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WO2018173679A1 - Résine de (méth)acrylate contenant un groupe acide et matière de résine pour réserve de soudure - Google Patents

Résine de (méth)acrylate contenant un groupe acide et matière de résine pour réserve de soudure Download PDF

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Publication number
WO2018173679A1
WO2018173679A1 PCT/JP2018/007724 JP2018007724W WO2018173679A1 WO 2018173679 A1 WO2018173679 A1 WO 2018173679A1 JP 2018007724 W JP2018007724 W JP 2018007724W WO 2018173679 A1 WO2018173679 A1 WO 2018173679A1
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group
meth
acid
resin
acrylate
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Japanese (ja)
Inventor
駿介 山田
亀山　裕史
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2019507486A priority Critical patent/JP6660575B2/ja
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  • the present invention provides an acid group-containing (meth) acrylate resin excellent in the balance between elongation and heat resistance in a cured product, a curable resin composition containing the resin, an insulating material comprising the curable resin composition, and a solder resist
  • the present invention relates to a resin material and a resist member.
  • an acid group-containing epoxy acrylate resin obtained by reacting an acid anhydride after an epoxy resin is acrylated with acrylic acid is widely used.
  • the required performance for the resin material for solder resist includes various properties such as curing with a small exposure amount, excellent alkali developability, and excellent heat resistance, strength, flexibility, dielectric properties, etc. in the cured product.
  • Patent Document 1 As a conventionally known resin material for solder resist, an acid obtained by further reacting a reaction product of cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin and bisphenol F with acrylic acid and tetrahydrophthalic anhydride.
  • a group-containing epoxy acrylate resin is known (see Patent Document 1 below).
  • the acid group-containing epoxy acrylate resin described in Patent Document 1 has characteristics that are excellent in solder resistance and heat resistance in a cured product, the elongation in the cured product is very low, and the cured product is easily cracked and has poor reliability. There existed problems, such as not being suitable for the use for which a softness
  • the problem to be solved by the present invention is an acid group-containing (meth) acrylate resin excellent in the balance between elongation and heat resistance in a cured product, a curable resin composition containing the acid group, and the curable resin composition.
  • An insulating material, a resin material for solder resist, and a resist member are provided.
  • an ester bond site derived from a polycarboxylic acid or a derivative thereof has a molecular structure as an epoxy resin that is a reaction raw material of an acid group-containing epoxy (meth) acrylate resin.
  • the resin material has an excellent balance between elongation and heat resistance in a cured product while maintaining performance such as photosensitivity and alkali developability, and the present invention has been completed. It was.
  • the present invention is an acid group-containing (meth) acrylate resin comprising an epoxy resin (A), an unsaturated monocarboxylic acid or derivative thereof (B), and a polycarboxylic acid anhydride (C) as essential reaction raw materials.
  • the epoxy resin (A) relates to an acid group-containing (meth) acrylate resin having an ester bond site derived from a polycarboxylic acid or a derivative thereof (a1) in the molecular structure.
  • the present invention further relates to a curable resin composition containing the acid group-containing (meth) acrylate resin and a photopolymerization initiator.
  • the present invention further relates to a cured product of the curable resin composition.
  • the present invention further relates to an insulating material comprising the curable resin composition.
  • the present invention further relates to a solder resist resin material comprising the curable resin composition.
  • the present invention further relates to a resist member made of the resin material for solder resist.
  • an acid group-containing (meth) acrylate resin excellent in the balance between elongation and heat resistance in a cured product, a curable resin composition containing the resin, an insulating material comprising the curable resin composition, and a solder A resist resin material and a resist member can be provided.
  • FIG. 1 is a GPC chart of the acid group-containing (meth) acrylate resin (1) obtained in Example 1.
  • FIG. 1 is a GPC chart of the acid group-containing (meth) acrylate resin (1) obtained in Example 1.
  • the acid group-containing (meth) acrylate resin of the present invention comprises an epoxy resin (A), an unsaturated monocarboxylic acid or derivative thereof (B), and a polycarboxylic acid anhydride (C) as essential reaction materials, and the epoxy resin.
  • (A) has an ester bond site derived from polycarboxylic acid or its derivative (a1) in the molecular structure.
