WO2013172009A1 - Composé de type polyester réactif et composition de résine durcissable sous l'effet d'un rayonnement d'énergie active - Google Patents

Composé de type polyester réactif et composition de résine durcissable sous l'effet d'un rayonnement d'énergie active Download PDF

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Publication number
WO2013172009A1
WO2013172009A1 PCT/JP2013/003030 JP2013003030W WO2013172009A1 WO 2013172009 A1 WO2013172009 A1 WO 2013172009A1 JP 2013003030 W JP2013003030 W JP 2013003030W WO 2013172009 A1 WO2013172009 A1 WO 2013172009A1
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Prior art keywords
resin composition
compound
acid anhydride
active energy
curable resin
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PCT/JP2013/003030
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English (en)
Japanese (ja)
Inventor
山本　和義
聡 小木
香津美 小淵
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日本化薬株式会社
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Publication of WO2013172009A1 publication Critical patent/WO2013172009A1/fr

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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/47—Polyesters chemically modified by esterification by unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • 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
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
    • C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates

Definitions

  • the present invention relates to a phenol aralkyl type epoxy resin (a) having an excellent balance of a hydroxyl group, an epoxy group and a softening point, one or more polymerizable ethylenically unsaturated groups in a molecule represented by acrylic acid, and the like.
  • Reactive polyester obtained by addition polymerization reaction of compound (b) having at least two carboxy groups and saturated or unsaturated polybasic acid anhydride (c) having at least two acid anhydride structures in one molecule It relates to compound (A).
  • the present invention relates to a reactive polyester compound (A ′) obtained by reacting the reactive polyester compound (A) with a saturated or unsaturated dibasic acid anhydride (d).
  • These reactive polyesters have good dispersibility in pigments, and from resin compositions containing these, film forming materials, solder resists, plating resists, color resists, color filter resists, black matrices, etc.
  • a tough cured product suitable for various resists and optical waveguides can be obtained.
  • the printed wiring board is required to have high accuracy and high density in order to reduce the size and weight of portable devices and improve the communication speed.
  • solder resist that covers the circuit itself has become increasingly sophisticated. For this reason, solder resists are required to have the ability to withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability.
  • a film-forming material having tougher cured properties that satisfies the requirements.
  • Patent Documents 1 and 2 a reactive polycarboxylic acid compound in which a carboxyl group is introduced with an acid anhydride for the purpose of patterning with an alkaline developer after carboxylating an epoxy resin with acrylic acid or the like is used for resist,
  • application to solder resist is generally known (Patent Documents 1 and 2).
  • An acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as a basic skeleton is generally known as a material exhibiting high toughness after curing, and as a solder resist using the same. The use is also being studied (Patent Document 3).
  • Patent Document 5 discloses that an alkali developing photosensitive fluorene polyester compound is used as a color filter ink material as a binder resin.
  • this binder resin is used, the film thickness is reduced due to the low heat resistance.
  • the balance between solubility and sensitivity is inferior, the penetration of the developer into the exposed area occurs simultaneously with the dissolution of the unexposed area, resulting in protrusions and irregularities on the edge of the pixel, which are not sharp and / or Problems such as poor adhesion of the pixel to the substrate may occur, and the level of the film forming compound is not yet satisfactory.
  • Japanese Patent Publication No.56-40329 Japanese Patent Publication No.57-45795 JP-A-11-140144 JP 2005-55814 A Japanese Patent No. 2575572
  • an epoxy resin having a specific structure that is, an epoxy resin (a) containing a large amount of the structure represented by the general formula (1) (hereinafter also simply referred to as an epoxy compound (a)).
  • Compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in one molecule (hereinafter also simply referred to as compound (b)) and at least two acids in one molecule
  • Activity comprising a reactive polyester compound (A) or (A ′) derived from a saturated or unsaturated polybasic acid anhydride (c) having an anhydride structure (hereinafter also simply referred to as polybasic acid anhydride (c))
  • the energy ray curable resin composition (hereinafter also simply referred to as the curable resin composition of the present invention) can provide a tough cured product, and further has excellent resin physical properties even when the solvent is dried. Have And found.
  • curable resin composition of the present invention is used to mean a resin composition that is cured by irradiation with an active energy ray, and an active energy ray curable resin composition or an active energy ray curable resin composition. Used interchangeably.
  • Epoxy resin represented by general formula (1) (a) Compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in one molecule and one molecule A reactive polyester compound (A) obtained by addition polymerization reaction with a saturated or unsaturated polybasic acid anhydride (c) having at least two acid anhydride structures;
  • R 1 is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, m is an integer of 1 to 4, and n is a positive number of 1 to 10 on average. Show.
  • the polybasic acid anhydride (c) is a monocyclic aromatic tetrabasic acid dianhydride, a bicyclic aromatic tetrabasic acid dianhydride, a polycyclic aromatic tetrabasic acid dianhydride, and
  • the above (1) or (2) which is any one or more selected from the group consisting of alicyclic acid dianhydrides obtained by nuclear hydrogenation reaction of these aromatic tetrabasic acid dianhydrides
  • the polybasic acid anhydride (c) has (i) pyromellitic acid anhydride, (ii) two benzene rings, and each benzene ring has one acid anhydride group. At least one selected from the group consisting of a tetrabasic dianhydride and (iii) a tetrabasic dianhydride containing a six-membered aliphatic ring in which the benzene ring of (i) and (ii) is nuclear hydrogenated
  • the reactive polyester compound (A) according to any one of the above (1) to (3), which is a tetrabasic acid dianhydride (5)
  • Polybasic acid anhydride (c) is (i) pyromellitic acid anhydride, biphenyl tetracarboxylic acid anhydride, naphthyl tetracarboxylic acid anhydride, benzophenone tetracarboxylic acid dianhydride, diphenyl ether
  • At least one aromatic anhydride selected from the group consisting of diphenylsulfonetetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, diol bistrimellitic anhydride, fluorene anhydride bisphthalate, and biphenol bistrimellitic anhydride
  • at least one tetrabase selected from the group consisting of butanetetracarboxylic anhydride and (iii) alicyclic acid dianhydride obtained by nuclear hydrogenation reaction of the aromatic anhydride
  • the dianhydride according to any one of (1) to (4) above, which is an acid dianhydride Reactive polyester compound (A).
