ultraviolet absorber antioxidant
• matting agent antifoaming agent
• Antistatic agents slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinone diazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; thermal acid generators; and the like.
• these may be used alone or in combination of two or more.
• the photosensitive resin composition preferably contains a polyfunctional thiol compound, since crosslinking with vinyl ether groups and promotion of cationic polymerization can be expected.
• polyfunctional thiol compounds include tris(3-mercaptopropionyloxy)ethyl isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3 -Mercaptopropionate, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)) (ethyl)-1,3,5-triazinane-2,4,6-trione, trimethylolpropane tris(3-mercaptobutyrate),
• the method for preparing the photosensitive resin composition of the present invention is not particularly limited and any known method may be used, such as a method of mixing and dispersing the above-mentioned components using various mixers and dispersers. can be mentioned.
• the mixing/dispersing step is not particularly limited and may be performed by a known method. Moreover, it may further include other steps that are normally performed.
• the photosensitive resin composition contains a coloring material, it is preferably prepared through a known coloring material dispersion process.
• the method for obtaining a cured product using the photosensitive resin composition of the present invention is not particularly limited, and any known method may be used. For example, coating the photosensitive resin composition above on a substrate, Alternatively, a method of obtaining a cured product by curing the molded product by heating, irradiation with active energy rays such as ultraviolet rays, or a combination thereof can be mentioned.
• the method for producing the cured product includes, for example, a step (1) of coating the photosensitive resin composition on a substrate to form a coating film, a step (2) of irradiating the formed coating film with light, Preferred methods include a step (3) of developing and removing unirradiated areas and a step (4) of heating the irradiated coating film.
• the above-mentioned base material is not particularly limited and may be appropriately selected depending on the purpose and use, and examples thereof include base materials made of various materials such as glass plates and plastic plates.
• the method of applying the photosensitive resin composition to form a coating film is not particularly limited, and may be performed by a known method such as spin coating, slit coating, roll coating, or casting coating. be able to.
• the above-mentioned drying can be performed by a known method, for example, using a hot plate, an IR oven, a convection oven, or the like.
• the drying conditions are appropriately selected depending on the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the dryer, etc., but it is usually carried out at a temperature of 50 to 160°C for 10 seconds to 300 seconds. suitable.
• the method of irradiating the formed coating film with light is not particularly limited, and any known method can be used.
• active light sources used for light irradiation include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps. , an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, a semiconductor laser, and the like.
• the irradiation may be performed through a photomask.
• the photomask it is preferable to use a mask in which a light-shielding portion is formed according to the intended pattern.
• step (3) after the light irradiation step described above, development is performed using a developer to remove unirradiated portions. By irradiating the light, the irradiated portion is cured, and the cured product is made insoluble or hardly soluble in the developer. On the other hand, since the unirradiated portions are dissolved in the developer, they are removed by the development process, and a patterned cured film can be obtained.
• the development treatment can be carried out usually at a development temperature of 10 to 50° C. by methods such as immersion development, spray development, brush development, and ultrasonic development.
• the developed coating film is preferably heated at 150° C. or lower.
• the heating temperature is preferably 130° C. or lower, more preferably 120° C. or lower.
• the curing reaction proceeds favorably even at relatively low temperatures, and it is possible to provide a cured product with excellent solvent resistance.
• the lower limit of the heating temperature is preferably 70° C. or higher, more preferably 80° C. or higher in terms of maintaining curability.
• the polymer and photosensitive resin composition of the present invention have excellent storage stability and can provide a cured product with excellent solvent resistance even under low temperature curing conditions, so storage stability and high solvent resistance are required. It can be suitably used for various purposes.