  • the (meth) acrylate resin refers to a resin having an acryloyl group, a methacryloyl group, or both in the molecule.
  • the (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group, and (meth) acrylate is a general term for acrylate and methacrylate.
  • the epoxy resin (A) is characterized by having an ester bond site derived from polycarboxylic acid or its derivative (a1) in the molecular structure. This feature is an essential requirement for obtaining an acid group-containing (meth) acrylate resin that has an excellent balance between elongation and heat resistance in the cured product.
  • the epoxy resin (A) is not limited as long as it has an ester bond site derived from polycarboxylic acid or its derivative (a1) in the molecular structure and has a plurality of epoxy groups in the molecular structure.
  • the structure is not particularly limited, and any structure may be used.
  • the epoxy resin obtained by using the said polycarboxylic acid or its derivative (a1) and raw material epoxy resin (a2) as an essential reaction raw material is mentioned.
  • Examples of the polycarboxylic acid or its derivative (a1) include compounds having two or more carboxy groups in the molecular structure, acid halides, acid anhydrides and the like thereof.
  • the polycarboxylic acid or its derivative (a1) is not particularly limited as long as it has two or more reactive points derived from a carboxy group and functions as a cross-linking agent by an ester bond. Compounds can be used.
  • the number and type of the carboxy group-derived functional group of the polycarboxylic acid or its derivative (a1) is appropriately selected according to the reactivity with the raw material epoxy resin (a2), the desired cured product performance, and the like.
  • the dicarboxylic acid compound which has two carboxy groups is preferable.
  • Specific examples of the dicarboxylic acid compound include compounds represented by the following structural formula (1).
  • X represents an aliphatic hydrocarbon group, an alicyclic structure-containing hydrocarbon group, an aromatic ring-containing hydrocarbon group, and one or more of the hydrogen atoms contained therein are substituted with an alkoxy group, an aryloxy group, a halogen atom, etc. It is a structured part.
  • the aliphatic hydrocarbon group may be linear or branched, and may have one or more unsaturated bonds.
  • an alkylene group having 1 to 6 carbon atoms is preferable because the acid group-containing (meth) acrylate resin is further excellent in the balance between elongation and heat resistance in the cured product.
  • the alicyclic structure of the alicyclic structure-containing hydrocarbon group include a cyclopentane structure, a cyclohexane structure, a norbornane structure, a norbornene structure, a tricyclodecane structure, a dicyclopentadiene structure, and an adamantane structure.
  • an aliphatic hydrocarbon group as a bonding group between the alicyclic structures or a bonding group between the alicyclic structure and the carboxy group. Etc. may be contained.
  • the aliphatic hydrocarbon group as the linking group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the aromatic ring structure possessed by the aromatic ring-containing hydrocarbon group include a benzene ring, a naphthalene ring, and an anthracene ring.
  • the aromatic ring-containing hydrocarbon group contains an aliphatic hydrocarbon group or the like as a bonding group between aromatic rings or a bonding group between an alicyclic ring and a carboxy group. You may do it.
  • the aliphatic hydrocarbon group as the linking group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkoxy group include alkoxy groups having about 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group, a pentyloxy group, and a hexyloxy group.
  • aryloxy group examples include a benzeneoxy group, a naphthyloxy group, and a structural site in which one or more of hydrogen atoms on the aromatic nucleus are substituted with an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, or the like. It is done.
  • the halogen atom examples include a chlorine atom, a bromine atom, and an iodine atom.
  • X in the structural formula (1) is an alicyclic structure-containing hydrocarbon.
  • a group or a structure site in which one or more hydrogen atoms in the alicyclic structure-containing hydrocarbon group are substituted with an alkoxy group, an aryloxy group, a halogen atom or the like is preferable.
  • what has a cyclohexane structure as an alicyclic structure is more preferable.
  • the raw material epoxy resin (a2) is not particularly limited as long as it is a resin having a plurality of epoxy groups, and a wide variety of materials can be used. Especially, since it becomes acid group containing (meth) acrylate resin with especially high heat resistance in hardened
  • One example is polyglycidyl ether of phenolic hydroxyl group-containing resin.