  • Reactive polyester obtained by reacting the reactive polyester compound (A) according to any one of (1) to (5) above with a saturated or unsaturated dibasic acid anhydride (d).
  • An active energy ray-curable resin composition comprising: (8) The active energy ray-curable resin composition according to (7), wherein the solvent is contained at a ratio of 0.1 to 10 parts by weight with respect to 1 part by weight of the reactive polyester compound (A) or (A ′). object.
  • the reactive polyester compound (A) or (A ′) is 10 to 90% by weight, the reactive compound (B) is 3 to 80% by weight, and the balance with respect to the total solid content of the resin composition
  • an active energy ray-curable resin composition according to the above (7) or (8) which contains other additive components.
  • (11) Any one of the above (7) to (10), wherein the reactive compound (B) contains a (meth) acrylate monomer in an amount of 3 to 80% by weight based on the total solid content of the resin composition.
  • the active energy ray-curable resin composition according to Item is any one of the above (7) to (10), wherein the reactive compound (B) contains a (meth) acrylate monomer in an amount of 3 to 80% by weight based on the total solid content of the resin composition.
  • the active energy ray-curable resin composition described in 1. The reactive compound (B) contains an epoxy resin in the range of 5 to 50% by weight with respect to the total solid content of the resin composition, and the total amount of the reactive compound (B) is 8 to 80% by weight.
  • the active energy ray-curable resin composition according to any one of (9) to (12), further comprising 0.5 to 10% by weight of a thermosetting catalyst.
  • An active energy ray-curable resin composition further comprising a color pigment.
  • the reactive polyester compound of the present invention is suitable for blending into an active energy ray-curable resin composition containing the reactive compound (B) and / or a photopolymerization initiator and the like, and includes the reactive polyester compound of the present invention.
  • the curable resin composition can form a tough cured product. Therefore, the cured product is extremely suitable as a film that requires thermal and mechanical toughness. For example, when used in a coating film or the like, the cured film can be cured to have a high hardness and high impact resistance. Further, the resin composition has excellent resin properties even when the solvent is simply dried.
  • the resin composition can be a resist resin composition.
  • the resin composition When the resin composition is used as a resist resin composition, it has excellent peelability from the support film, has high sensitivity during development, and good developability. A dry film can be obtained. Further, the physical properties of the cured product after development of the dry film are tough cured products similar to the cured product of the coating film, and are excellent in, for example, hardness. In addition, since the curable resin composition of the present invention is excellent in pigment dispersibility, it is also suitable as a photosensitive colored resin composition for color filters and the like.
  • the resist resin composition examples include printed wiring board solder resists, flexible printed wiring board solder resists, plating resists, resists for interlayer insulating materials for multilayer printed wiring boards, and resists for forming photosensitive optical waveguides, etc. It can be used for applications that require particularly high characteristics.
  • the excellent pigment dispersibility of the curable resin composition of the present invention has particularly high dispersibility of colored pigments such as carbon black, and can exhibit good developability even at a high pigment concentration. I can do it. Therefore, it can be suitably used for color resists, resist materials for color filters, particularly black matrix materials. *
  • the reactive polyester compound (A) of the present invention has one or more polymerizable molecules in the molecule in order to impart reactivity to the epoxy resin (a) represented by the following formula (1) having a characteristic biphenyl skeleton.
  • Addition polymerization reaction of a compound (b) having both an ethylenically unsaturated group and one or more carboxy groups and a saturated or unsaturated polybasic acid anhydride (c) having at least two acid anhydride structures in one molecule Can be obtained.
  • R 1 is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, m is an integer of 1 to 4 and n is a positive number of 1 to 10 on average. Respectively.
  • the ethylenically unsaturated group and the hydroxyl group can be simultaneously introduced into the molecular chain by epoxycarboxylation with the compound (b).
  • the epoxy resin (a) represented by the general formula (1) used in the present invention has a specific structure having a biphenyl skeleton.
  • R 1 is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • the halogen atom shown here represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • the hydrocarbon group having 1 to 4 carbon atoms refers to a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an ethylene group, a propyl group, a propylene group, a butyl group, and a butylene group.
  • m represents an integer of 1 to 4, and represents the number of functional groups to be introduced.
  • n is an average value and represents a positive number of 1 to 10, preferably 1 to 6, respectively. When the value of n is 10 or less, preferably less than 6, a suitable viscosity range is obtained.
  • the epoxy resins (a) represented by the general formula (1) those in which R 1 is all hydrogen atoms are preferred because they are available at low cost. Furthermore, the method for producing the epoxy resin (a) represented by the general formula (1) is known and described in detail in Patent Document 4. Generally, commercial products are available from Nippon Kayaku Co., Ltd. as NC-3000 series. In the NC-3000 series, in the above formula, R 1 is all hydrogen atoms, and n is an average value and represents a positive number of 1 to 10. In the present invention, a suitable one of the series grades can be appropriately selected.
  • the epoxy resin preferably has an epoxy equivalent of about 200 g / equivalent to 300 g / equivalent, and more preferably 240 g / equivalent to 270 g / equivalent. Most preferred is NC-3100.
  • the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in one molecule used in the present invention has a reactive group that reacts with active energy rays in the epoxy resin. Used to introduce.
  • Examples of the compound (b) include a monocarboxylic acid compound or a polycarboxylic acid compound having at least one ethylenically unsaturated group.