• the polymer and photosensitive resin composition of the present invention are suitably used for optical materials, and preferably for resists.
• the curable resin composition of the present invention can be suitably used for both negative and positive types.
• the polymer and photosensitive resin composition of the present invention can be used, for example, in color filters, black matrices, photo spacers, etc. used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state image sensors, touch panel display devices, etc.
• Suitable for use in various optical components and components of electrical and electronic equipment such as black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, films, and organic protective films. be able to. Among these, it is preferably used for forming color filters.
• ⁇ Acid value> 3g of the polymer solution was accurately weighed, dissolved in a mixed solvent of 90g of acetone and 10g of water, and titrated using a 0.1N KOH aqueous solution as a titrant. Titration was performed using an automatic titration device (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solid content (mgKOH/g) was determined from the acid value of the polymer solution and the solid content of the polymer solution. I asked for it. In addition, the solid content of the polymer solution was determined by the following method.
• the weight average molecular weight of the polymer was determined by GPC (gel permeation chromatography) 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. was measured.
• the photosensitive resin composition was spin-coated onto a 5 cm square glass substrate, dried at 90°C for 2 minutes, exposed to light at 100 mJ using a high-pressure mercury lamp, and heat-treated (post-cured) at 90°C for 30 minutes to form a film. A cured film with a thickness of 2 ⁇ m was obtained. Then, the cured film was immersed in 20 g of propylene glycol monomethyl ether at 30° C. for 5 minutes and then taken out, and the absorbance of the immersion liquid after taking out the cured film was measured using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The larger the absorbance value, the more the coloring material eluted into the immersion liquid, and the lower the solvent resistance of the photosensitive resin composition was evaluated.
• a photosensitive resin composition was applied to a 10 cm square glass substrate by spin coating, and after heat treatment (90°C, 3 minutes), a 30 ⁇ m line-and-space opening was provided at a distance of 50 ⁇ m from the coating film.
• a UV aligner manufactured by Dainihon Kaken Co., Ltd., product name "MA-1100" equipped with a 2.0 kW ultra-high pressure mercury lamp was used to expose to light at an exposure amount of 60 mJ/cm 2 (365 nm illuminance conversion).
• Example 1 Synthesis of Polymer (B-1) 146.7 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, and the mixture was purged with nitrogen and heated. The temperature was raised to 60°C.
• a dropping tank (A) 25.0 parts of propylene glycol monomethyl ether acetate, 23.1 parts of acetic acid, and 0.01 part of p-toluenesulfonic acid were placed in a beaker and mixed with stirring to obtain a uniform liquid mixture.
• Example 2 Synthesis of Polymer (B-2) 133.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, and the mixture was purged with nitrogen and then heated. The temperature was raised to 50°C.
• Example 3 Synthesis of Polymer (B-3) 109.3 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, and the mixture was purged with nitrogen and heated. The temperature was raised to 60°C. On the other hand, in a beaker as a dropping tank, 100.0 parts of propylene glycol monomethyl ether acetate, 100.0 parts of 2-(2-(1-ethoxyethoxy)ethoxy)ethyl methacrylate, and 3.5 parts of n-dodecyl mercaptan were mixed with stirring.
• Example 4 Synthesis of Polymer (B-4) 115.3 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, and the mixture was purged with nitrogen and then heated. The temperature was raised to 60°C.
• a dropping tank 10.0 parts of N-phenylmaleimide, 50.0 parts of cyclohexyl methacrylate, 10.0 parts of 2-hydroxyethyl methacrylate, 10.0 parts of acrylic acid, and 2-(2- Prepare a stirred mixture of 20.0 parts of (1-ethoxyethoxy)ethyl, 20.0 parts of propylene glycol monomethyl ether acetate, and 4.0 parts of n-dodecyl mercaptan, and place it in a beaker as an initiator tank.
• an initiator tank 2.0 parts of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-70) and 28.0 parts of propylene glycol monomethyl ether acetate. A stirred mixture was prepared. After the temperature of the reaction tank reached 50° C., while maintaining the same temperature, dropping was started from the dropping tanks (A) and (B) over a period of 3 hours to carry out polymerization. A total of 30 parts of the initiator tank was divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the polymerization start, and 5 parts each was added to the reaction tank. . After the completion of the dropwise addition, the temperature was kept at 50°C and the mixture was aged for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a polymer (B-8). Table 2 shows various physical properties of the obtained polymer.