  • a polyglycidyl ether of a novolak type resin (hereinafter referred to as “raw material epoxy resin (a2-1)”) using one or more phenolic hydroxyl group-containing compounds (P) as a reaction raw material
  • a reaction product comprising one or more phenolic hydroxyl group-containing compounds (P) and a compound (y) represented by any one of the following structural formulas (y-1) to (y-5) as essential reaction raw materials
  • polyglycidyl ether hereinafter referred to as “raw material epoxy resin (a2-2)”.
  • R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, and i is an integer of 0 or 1 to 4.
  • Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group.
  • Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group.
  • j is an integer of 1 to 4.
  • the phenolic hydroxyl group-containing compound (P) includes, for example, phenol, polyhydroxybenzene, naphthol, polyhydroxynaphthalene, anthracenol, polyhydroxyanthracene, biphenol, bisphenol, and one or more of these on the aromatic nucleus. Examples thereof include compounds having a substituent. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure.
  • Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and a nonyl group.
  • the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • aryl group examples include a phenyl group, a naphthyl group, an anthryl group, and a structural site in which the aromatic hydrocarbon group, the alkoxy group, the halogen atom, or the like is substituted on the aromatic nucleus.
  • aryloxy group examples include a phenyloxy group, a naphthyloxy group, an anthryloxy group, and a structural site in which the alkyl group, alkoxy group, halogen atom, or the like is substituted on the aromatic nucleus.
  • aralkyl group examples include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site in which the alkyl group, alkoxy group, halogen atom, or the like is substituted on the aromatic nucleus.
  • the phenolic hydroxyl group-containing compound (P) may be used singly or in combination of two or more.
  • a compound having one or more substituents on the aromatic nucleus of phenol or phenol is phenol or alkylphenol having one or more alkyl groups having 1 to 6 carbon atoms.
  • R 1 in the structural formulas (y-1) to (y-5) is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group. Specific examples thereof include those exemplified above.
  • the compound represented by the structural formula (y-1) is preferable because the acid group-containing (meth) acrylate resin is further excellent in the balance between elongation and heat resistance in the cured product.
  • the novolac resin using the phenolic hydroxyl group-containing compound (P) as a reaction raw material can be produced by the same production method as a general novolac resin.
  • the molecular weight and the like of the novolac resin is preferably adjusted so that the softening point of the obtained raw material epoxy resin (a2-1) is about 50 to 120 ° C.
  • the reaction between the phenolic hydroxyl group-containing compound (P) and the compound (y) can be carried out by a method of heating and stirring under acid catalyst conditions and at a temperature of about 70 to 180 ° C.
  • the reaction ratio between the phenolic hydroxyl group-containing compound (P) and the compound (y) is such that the phenolic hydroxyl group-containing compound (P) is 1.5 to 5 moles per mole of the compound (y). It is preferable that
  • the polyglycidyl etherification reaction of the phenolic hydroxyl group-containing resin can be performed by a known and conventional method.
  • 2 to 10 mol of epihalohydrin is used with respect to 1 mol of phenolic hydroxyl group contained in the phenolic hydroxyl group-containing resin, and 0.9 to 2.0 mol of basicity with respect to 1 mol of phenolic hydroxyl group.
  • Examples thereof include a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding the catalyst all at once or dividedly.
  • the epoxy group equivalent of the raw material epoxy resin (a2) is an acid group-containing (meth) acrylate resin that is excellent in developability in addition to elongation and heat resistance in the cured product, and is in the range of 160 to 400 g / equivalent. Preferably there is.
  • the raw material epoxy resin (a2) may be used alone or in combination of two or more.
  • the raw material epoxy resin (a2-2) is preferably used as an essential component because the acid group-containing (meth) acrylate resin is further excellent in the balance of elongation and heat resistance in the cured product.
  • the obtained acid group-containing (meth) acrylate resin in addition to the elongation and heat resistance in the cured product, various performances can be imparted, and balance control of each performance becomes easy.
  • the ratio of the raw material epoxy resin (a2-2) to the total weight of the raw material epoxy resin (a2) is preferably 30% by mass or more, more preferably in the range of 30 to 80% by mass, and 40 to 70%. It is particularly preferable that the mass range. Further, the total mass of the raw material epoxy resin (a2-1) and the raw material epoxy resin (a2-2) with respect to the total mass of the raw material epoxy resin (a2) is preferably 50% by mass or more, and 80% by mass. More preferably.