  • Examples of the monocarboxylic acid compound include (meth) acrylic acids ((meth) acrylic group-containing monocarboxylic acid compounds), crotonic acid, ⁇ -cyanocinnamic Examples thereof include a reaction product of an acid, cinnamic acid, or a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound.
  • (meth) acrylic acid ((meth) acrylic group-containing monocarboxylic acid compound) is, for example, (meth) acrylic acid, ⁇ -styrylacrylic acid, ⁇ -furfurylacrylic acid, (meth) acrylic acid dimer , Half-ester, saturated or unsaturated dibasic acid and monoglycidyl (meth) acrylate, which is an equimolar reaction product of saturated or unsaturated dibasic acid anhydride and (meth) acrylate having one hydroxyl group in one molecule A half ester which is an equimolar reaction product with a derivative, and the like can be mentioned.
  • a polycarboxylic acid compound (carboxylic acid compound having a plurality of carboxy groups in one molecule), a polybasic acid anhydride of tribasic acid or more (meth) acrylate having a plurality of hydroxyl groups in one molecule Is an equimolar amount of a half ester, a saturated or unsaturated dibasic acid, and a glycidyl (meth) acrylate having a plurality of epoxy groups, which is a reaction product obtained by reacting the acid anhydride with an acid anhydride group of the acid anhydride.
  • the half-ester etc. which are reaction materials are mentioned.
  • the compound (b) is preferably a compound having no hydroxyl group in the compound.
  • a preferred compound (b) is the above monocarboxylic acid compound having no hydroxyl group in the compound and having at least one ethylenically unsaturated group.
  • the monocarboxylic acids (meth) acrylic acid, a reaction product of (meth) acrylic acid and ⁇ -caprolactone, or cinnamic acid is used in terms of sensitivity when the curable resin composition of the present invention is used. More preferred. More preferred is (meth) acrylic acid, and most preferred is acrylic acid.
  • the term “(meth) acryl” is used to mean “acryl or methacryl”. Therefore, (meth) acrylic acid is used in the meaning of acrylic acid or methacrylic acid.
  • any compound having at least two acid anhydride structures in the molecule can be used. That is, a saturated or unsaturated tetrabasic acid anhydride or a polybasic acid anhydride having at least two acid anhydride structures in one molecule can be used. In the present invention, it is preferable to use a saturated or unsaturated 4-basic acid dianhydride having two acid anhydride structures.
  • preferred polybasic acid anhydrides include monocyclic aromatic tetrabasic acid dianhydrides, bicyclic aromatic tetrabasic acid dianhydrides, polycyclic aromatic tetrabasic acid dianhydrides, And tetrabasic acid dianhydrides selected from the group consisting of alicyclic acid anhydrides obtained by a nuclear hydrogenation reaction of these aromatic acid anhydrides.
  • monocyclic aromatic tetrabasic acid dianhydrides such as pyromellitic acid anhydride; biphenyltetracarboxylic acid anhydride, naphthyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid dianhydride, diphenyl ether Tetracarboxylic anhydride, diphenylsulfonetetracarboxylic dianhydride, diol bistrimellitic dianhydride (for example, C2-C6 diol bistrimellitic acid such as ethylene glycol bistrimellitic dianhydride, hexanediol bistrimellitic anhydride, etc.)
  • a bicyclic aromatic tetrabasic dianhydride such as a dianhydride (more preferably a tetrabasic acid dianhydride having two benzene rings and each benzene ring having one anhydride group.
  • Polycyclic aromatic tetracarboxylic acid dianhydride having 1-4 ring; aromatic tetracarboxylic acid dianhydride with 2 to 4 rings such as include (ii) butane tetracarboxylic dianhydride.
  • aromatic acid anhydrides alicyclic polybasic acid dianhydrides obtained by a nuclear hydrogenation reaction of the aromatic tetrabasic acid dianhydride can also be suitably used.
  • One or more polybasic acid anhydrides selected from these groups are preferred.
  • 4-basic acid dianhydride having the above two benzene rings and each benzene ring having one anhydride group one naphthyltetracarboxylic dianhydride and one anhydride group are included.
  • the bridging group include —O—, —CO—, —CO—O—C1 to C4 alkylene—O—CO—, —CO—O—C6H5-C6H5-O—CO—, and the like. Bonding is more preferred.
  • More preferable tetrabasic acid dianhydrides include (i) pyromellitic acid anhydride, (ii) tetrabasic acid having two benzene rings and each benzene ring having one anhydride group. Dianhydride and (iii) at least one 4 base selected from the group consisting of a tetrabasic dianhydride containing a 6-membered aliphatic ring in which the benzene ring of (i) and (ii) is nuclear hydrogenated Acid dianhydride.
  • Preferred examples of the above (ii) include biphenyl tetracarboxylic dianhydride, naphthyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride Products, C2 to C6 diol bistrimellitic dianhydride, fluorene dianhydride bisphthalate, biphenol bistrimellitic anhydride, butanetetracarboxylic dianhydride, and the like, more preferably biphenyltetracarboxylic dianhydride.
  • Further preferred polybasic acid anhydride (c) is pyromellitic acid anhydride or biphenyltetracarboxylic dianhydride.
  • the reactive polyester compound (A) of the present invention comprises the aforementioned epoxy compound (a) and compound (b) (preferably a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule, more preferably (meth) acrylic acid. ) And a carboxylation reaction (hereinafter referred to as the first reaction) to produce an alcoholic hydroxyl group to obtain a diol compound, and then polyester obtained from the obtained diol compound and polybasic acid anhydride (c). It can be obtained as an addition polymer by carrying out a polymerization reaction (hereinafter referred to as a second reaction).
  • a polymerization reaction hereinafter referred to as a second reaction.