• Example 9 Synthesis of Polymer (B-9) 145.8 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, and after purging with nitrogen, the mixture was heated. The temperature was raised to 60°C.
• Example 10 Synthesis of Polymer (B-10) 228.3 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, and after purging with nitrogen, heating was performed. The temperature was raised to 60°C.
• the dropping tank (A) 15.0 parts of cyclohexyl methacrylate, 55.0 parts of 2-hydroxyethyl methacrylate, and 30.0 parts of 2-(2-(1-acetoxyethoxy)ethoxy)ethyl methacrylate were placed in a beaker.
• a mixture of 25.0 parts of -(1-isopropoxyethoxy)ethoxy)ethyl, 3.0 parts of n-dodecylmercaptan, and 25.0 parts of propylene glycol monomethyl ether acetate was prepared.
• As an initiator tank 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-65) and 28.0 parts of propylene glycol monomethyl ether acetate were stirred in a beaker. A mixture was prepared. After the temperature of the reaction tank reached 60°C, while maintaining the same temperature, dropping was started from the dropping tank over 3 hours to carry out polymerization.
• a total of 30 parts of the initiator tank was divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the polymerization start, and 5 parts each was added to the reaction tank. .
• the temperature of the reaction tank was raised to 70°C, and aging was performed for 10 hours. Thereafter, it was cooled to room temperature, and 5.1 parts of acrylic acid, 12.2 parts of triethylamine, and 0.2 parts of Antige W400 were added, and an oxygen/nitrogen mix gas adjusted to an oxygen concentration of 7% was bubbled at 20 ml/min.
• the reaction was carried out at °C for 7 hours.
• a dropping tank (B) As an initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-65) and 28.0 parts of propylene glycol monomethyl ether acetate were stirred in a beaker. A mixture was prepared. After the temperature of the reaction tank reached 60° C., while maintaining the same temperature, dropping was started from the dropping tanks (A) and (B) over a period of 3 hours to carry out polymerization.
• a total of 30 parts of the initiator tank was divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the polymerization start, and 5 parts each was added to the reaction tank. .
• the temperature of the reaction tank was raised to 70°C, and aging was performed for 10 hours. Thereafter, it was cooled to room temperature, and 14.0 parts of methacrylic acid, 26.9 parts of triethylamine, and 0.2 parts of Antige W400 were added, and an oxygen/nitrogen MIX gas adjusted to an oxygen concentration of 7% was bubbled at 20 ml/min.
• the reaction was carried out at °C for 7 hours.
• the dropping tank (A) 2.0 parts of N-benzylmaleimide, 38.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, n - Prepare a stirred mixture of 2.0 parts of dodecyl mercaptan, and add 30.0 parts of propylene glycol monomethyl ether acetate, 7.3 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid to a beaker as a dropping tank (B). The mixture was prepared and stirred to obtain a uniform mixed solution.
• an initiator tank As an initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-65) and 28.0 parts of propylene glycol monomethyl ether acetate were stirred in a beaker. A mixture was prepared. After the temperature of the reaction tank reached 60°C, while maintaining the same temperature, dropping was started from the dropping tanks (A) and (B) over a period of 3 hours to carry out polymerization. A total of 30 parts of the initiator tank was divided into 6 times: 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the polymerization start, and 5 parts each was added to the reaction tank. .
• Example 16 Synthesis of Polymer (B-16) 159.8 parts of propylene glycol monomethyl ether acetate was charged into a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet, and the mixture was purged with nitrogen and heated. The temperature was raised to 60°C.
• the dropping tank (A) 2.0 parts of N-benzylmaleimide, 22.5 parts of cyclohexyl methacrylate, 1.0 parts of methyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, and propylene glycol monomethyl were placed in a beaker.
• a dropping tank (B) As an initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-65) and 28.0 parts of propylene glycol monomethyl ether acetate were stirred in a beaker. A mixture was prepared. After the temperature of the reaction tank reached 60°C, while maintaining the same temperature, dropping was started from the dropping tanks (A) and (B) over a period of 3 hours to carry out polymerization.
• a total of 30 parts of the initiator tank was divided into 6 times: 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the polymerization start, and 5 parts each was added to the reaction tank. .