  • the raw material epoxy resin (a2) produced separately may be used, or it may be used at the stage of the phenolic hydroxyl group-containing resin to be polyglycidyl etherified. You may use what you did.
  • the reaction between the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2) can be performed, for example, in the presence of an esterification catalyst at a temperature range of 100 to 150 ° C.
  • the reaction ratio between the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2) is an acid group-containing (meth) acrylate resin that is excellent in developability in addition to elongation and heat resistance in the cured product. From the above, it is preferable to use the polycarboxylic acid or its derivative (a1) in the range of 0.5 to 20% by mass, and in the range of 1 to 10% by mass, based on the total mass of the raw material epoxy resin (a2). It is more preferable.
  • esterification reaction catalyst examples include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, and amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine. These may be used alone or in combination of two or more.
  • the amount of the catalyst added is preferably in the range of 0.05 to 5% by mass with respect to the total mass of the polycarboxylic acid or derivative (a1) and the raw material epoxy resin (a2).
  • the reaction between the polycarboxylic acid or its derivative (a1) and the raw material epoxy resin (a2) may be performed in an organic solvent as necessary.
  • the organic solvent to be used is appropriately selected depending on the solubility of the acid group-containing (meth) acrylate resin that is the reaction raw material and the product and the reaction temperature conditions.
  • methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone examples include methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, dialkylene glycol acetate and the like. These may be used alone or as a mixed solvent of two or more.
  • the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.
  • epoxy resin (A) an epoxy resin having an oxazolidone ring structure in the molecular structure can also be used.
  • the epoxy resin having an oxazolidone ring structure in the molecular structure is not particularly limited as long as it has an oxazolidone ring structure in the molecular structure, and various kinds of resins can be used. .
  • the epoxy resin having an oxazolidone ring structure in the molecular structure for example, the polyglycidyl etherified product of the phenolic hydroxyl group-containing compound (P) described above and the polyisocyanate compound (a3) are used as essential reaction raw materials. Reaction products are mentioned.
  • the polyisocyanate compound (a3) is a compound having a plurality of isocyanate groups in the molecule, the specific structure and the presence or absence of other functional groups are not particularly limited, and various types can be used.
  • Specific examples of the polyisocyanate compound (a3) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; Alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; aromas such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene di
  • R 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 2 is each independently an alkyl group having 1 to 4 carbon atoms or a bonding point linked to a structural moiety represented by the structural formula (2) via a methylene group marked with *.
  • m is 0 or an integer of 1 to 3
  • l is an integer of 1 or more.
  • Examples of the unsaturated monocarboxylic acid or its derivative (B) include compounds having a (meth) acryloyl group and a carboxy group in one molecule such as acrylic acid and methacrylic acid, acid halides, acid anhydrides thereof, and the like. It is done. These may be used alone or in combination of two or more.
  • any acid anhydride of a compound having two or more carboxy groups in one molecule can be used.
  • oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid examples thereof include acid anhydrides of dicarboxylic acid compounds such as hexahydrophthalic acid and methylhexahydrophthalic acid.
  • Polycarboxylic acid anhydrides (C) may be used alone or in combination of two or more.
  • phthalic acid isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc.
  • An acid anhydride of a compound having a cyclic structure is preferred.
  • a succinic anhydride is preferable in that the acid group-containing (meth) acrylate resin is excellent in developability.
  • the acid group-containing (meth) acrylate resin of the present invention uses the epoxy resin (A), the unsaturated monocarboxylic acid or its derivative (B), and the polycarboxylic acid anhydride (C) as essential reaction raw materials. If it is a thing, the manufacturing method will not be specifically limited, For example, either the method of reacting all the reaction raw materials collectively, or the method of reacting sequentially may be sufficient. Among them, since the reaction is easily controlled, the epoxy resin (A) is first reacted with the unsaturated monocarboxylic acid or derivative (B), and then the polycarboxylic acid anhydride (C) is reacted. The method is preferred.
  • the reaction is performed, for example, by reacting the epoxy resin (A) with the unsaturated monocarboxylic acid or derivative (B) in the presence of an esterification reaction catalyst in a temperature range of 100 to 150 ° C.