  • the proportion of the raw material epoxy compound (a) and the compound (b) used is such that the carboxy group of the compound (b) is 0.8 to 1 with respect to 1 equivalent of the epoxy of the epoxy compound (a). .2 equivalents, preferably 1 to 1.2 equivalents, more preferably 1 to 1.1 equivalents.
  • the first reaction can be carried out without solvent or diluted with a solvent.
  • the solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction. Usually an organic solvent is used. A preferable amount of the solvent used is appropriately adjusted depending on the viscosity and usage of the obtained resin.
  • the solvent is preferably used so that the solid content is 90 to 30% by weight, more preferably 80 to 50% by weight, based on the total amount of the charged solution.
  • the “solid content” means components other than the solvent (excluding the reactive compound (B)).
  • solvents examples include (i) aliphatic or aromatic hydrocarbon solvents, (ii) ester solvents, (iii) ether solvents, (iv) ketone solvents, and (v) (A) or Examples thereof include reactive compounds (B) other than (A ′) (hereinafter also simply referred to as reactive compounds (B)). Specific examples include the following solvents.
  • Aliphatic or aromatic hydrocarbon solvents for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, tetramethylbenzene, etc., aliphatic hydrocarbon solvents such as hexane, octane, decane, etc., and petroleum that is a mixture thereof Examples include ether, white gasoline, and solvent naphtha.
  • Ester solvent alkyl acetate (preferably C1-C4 alkyl acetate) such as ethyl acetate, propyl acetate, butyl acetate; cyclic ester such as ⁇ -butyrolactone; ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol mono Mono, such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether monoacetate (preferably mono, di Or tri C2-C4 alkylene glycol mono C1- 3 alkyl ether monoacetate); glutaric acid dialkyl, dialkyl succinate, polycarboxylic acid alkyl esters of dialkyl adipate; and the like.
  • Ether solvents alkyl ethers such as diethyl ether and ethyl butyl ether; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether Cyclic ethers such as tetrahydrofuran; and the like.
  • Ketone solvent acetone, methyl ethyl ketone, cyclohexanone, isophorone and the like can be mentioned.
  • Reactive compound (B) Specific examples of the reactive compound (B) described later can be used as a solvent. In this case, when it is used as a curable composition, it can be used directly as a composition, which is preferable.
  • the solvents (i) to (v), (ii) an ester solvent and (iv) a ketone solvent are preferable.
  • the ester solvent (ii) is preferable as a solvent used in the synthesis of the reactive polyester compounds (A) and (A ′) of the present invention, and among these ester solvents, mono, di or tri C2-C4 alkylene glycol mono C1-C3 alkyl ether monoacetate is more preferable, and propylene glycol monomethyl ether acetate is more preferable.
  • a ketone solvent is preferable as a solvent for diluting the reactive polyester compound (A) or (A ′) of the present invention.
  • the amount of the catalyst used is the total amount of the compound used in the reaction, including the raw material compound, the solvent, and other additives such as a catalyst, that is, the above epoxy.
  • the amount is 0.1 to 10% by weight based on the total amount of the reaction liquid to which the resin (a), the carboxylic acid compound (b), and optionally other additives including a solvent and a catalyst are added.
  • the reaction temperature of the first reaction is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.
  • the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include known general basic catalysts such as zirconium octoate.
  • thermal polymerization inhibitor examples include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like.
  • the addition amount of the thermal polymerization inhibitor is not particularly limited as long as polymerization as a side reaction can be suppressed, and is usually small, for example, about 1/20 to the same amount as the addition amount of the catalyst.
  • the end point is when the acid value of the sample is 5 mgKOH / g or less, preferably 2 mgKOH / g or less, while sampling as appropriate.
  • the second reaction is an esterification reaction in which, after the completion of the first reaction, the polybasic acid anhydride (c) is gradually added to the reaction solution and reacted with the diol compound obtained in the first reaction.
  • a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by weight or less based on the total amount of the charged raw materials.
  • the reaction temperature of the second reaction is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.
  • the amount of polybasic acid anhydride (c) charged in the second reaction is the same as that in the first reaction so that no acid anhydride remains at the end of the reactive polyester compound (A) obtained after the reaction. It is preferable that the equivalent number of the anhydride group of the polybasic acid anhydride (c) is 1 or less with respect to 1 equivalent of the hydroxyl group of the obtained diol compound.
  • the reactive polyester compound (A) of the present invention has a solid content acid value of 50 to 150 mg ⁇ KOH / g in the range of calculated values, and ⁇ number of moles of carboxylated reaction product (diol compound) ⁇ / ( It is preferable to charge the polybasic acid anhydride (c) in a molar ratio of 1 to 5.
  • this value is less than 1, an acid anhydride group will remain at the terminal of the reactive polyester compound (A) of the present invention, and the thermal stability is low and there is a possibility of gelation during storage.
  • this value exceeds 5, the molecular weight of the reactive polyester compound (A) becomes low, which may cause a problem of tackiness or a low sensitivity.
  • the solubility in an alkaline aqueous solution is insufficient, and when patterning is performed, there is a fear that it remains as a residue or in the worst case, patterning cannot be performed.
  • the solid content acid value exceeds 150 mg ⁇ KOH / g, the solubility in an alkaline aqueous solution becomes too high, and the photocured pattern may be peeled off.
  • the second reaction can be carried out using a reactive compound (B) or the like, which will be described later, alone or as a mixture as an organic solvent.
  • a reactive compound (B) or the like which will be described later, alone or as a mixture as an organic solvent.
  • the obtained reaction liquid is used as the curable resin composition of the present invention, it is preferable because it can be directly used for curing with active energy rays without removing the solvent.
  • the reactive polyester compound (A) is further subjected to ester reaction with a saturated or unsaturated dibasic acid anhydride (d).
  • a saturated or unsaturated dibasic acid anhydride (d) can be obtained.
  • the saturated or unsaturated dibasic anhydride (d) include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride Examples include acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride, and trimellitic anhydride.