• the temperature was raised to 70°C and ripened for 6 hours.
• 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were charged into the reaction tank, and a reaction was carried out at 50° C. for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain a polymer (B-16).
• Table 2 shows various physical properties of the obtained polymer.
• a dropping tank (A) a beaker containing 28.0 parts of 3-carboxyadamantyl methacrylate, 12.8 parts of azobisisobutyronitrile, and 72.0 parts of propylene glycol monomethyl ether acetate was prepared with stirring, A beaker containing 72.0 parts of 4-(1-methoxy)ethoxycyclohexyl methacrylate and 18.0 parts of propylene glycol monomethyl ether acetate was prepared as the dropping tank (B). After the temperature of the reaction tank reached 70°C, while maintaining the same temperature, dropping was started from the dropping tanks (A) and (B) over a period of 3 hours to carry out polymerization. After the dropwise addition was completed, the temperature was kept at 70°C and the mixture was aged for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a polymer (B-17). Table 2 shows various physical properties of the obtained polymer.
• V-70 V65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-65)
• AIBN Azobisisobutyronitrile
• L11 t-butyl peroxypivalate (“Luperox 11” manufactured by Arkema Yoshitomi)
• TEA triethylamine
• DEMA diethylmethylamine
• 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 basic dispersant, C.I. I. 2.25 parts of Pigment Green 58 and C.I. I. Pigment Yellow 138 was mixed with 1.5 parts and dispersed in a paint shaker for 3 hours to obtain Pigment Dispersion 1 (solid content: 22% by mass).
• Photosensitive resin compositions (C-2) to (C-19) were obtained in the same manner as in Example 1, except that the formulations shown in Table 3 were used. The developability, solvent resistance, and storage stability of the resulting photosensitive resin composition were evaluated using the methods described above. Table 3 shows the results.
• the forms of Examples with linear or branched chains have good stability as the vinyl ether does not easily desorb during storage, and desorbs all at once during low-temperature calcination, reducing the reactivity of the desorbed vinyl ether. Since it has a high solvent resistance, it also has good solvent resistance and can overcome the trade-off between storage stability and solvent resistance. Furthermore, in Comparative Example 1, since there is no basic compound that neutralizes the acid group-containing monomer unit, the protective group of the vinyl ether progresses during storage of the polymer solution, and the vinyl ether group is regenerated. It is considered that storage stability deteriorated compared to Comparative Example 2 because crosslinking progressed. It is considered that Example 6 also had worse storage stability than the other Examples for the same reason.
• the resin solutions of Examples 22 to 25 had smaller changes in acid value than the resin solutions of Comparative Examples 4 to 5, and had better storage stability. Comparing Examples 22 and 23 containing the polymer (B-5) with Examples 24 and 25 containing the polymer (B-11), it was found that the resin solution of the example containing the polymer (B-5) was However, the amount of change in acid value was smaller regardless of the presence or absence of an amine-based dispersant. Considering these results, it was found that the lower the amount of epoxy groups in the resin, the better the storage stability.
• Example 22 and Example 23 it was found that the resin solution of Example 22 containing an amine dispersant had a smaller change in acid value and had better storage stability. This was thought to be due to the addition of the amine dispersant suppressing the deprotection of the acetal.
• Example 24 and Example 25 it was found that the resin solution of Example 24 containing an amine dispersant had a larger change in acid value. This tendency was also observed in the comparison between Comparative Example 4 and Comparative Example 5. From these results, it was considered that amine dispersants reduce the storage stability of resins containing epoxy groups. This was thought to be due to the addition of the amine dispersant promoting the reaction between acid groups and epoxy groups.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Optics & Photonics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (3)

Applications Claiming Priority (6)

Publications (1)

Family

ID=89379982

Family Applications (1)

Country Status (5)

Citations (4)

Family Cites Families (10)

• 2023
  • 2023-06-19 JP JP2024529002A patent/JPWO2023248976A1/ja active Pending
  • 2023-06-19 KR KR1020247038200A patent/KR20250007561A/ko active Pending
  • 2023-06-19 WO PCT/JP2023/022596 patent/WO2023248976A1/ja not_active Ceased
  • 2023-06-19 CN CN202380048853.XA patent/CN119403843A/zh active Pending
  • 2023-06-20 TW TW112123158A patent/TW202413484A/zh unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events