  • the polycarboxylic acid anhydride (C) can be added to the mixture and reacted in a temperature range of 90 to 120 ° C.
  • the reaction ratio of the epoxy resin (A) to the unsaturated monocarboxylic acid or its derivative (B) is the ratio of the unsaturated monocarboxylic acid or its derivative (B) to 1 mol of the epoxy group in the epoxy resin (A). It is preferably used in the range of 0.9 to 1.1 mol.
  • the reaction rate of the polycarboxylic acid anhydride (D) is preferably in the range of 0.2 to 1.0 mol with respect to 1 mol of the epoxy group in the epoxy resin (A).
  • esterification catalyst examples include the same compounds as those used in the reaction of the polycarboxylic acid or its derivative (a1) with the raw material epoxy resin (a2).
  • the addition amount of the catalyst is preferably in the range of 0.03 to 5% by mass with respect to the total mass of the reaction raw materials.
  • the reaction may be performed in an organic solvent as necessary.
  • the organic solvent to be used include the same compounds as those used in the reaction of the polycarboxylic acid or its derivative (a1) with the raw material epoxy resin (a2).
  • the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials because the reaction efficiency is good.
  • the acid value of the acid group-containing (meth) acrylate resin of the present invention is an acid group-containing (meth) acrylate resin that is excellent in developability in addition to elongation and heat resistance in the cured product, 40 to 90 mgKOH / g It is preferable that it is the range of these.
  • the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method of JIS K 0070 (1992).
  • the acid group-containing (meth) acrylate resin of the present invention has a polymerizable (meth) acryloyl group in the molecular structure, for example, it can be used as a curable resin composition by adding a photopolymerization initiator. Can do.
  • the photopolymerization initiator may be selected and used according to the type of active energy ray to be irradiated. Moreover, you may use together with photosensitizers, such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile compound.
  • photosensitizers such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, a nitrile compound.
  • photopolymerization initiator examples include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) Alkylphenone photopolymerization initiators such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples include acylphosphine oxide photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.
  • the addition amount of the photopolymerization initiator is preferably in the range of 0.05 to 15% by mass, for example, in the range of 0.1 to 10% by mass with respect to the total of components other than the solvent of the curable resin composition. It is more preferable that
  • the curable resin composition of the present invention may contain a resin component other than the acid group-containing (meth) acrylate resin of the present invention.
  • the resin component is obtained, for example, by reacting an epoxy resin such as a bisphenol type epoxy resin or a novolak type epoxy resin with (meth) acrylic acid, dicarboxylic acid anhydride, and unsaturated monocarboxylic acid anhydride as required.
  • an epoxy resin such as a bisphenol type epoxy resin or a novolak type epoxy resin
  • acrylic acid, dicarboxylic acid anhydride dicarboxylic acid anhydride
  • unsaturated monocarboxylic acid anhydride unsaturated monocarboxylic acid anhydride
  • Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic mono (meth) acrylate compounds such as meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate,
  • Aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate
  • alicyclic di (meth) acrylate compounds aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate;
  • Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; (poly) oxyethylene chain in the molecular structure of the aliphatic tri (meth) acrylate compound, (poly) (Poly) oxyalkylene-modified tri (meth) acrylate compound introduced with (poly) oxyalkylene chain such as oxypropylene chain and (poly) oxytetramethylene chain; in the molecular structure of the aliphatic tri (meth) acrylate compound ( A lactone-modified tri (meth) acrylate compound having a poly) lactone structure;
  • Tetra- or higher functional aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; (Poly) oxyalkylene-modified poly (meth) having 4 or more functionalities in which (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, or other (poly) oxyalkylene chain is introduced into the molecular structure Acrylate compounds; tetrafunctional or higher functional lactone-modified poly (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound.
  • the curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity.
  • the kind and addition amount are appropriately adjusted according to the desired performance. Generally, it is used in the range of 10 to 90% by mass with respect to the total of the curable resin composition.
  • Specific examples of the solvent include, for example, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate and butyl acetate; aromatics such as toluene and xylene.