  • dibasic acid anhydrides selected from the group consisting of phthalic anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and nuclear hydrogenated products thereof are preferred, most preferably tetrahydrophthalic anhydride.
  • It is an acid.
  • the reaction between the reactive polyester compound (A) and the dibasic acid anhydride (d) is performed by adding 0.1% of saturated or unsaturated dibasic acid anhydride (d) to one equivalent of hydroxyl group in the reactive polyester compound (A). It is preferable to carry out a reaction of ⁇ 1.0 equivalent.
  • the reaction temperature is preferably 60 to 150 ° C., and the reaction time is preferably 1 to 10 hours.
  • the solid content acid value of the reactive polyester compound (A ′) thus obtained is preferably about 50 to 150 mg ⁇ KOH / g.
  • the molecular weights of the reactive polyester compounds (A) and (A ′) of the present invention obtained above are both about 3,000 to 30,000 as an average molecular weight. Preferably, it is about 10,000 to 30,000, more preferably about 13,000 to 25,000.
  • the content of the reactive polyester compound (A) or (A ′) of the present invention in the obtained reaction solution may be in the range of 10 to 90% by weight, preferably 20%, based on the total amount of the reaction solution. -80% by weight, more preferably about 40-80% by weight, most preferably 50-70% by weight, and the balance is a solvent.
  • the reactive polyester compound of the present invention obtained above can be isolated from the obtained reaction solution, but usually the obtained reaction solution is used as it is, diluted or concentrated, or as necessary. In addition, an additional component can be added to form the curable resin composition of the present invention.
  • the term “reactive polyester compound of the present invention” means “one of the reactive polyester compounds (A) and (A ′) or both” unless otherwise specified.
  • the curable resin composition of the present invention may be the reactive polyester compound of the present invention alone or may contain a solvent. When the solvent is included, the solvent content may be in the range of 0.1 to 10 parts by weight with respect to 1 part by weight of the reactive polyester compound of the present invention. Moreover, it is usually preferable to further contain the reactive compound (B). In this case, the content of the reactive compound (B) with respect to the total solid content of the resin composition is 1 to 90% by weight, preferably 3 to 80% by weight, more preferably 5 to 80% by weight.
  • the content of the reactive polyester compound of the invention is usually 10 to 99% by weight, preferably 10 to 90% by weight, more preferably 20 to 90% by weight, still more preferably 20 to 87% by weight, and most preferably 20 to 80% by weight. % By weight.
  • the aspect in which this curable resin composition contains a photoinitiator as another additive component is also one of the preferable aspects.
  • the content of the photopolymerization initiator is about 0.1 to 20% by weight, preferably about 0.4 to 15% by weight, based on the total solid content of the resin composition.
  • One of the more preferable embodiments of the present invention is an embodiment including both the photopolymerization initiator and the reactive compound (B), and the content of both in this case is preferably in the above-described range, Each preferred range and more preferred range is a preferred range and a more preferred range as the respective contents of both. Furthermore, the total of both is 5 to 80% by weight with respect to the total solid content of the resin composition, and the reactive polyester compound of the present invention is more preferably 20 to 90% by weight.
  • Specific examples of the reactive compound (B) that can be used in the present invention include a radical reaction type (meth) acrylate monomer; a cation reaction type epoxy compound; a vinyl monomer ((meth) acrylate monomer). Reactive oligomers that are sensitive to both radicals and cations. Examples of the radical reaction type (meth) acrylate monomer that can be used include monofunctional (meth) acrylate and polyfunctional (meth) acrylate.
  • Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenyl Examples include ethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.
  • (meth) acrylate having 2 to 6 (meth) acrylate groups is preferable.
  • vinyl compounds examples include vinyl ethers, styrene compounds, and other vinyl compounds.
  • the vinyl ether examples include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether and the like.
  • the styrene compound examples include styrene, methyl styrene, and ethyl styrene.
  • Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.
  • a reactive oligomer sensitive to both radical and cation a reactive oligomer having a functional group sensitive to active energy rays and a urethane bond in the same molecule, preferably urethane acrylate;
  • a reactive oligomer having a sensitive functional group specifically vinyl group
  • a polyester bond in the same molecule preferably polyester acrylate;
  • a functional group derived from an epoxy resin and sensitive to active energy rays specifically Includes a reactive oligomer having both a vinyl group and an epoxy group in the same molecule, preferably an epoxy group-containing epoxy acrylate; a reactive oligomer in which a urethane bond and a polyester bond are used in combination.
  • the cation reaction type epoxy compound is not particularly limited as long as it is generally a compound having an epoxy group (epoxy compound).
  • a radical curable (meth) acrylate monomer is preferable.
  • the (meth) acrylate monomers polyfunctional (meth) acrylates are preferable, and polyfunctional (meth) acrylates having 2 to 6 (meth) acrylate groups are more preferable.
  • preferable (meth) acrylate monomers include the above-described di (meth) acrylate compounds and tri- to 6-functional poly (meth) acrylates such as dipentaerythritol hexaacrylate, and more preferable.
  • di (meth) acrylate and dipentaerythritol hexaacrylate of ⁇ -caprolactone adduct of neopentyl glycol hydroxybivalate In the case of the cationic type, the carboxylic acid and the epoxy react with each other, so that it is necessary to use a two-component mixed type.
  • the curable resin composition of the present invention can be obtained by mixing the reactive polyester compound (A) or (A ′) of the present invention with the reactive compound (B) as necessary. Further, the reactive polyester compounds (A) and (A ′) may be used in combination with the curable resin composition of the present invention. At this time, other additive components may be appropriately added as components other than the reactive polyester compound (A) or (A ′) and the reactive compound (B) depending on the application.
  • additive components are added to the resin composition up to 70% by weight based on the total amount of the resin composition. You can also.
  • Other additive components include photopolymerization initiators, color pigments, volatile solvents added for viscosity adjustment for the purpose of imparting coating suitability, heat-sensitive polymerization initiators, and other additives. It is done. The other additive components that can be used will be specifically described below.
  • any of radical photopolymerization initiator and cationic photopolymerization initiator can be used. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination. Specific examples of each are described below.
  • radical photopolymerization initiators examples include benzoins (benzoin compound polymerization initiators) such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl- Acetophenones (acetophenone compound polymerization initiator) such as 1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2-ethylanthraquinone, 2-t-butylanthraquinone Anthraquinones such as 2-chloroanthraquinone and 2-amylanthraquinon
  • cationic photopolymerization initiator Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine-based initiator, borate-based initiator, and Other photoacid generators can be mentioned.
  • Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc. manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
  • Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate.
  • Examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-manufactured by Union Carbide). 6990), triphenylsulfonium hexafluoroantimonate (Union Carbide Cyracure UVI-69) 4, etc.). Examples of the phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.
  • halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (Trigonal PI, etc., manufactured by AKZO), 2.2-dichloro-1--4- (phenoxyphenyl) Etanone (Sandoz Co., Ltd., Sandray Co., Ltd.
  • triazine-based initiator examples include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchi), 2, 4-trichloromethyl- (4′-methoxystyryl) -6-triazine (such as Triazine® PMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as Triazine® PP manufactured by Panchim), 2, 4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (eg, Triazine B® from Panchi), 2 [2 ′ (5 ′′ -methylfuryl)
  • borate initiator examples include NK-3876 and NK-3881 manufactured by Nippon Senshoku Dye Co., Ltd.
  • Other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (Kurokinkasei Co., Ltd., biimidazole, etc.), 2,2-azobis (2-amino-propane) dihydrochloride (Wako Pure Chemical Industries, Ltd.) V50 manufactured by the company), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [eta-5-2-4- (cyclopentadecyl) ( 1,2,3,4,5,6, eta)-(methylethyl) -benzene] Iron (II) hexafluorophosphonate (Irga
  • thermopolymerization initiator in addition to the photopolymerization initiator, other heat-sensitive polymerization initiators can be used in combination.
  • an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination.
  • thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants, and coloring pigments
  • thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents
  • polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether
  • stabilizers such as stabilizers, antioxidants, and coloring pigments
  • a pigment material other than the colored pigment for example, a so-called extender pigment that is not intended for coloring can be used.
  • extender pigment examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.
  • resins that do not react with active energy rays such as phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins
  • inert polymers such as phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins
  • Natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40% by weight.
  • the reactive polyester compound of the present invention when using the reactive polyester compound of the present invention for solder resist applications, it is preferable to use a general epoxy resin known as a resin that does not show reactivity to active energy rays.
  • the epoxy resin can be added as one of the reactive compounds (B). Examples thereof include (1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane) glycidyl ether (trade name: GTR-1800, manufactured by Nippon Kayaku Co., Ltd.). This is because the carboxy group derived from (A) or (A ′) remains even after being reacted and cured by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using an epoxy resin, the remaining carboxy group is further carboxylated to form a stronger crosslinked structure.
  • the content of the epoxy resin with respect to the total solid content of the curable resin composition of the present invention may be in the range of 5 to 40% by weight.
  • a volatile solvent is added to the resin composition in a range of 50% by weight, more preferably 35% by weight, based on the total amount of the resin composition. You can also
  • the curable resin composition of the present invention contains 5 to 90% by weight of the reactive polyester compound (A) or (A ′) in the composition, preferably 10 to 90% by weight, more preferably 20 to 87% by weight,
  • the reactive compound (B) contains 3 to 80% by weight, more preferably 5 to 70% by weight. If necessary, other components may be contained up to about 70% by weight.
  • the curable resin composition of the present invention is easily cured by active energy rays.
  • active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays.
  • ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.
  • the color pigment that can be used in the present invention is used for coloring the active energy ray-curable resin composition of the present invention. Since the reactive polyester compound (A) or (A ′) used in the present invention has a specific skeleton, it is presumed that particularly excellent affinity to the pigment, that is, dispersibility is exhibited.
  • the color pigment examples include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide. Of these, carbon black is most preferred because of its high dispersibility.
  • the content of the color pigment in the curable resin composition of the present invention is not particularly limited, but is usually in the range of 1 to 100 parts by weight, preferably 2 to 100 parts by weight with respect to 10 parts by weight of the polyester compound of the present invention. 50 parts by weight, more preferably 5 to 30 parts by weight.
  • the molding material refers to a material in which an uncured composition is put into a mold or an object is molded by pressing the mold and then a curing reaction is caused by active energy rays, or a laser is applied to the uncured composition. It refers to a material that is used for applications in which it is irradiated with a focused light such as to cause a curing reaction to be molded.
  • Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold” that has been micro-processed into an uncured composition, Furthermore, particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have particularly severe thermal requirements.
  • the film-forming material is used for the purpose of coating the surface of the substrate.
  • Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives.
  • Such materials include adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines.
  • dry film also corresponds to the film forming material. .
  • the carboxy group of the reactive polyester compound of the present invention increases the adhesion to the substrate, and therefore, it is preferably used as an application for coating a plastic substrate or a metal substrate.
  • the unreacted reactive polyester compound of the present invention as an alkaline water developing resist material composition taking advantage of the feature that it is soluble in an alkaline aqueous solution.
  • the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts.
  • active energy rays such as ultraviolet rays
  • the composition is used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or the non-irradiated part with, for example, a solvent or an alkaline solution.
  • the curable resin composition of the present invention for resist ridges can be applied to various materials that can be patterned. For example, it is particularly useful as a solder resist material, an interlayer insulating material for a build-up method, and further printed as an optical waveguide. It is also used for wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates.