  • Solvents include cycloaliphatic, methylcyclohexane and other alicyclic solvents; carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohol solvents; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol mono Examples include glycol ether solvents such as alkyl ether acetates. These may be used alone or in combination of two or more.
  • the curable resin composition of the present invention may contain various additives such as inorganic fine particles and polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers. .
  • the acid group-containing (meth) acrylate resin of the present invention is characterized by an excellent balance between elongation and heat resistance in a cured product.
  • the acid group-containing (meth) acrylate resin of the present invention has a performance that defeats the conventional technical knowledge in that both of these difficult performances are combined at a high level.
  • the acid group-containing (meth) acrylate resin of the present invention is used as an application in which the balance between elongation and heat resistance in a cured product is utilized, for example, as a semiconductor device-related application, a solder resist, an interlayer insulating material, It can be used as a package adhesive layer such as a package material, an underfill material or a circuit element, or an adhesive layer between an integrated circuit element and a circuit board.
  • thin film display applications such as LCD and OELD can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like.
  • the acid group-containing (meth) acrylate resin of the present invention is excellent in developability as well as elongation and heat resistance in a cured product, it can be suitably used for solder resist applications.
  • the resin material for solder resist of the present invention includes, for example, each component such as a curing agent, a curing accelerator, and an organic solvent in addition to the acid group-containing (meth) acrylate resin, the photopolymerization initiator, and various additives. Become.
  • the curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxy group in the acid group-containing (meth) acrylate resin, and examples thereof include an epoxy resin.
  • examples of the epoxy resin used here include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin.
  • Bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol Examples include addition reaction type epoxy resins. These may be used alone or in combination of two or more. Among these epoxy resins, phenolic novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin because of excellent heat resistance in cured products.
  • Novolak type epoxy resins such as naphthol-cresol co-condensed novolak type epoxy resins are preferable, and those having a softening point in the range of 50 to 120 ° C. are particularly preferable.
  • the curing accelerator accelerates the curing reaction of the curing agent.
  • a phosphorus compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid examples include amine complex salts. These may be used alone or in combination of two or more.
  • the addition amount of the curing accelerator is, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.
  • the organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth) acrylate resin and the curing agent.
  • methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol examples include cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • the method of obtaining a resist member using the solder resist resin material of the present invention is, for example, by applying the solder resist resin material on a substrate and evaporating and drying the organic solvent in a temperature range of about 60 to 100 ° C. Thereafter, there is a method in which a non-exposed portion is exposed with an ultraviolet solution or an electron beam through a photomask having a desired pattern formed, and an unexposed portion is developed with an alkaline aqueous solution, and further heated and cured in a temperature range of about 140 to 180 ° C. .
  • the acid value of the acid group-containing (meth) acrylate resin was measured by the neutralization titration method of JIS K 0070 (1992).
  • curable resin composition 100 g of acid group-containing (meth) acrylate resin obtained above, “EPICLON N-680” (cresol novolac type epoxy resin) manufactured by DIC Corporation 24 g, “Irgacure 907” [2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one] manufactured by BASF, and 13 g of diethylene glycol monomethyl ether acetate were blended to prepare a curable resin composition. Obtained.
  • the curable resin composition was apply
  • curable resin composition 100 g of the acid group-containing (meth) acrylate resin obtained previously, 24 g of “EPICLON N-680” (cresol novolac type epoxy resin) manufactured by DIC Corporation, Toagosei 10 g of “Lumicure DPA-600T” (composition containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a molar ratio of 40/60), “Irgacure 907” [2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one], 13 g of diethylene glycol monomethyl ether acetate, and 0.65 g of phthalocyanine green as a pigment were blended and kneaded by a roll mill to obtain a curable resin composition.
  • Step Tablet No. 2 was irradiated with ultraviolet rays of 500 mJ / cm 2 using a metal halide lamp. This was developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds and evaluated by the number of remaining steps. The greater the number of remaining stages, the higher the photosensitivity.