  • a tough cured product taking advantage of the property that a tough cured product can be obtained, making use of a permanent resist application such as a solder resist, and the property of good pigment dispersibility, printing inks, color filters, etc.
  • a color resist particularly a black matrix resist is preferred.
  • the reactive polyester compound of the present invention is excellent in spite of its relatively high molecular weight. Developability can be exhibited.
  • an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.
  • the cured product of the curable resin composition of the present invention refers to a product obtained by irradiating and curing the active energy ray on the curable resin composition of the present invention.
  • the following aspect can be mentioned as a preferable aspect of the curable resin composition of this invention.
  • the “active energy ray-curable resin composition” is simply referred to as “curable resin composition”.
  • the reactive polyester compound of the present invention is an epoxy compound (a), an epoxy compound in which all R 1 s in formula (1) are hydrogen atoms, (meth) acrylic acid as compound (b), and saturation Or the reactive polyester compound (A) obtained using tetrabasic acid dianhydride as the unsaturated polybasic acid anhydride (c) or the reactive polyester compound (A ′) obtained using the same.
  • Tetrabasic dianhydride is (i) pyromellitic anhydride, (ii) four bases each having two benzene rings, and each benzene ring has one acid anhydride group.
  • At least one tetrabase selected from the group consisting of an acid dianhydride and (iii) a tetrabasic acid dianhydride containing a 6-membered aliphatic ring in which the benzene rings of (i) and (ii) are nuclear hydrogenated
  • tetrabasic acid dianhydride is (i) pyromellitic acid anhydride, biphenyltetracarboxylic acid anhydride, naphthyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid anhydride, diphenyl At least one aromatic anhydride selected from the group consisting of sulfonetetracarboxylic acid anhydride, ethylene glycol bistrimellitic acid anhydride, diol bistrimellitic acid anhydride, bisphthalic acid fluorene anhydride and biphenol bistrimellitic acid anhydride, And (ii) at least one tetrabasic acid selected from the group consisting of butanetetracarboxylic anhydride and (iii) alicyclic acid dianhydride obtained by nuclear hydrogenation reaction of the aromatic anhydride
  • the dianhydride according to any one of (I)
  • the reaction solution was reacted until the acid value was 0.5 mg ⁇ KOH / g or less to obtain a diol compound solution (Geo Theoretical molecular weight of Le Compound: 658.12).
  • a diol compound solution (Geo Theoretical molecular weight of Le Compound: 658.12).
  • propylene glycol monomethyl ether monoacetate was added to the resulting diol compound solution as a solvent so that the solid content was 65% by weight.
  • Example 2 Synthesis of reactive polyester compound (A-2) NC-3100 manufactured by Nippon Kayaku Co., Ltd. as an epoxy compound (a) represented by formula (1) in a 2 L flask equipped with a stirrer and a reflux tube.
  • 257 g of (phenol aralkyl type epoxy resin, epoxy equivalent: 257 g / equivalent), propylene glycol monomethyl ether monoacetate as a solvent is added so as to have a solid content of 70%, and a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule
  • the diol compound (theoretical molecular weight: 658) 12) was obtained.
  • propylene glycol monomethyl ether monoacetate was added to the resulting diol compound solution as a solvent so that the solid content was 65% by weight.
  • 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (abbreviation BPDA, Mw 294.2) was added as a polybasic acid anhydride (c). After the addition, the temperature was raised to 95 ° C.
  • AA acrylic acid
  • Mw 72
  • the diol compound (theoretical molecular weight: 6) was reacted until the acid value of the reaction solution reached 0.5 mg ⁇ KOH / g or less. 8.12) was obtained.
  • propylene glycol monomethyl ether monoacetate was added as a solvent to the obtained diol compound solution so that the solid content was 65% by weight, and polymellitic anhydride (c) was added to this solution as polybasic acid anhydride (c).
  • PMDA, Mw 218.1) 109.1 g was added. After the addition, the temperature was raised to 95 ° C.
  • THPA tetrahydrophthalic anhydride
  • Mw 152.2
  • Propylene glycol monomethyl ether monoacetate was added so that the content was 65% by weight.
  • the obtained liquid was reacted at 100 ° C. for 6 hours to obtain a resin solution containing 65% by weight of the alkaline aqueous solution-soluble polyester compound (A) of the present invention (this alkaline aqueous solution-soluble polyester compound is referred to as A′-3).
  • AA, Mw 72
  • a carboxylate compound solution was obtained.
  • H-1 reactive polycarboxylate solution
  • the average molecular weight of the compound (H-1) 3,500.
  • Comparative Example 2 Synthesis of reactive polyester compound (H-2) (Compound of Synthesis Example 1 of Patent Document 5) In a 500 ml four-necked flask, 231 g of bisphenolfluorene type epoxy resin (epoxy equivalent 231 g / eq), 0.45 g of triethylbenzylammonium chloride, 0.1 g of 2,6-di-isobutylphenol, 72.0 g of acrylic acid, Were mixed, and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 25 ml per minute. Although this solution was cloudy, the temperature was gradually raised as it was, and the solution was heated to 120 ° C. to be completely dissolved.
  • Example 4 Preparation of composition for hard coat 20 g of the solution of the reactive polyester compound (A-1, A-2, A′-3, H-1 or H-2) synthesized in Examples 1 to 3 and Comparative Examples 1 and 2, 4 g of dipentaerythritol hexaacrylate as the monomer (B) and 1.5 g of Irgacure 184 as an ultraviolet reactive initiator were dissolved by heating. Further, this was coated on a polycarbonate plate with a hand applicator so as to have a film thickness of 20 ⁇ m at the time of drying, and dried in order to remove the solvent in an electric oven at 80 ° C. for 30 minutes.
  • the reactive polyester compound A-1, A-2, A′-3, H-1 or H-2
  • an ultraviolet-ray exposure apparatus manufactured by Oak Seisakusho
  • a high-pressure mercury lamp was irradiated with an ultraviolet ray with an irradiation dose of 1000 mJ and cured to obtain an article overcoated with the resin composition.
  • the hardness of the coating film of the article overcoated with this resin composition was measured according to JIS K5600-5-4: 1999, and an impact test (impact resistance test) was conducted according to ISO6272-1: 2002.
  • the evaluation criteria in the impact resistance test are as follows. ⁇ : no scratch or peeling, ⁇ : slight scratch, ⁇ : peeling occurred.
  • Table 1 Physical properties of coating film Examples Compound (A) Pencil hardness Impact resistance test Example 4-1 A-1 3H ⁇ Example 4-2 A-2 3H ⁇ Example 4-3 A′-3 3H ⁇ Comparative Example 4-1 H-1 2H ⁇ Comparative Example 4-2 H-2 3H
  • the photocurable resin composition in the present invention has excellent impact resistance while having a relatively high hardness.
  • Example 5 Preparation of dry film type resist composition 54.44 g of reactive polyester compound (A-1, A-2, A′-3, H-1 or H-2) solution obtained in Examples 1 to 3 and Comparative Examples 1 and 2, reactive compound (B) 3.54 g of HX-220 (manufactured by Nippon Kayaku Co., Ltd.), 4.72 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) and Kayacure DETX-S (photochemical initiator) 0.47 g of Nippon Kayaku Co., Ltd.) and (1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane) glycidyl ether (GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) as a curing component 14.83 g, 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent are kn
  • the obtained composition was uniformly applied to a polyethylene terephthalate film as a support film by a roll coating method, passed through a hot air drying furnace at a temperature of 70 ° C., and a resin layer having a thickness of 30 ⁇ m was formed.
  • a polyethylene film to be a protective film was attached to obtain a dry film.
  • the obtained dry film was attached to the entire surface of the substrate while peeling off the protective film using a heating roll at a temperature of 80 ° C. on a polyimide printed board (copper circuit thickness: 12 ⁇ m, polyimide film thickness: 25 ⁇ m).
  • a mask on which a circuit pattern was drawn using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), and Kodak Step Tablet No.
  • the reactive polyester compound-containing resin layer of the present invention on the polyimide substrate was irradiated with ultraviolet rays through 2. Then, the support film on a dry film was peeled and the peeling state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air dryer at 150 ° C. for 60 minutes to obtain a cured film. The Kodak Step Tablet No. used at the time of ultraviolet irradiation was used. 2 was used to see the sensitivity.
  • Sensitivity evaluation Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).
  • the resist composition of the present invention has a balance between sensitivity and developability in addition to good peelability.
  • Example 6 Preparation of photosensitive colored resin composition for color filter Reactive polyester compounds obtained in Examples 1 to 3 and Comparative Examples 1 and 2 (A-1, A-2, A'-3, H- 1 or H-2) 50 g of solution (32.5 g in solid content), 5 g of dipentaerythritol hexaacrylate, 4 g of CGI-124 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, Discrbyk (urethane type) 224 g of carbon black dispersion solution (solid content conversion: 56 g, including 43 g of carbon black and 13 g of polymer dispersant) dispersed in propylene glycol monomethyl ether acetate was mixed with 218 g of propylene glycol monomethyl ether acetate. Thus, a photosensitive black resin composition was obtained.
  • A-1, A-2, A'-3, H- 1 or H-2 50 g of solution (32.5 g in solid content), 5 g of dipenta
  • the photosensitive black resin composition thus obtained was spin-coated on a 10 cm square glass substrate and dried at 90 ° C. for 150 seconds on a hot plate. The film thickness after drying was 1 ⁇ m. Next, this sample was image-exposed with a high-pressure mercury lamp through a mask, and then subjected to spray development using a KOH aqueous solution at a temperature of 23 ° C. and a concentration of 0.1% by weight to form a black pixel (black matrix).
  • Heat-resistant A heat resistance test (300 ° C., 1 hour) is performed on the 20 ⁇ m mask pattern, and the film thickness reduction rate (%) after the test with respect to the film thickness before the test is shown.
  • the active energy ray-curable resin of the present invention as a material having both curability and toughness, a hard coat material, a resist material that can be developed with an alkali, and an application that exhibits good pigment dispersibility have been shown.

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Abstract

La présente invention concerne un composé de type polyester réactif (A) obtenu par une réaction de polymérisation par addition d'un composé époxy (a) représenté par la formule (1), d'un composé (b) comportant au moins un groupe éthyléniquement insaturé polymérisable et au moins un groupe carboxyle par molécule, et d'un anhydride d'acide polybasique saturé ou insaturé (c) comportant au moins deux structures de type anhydride d'acide par molécule. L'invention concerne également un composé de type polyester réactif (A') obtenu par une autre réaction entre un anhydride d'acide dibasique saturé ou insaturé (d) et le composé (A). L'invention concerne, en outre, une composition de résine durcissable sous l'effet d'un rayonnement d'énergie active utilisant lesdits composés. La composition de résine peut durcir sous l'effet, entre autres, d'un rayonnement d'énergie active, tel que, par exemple , un rayonnement ultraviolet, pour former un film résistant et la composition de résine, si elle est utilisée en tant que composition de résine de masquage, présente des propriétés intéressantes en matière de développement et si elle est utilisée en tant que filtre coloré, est caractérisée par des pixels nets, son brillant et une remarquable résistance à la chaleur.
PCT/JP2013/003030 2012-05-15 2013-05-13 Composé de type polyester réactif et composition de résine durcissable sous l'effet d'un rayonnement d'énergie active WO2013172009A1 (fr)

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JP2012-111543 2012-05-15
JP2012111543A JP2015134844A (ja) 2012-05-15 2012-05-15 反応性ポリエステル化合物、それを用いた活性エネルギー線硬化型樹脂組成物

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