Landscapes

  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

La présente invention concerne une résine de (méth)acrylate contenant un groupe acide obtenue à partir de matières premières qui comprennent (A) une résine époxy, (B) un acide monocarboxylique insaturé ou un dérivé correspondant et (C) un anhydride polycarboxylique en tant que réactifs essentiels, la résine époxy (A) présentant une structure moléculaire qui contient une partie de liaison ester dérivée de (a1) un acide polycarboxylique ou un dérivé correspondant. Cette résine de (méth)acrylate contenant un groupe acide peut donner des objets durcis présentant un excellent équilibre entre l'allongement et la résistance à la chaleur.
PCT/JP2018/007724 2017-03-22 2018-03-01 Résine de (méth)acrylate contenant un groupe acide et matière de résine pour réserve de soudure Ceased WO2018173679A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021046520A (ja) * 2019-09-20 2021-03-25 日鉄ケミカル＆マテリアル株式会社 エポキシアクリレート樹脂、アルカリ可溶性樹脂、それを含む樹脂組成物及びその硬化物
JP2022017669A (ja) * 2020-07-14 2022-01-26 日鉄ケミカル＆マテリアル株式会社 保護膜及びそれを得るための感光性樹脂組成物
EP4230668A1 (fr) * 2022-02-22 2023-08-23 DIC Corporation Résine époxy ester, résine époxy ester modifiée par vinyle, composition de résine, peinture et article revêtu de la peinture

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5936246A (ja) * 1975-12-19 1984-02-28 バイエル・アクチエンゲゼルシヤフト 樹脂組成物
WO2002077058A1 (fr) * 2001-03-23 2002-10-03 Taiyo Ink Manufacturing Co., Ltd. Résine durcissant aux rayonnements actiniques, composition de résine photodurcissante ou thermodurcissante la contenant, et article durci ainsi obtenu
WO2003087186A1 (fr) * 2002-03-29 2003-10-23 Taiyo Ink Manufacturing Co., Ltd. Composes insatures a ramifications multiples, compositions durcissables les contenant, et articles durcis qu'ils permettent de realiser
JP2004045792A (ja) * 2002-07-12 2004-02-12 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びその硬化物
JP2004067814A (ja) * 2002-08-05 2004-03-04 Showa Highpolymer Co Ltd ポリカルボン酸樹脂およびポリカルボン酸樹脂組成物、ならびにその硬化物
JP2004300303A (ja) * 2003-03-31 2004-10-28 Taiyo Ink Mfg Ltd 不飽和基含有多分岐化合物、それを含有する硬化性組成物及びその硬化物
JP2005206803A (ja) * 2003-12-22 2005-08-04 Japan U-Pica Co Ltd 酸変性エポキシ（メタ）アクリレート化合物及び該酸変性エポキシ（メタ）アクリレート化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物。
JP2006321953A (ja) * 2005-05-20 2006-11-30 Japan U-Pica Co Ltd 酸変性エポキシ（メタ）アクリレート化合物及び該化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物
JP2008116813A (ja) * 2006-11-07 2008-05-22 Taiyo Ink Mfg Ltd アルカリ現像可能な感光性樹脂組成物およびそれを用いたプリント配線板
WO2009025190A1 (fr) * 2007-08-21 2009-02-26 Nippon Kayaku Kabushiki Kaisha Composé carboxylate réactif, composition de résine durcissable par rayonnement d'énergie active utilisant celui-ci et son utilisation
WO2010113478A1 (fr) * 2009-03-31 2010-10-07 太陽インキ製造株式会社 Composition de résine durcissable et carte de câblage imprimée
JP2010248308A (ja) * 2009-04-13 2010-11-04 Japan U-Pica Co Ltd 多官能エポキシ（メタ）アクリレート化合物及び該化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物
JP2011001509A (ja) * 2009-06-22 2011-01-06 Air Water Inc エポキシ（メタ）アクリレート樹脂、硬化性樹脂組成物およびその硬化物
JP2011144230A (ja) * 2010-01-13 2011-07-28 Japan U-Pica Co Ltd 多官能エポキシ（メタ）アクリレート化合物及び該化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物
JP2011257687A (ja) * 2010-06-11 2011-12-22 Toagosei Co Ltd 感光性樹脂組成物、ソルダーレジスト及び感光性ドライフィルム

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007153978A (ja) * 2005-12-02 2007-06-21 Nippon Shokubai Co Ltd 酸変性エポキシ（メタ）アクリレートおよび画像形成用感光性樹脂組成物
JP2013151595A (ja) * 2012-01-25 2013-08-08 Unitika Ltd 熱硬化性樹脂組成物およびそれを加熱硬化してなる硬化物

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5936246A (ja) * 1975-12-19 1984-02-28 バイエル・アクチエンゲゼルシヤフト 樹脂組成物
WO2002077058A1 (fr) * 2001-03-23 2002-10-03 Taiyo Ink Manufacturing Co., Ltd. Résine durcissant aux rayonnements actiniques, composition de résine photodurcissante ou thermodurcissante la contenant, et article durci ainsi obtenu
WO2003087186A1 (fr) * 2002-03-29 2003-10-23 Taiyo Ink Manufacturing Co., Ltd. Composes insatures a ramifications multiples, compositions durcissables les contenant, et articles durcis qu'ils permettent de realiser
JP2004045792A (ja) * 2002-07-12 2004-02-12 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びその硬化物
JP2004067814A (ja) * 2002-08-05 2004-03-04 Showa Highpolymer Co Ltd ポリカルボン酸樹脂およびポリカルボン酸樹脂組成物、ならびにその硬化物
JP2004300303A (ja) * 2003-03-31 2004-10-28 Taiyo Ink Mfg Ltd 不飽和基含有多分岐化合物、それを含有する硬化性組成物及びその硬化物
JP2005206803A (ja) * 2003-12-22 2005-08-04 Japan U-Pica Co Ltd 酸変性エポキシ（メタ）アクリレート化合物及び該酸変性エポキシ（メタ）アクリレート化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物。
JP2006321953A (ja) * 2005-05-20 2006-11-30 Japan U-Pica Co Ltd 酸変性エポキシ（メタ）アクリレート化合物及び該化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物
JP2008116813A (ja) * 2006-11-07 2008-05-22 Taiyo Ink Mfg Ltd アルカリ現像可能な感光性樹脂組成物およびそれを用いたプリント配線板
WO2009025190A1 (fr) * 2007-08-21 2009-02-26 Nippon Kayaku Kabushiki Kaisha Composé carboxylate réactif, composition de résine durcissable par rayonnement d'énergie active utilisant celui-ci et son utilisation
WO2010113478A1 (fr) * 2009-03-31 2010-10-07 太陽インキ製造株式会社 Composition de résine durcissable et carte de câblage imprimée
JP2010248308A (ja) * 2009-04-13 2010-11-04 Japan U-Pica Co Ltd 多官能エポキシ（メタ）アクリレート化合物及び該化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物
JP2011001509A (ja) * 2009-06-22 2011-01-06 Air Water Inc エポキシ（メタ）アクリレート樹脂、硬化性樹脂組成物およびその硬化物
JP2011144230A (ja) * 2010-01-13 2011-07-28 Japan U-Pica Co Ltd 多官能エポキシ（メタ）アクリレート化合物及び該化合物を含有する感光性熱硬化性樹脂組成物並びにその硬化物
JP2011257687A (ja) * 2010-06-11 2011-12-22 Toagosei Co Ltd 感光性樹脂組成物、ソルダーレジスト及び感光性ドライフィルム

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021046520A (ja) * 2019-09-20 2021-03-25 日鉄ケミカル＆マテリアル株式会社 エポキシアクリレート樹脂、アルカリ可溶性樹脂、それを含む樹脂組成物及びその硬化物
JP7479130B2 (ja) 2019-09-20 2024-05-08 日鉄ケミカル＆マテリアル株式会社 エポキシアクリレート樹脂、アルカリ可溶性樹脂、それを含む樹脂組成物及びその硬化物
JP2022017669A (ja) * 2020-07-14 2022-01-26 日鉄ケミカル＆マテリアル株式会社 保護膜及びそれを得るための感光性樹脂組成物
JP7621751B2 (ja) 2020-07-14 2025-01-27 日鉄ケミカル＆マテリアル株式会社 保護膜及びそれを得るための感光性樹脂組成物
EP4230668A1 (fr) * 2022-02-22 2023-08-23 DIC Corporation Résine époxy ester, résine époxy ester modifiée par vinyle, composition de résine, peinture et article revêtu de la peinture

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