WO2024038761A1 - Produit durci, article pourvu d'un produit durci et procédé de diminution de la contrainte interne d'un produit durci - Google Patents

Produit durci, article pourvu d'un produit durci et procédé de diminution de la contrainte interne d'un produit durci Download PDF

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WO2024038761A1
WO2024038761A1 PCT/JP2023/028212 JP2023028212W WO2024038761A1 WO 2024038761 A1 WO2024038761 A1 WO 2024038761A1 JP 2023028212 W JP2023028212 W JP 2023028212W WO 2024038761 A1 WO2024038761 A1 WO 2024038761A1
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meth
cured product
epoxy
acrylic polymer
acrylate
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PCT/JP2023/028212
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Japanese (ja)
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秀典 田中
仁 玉井
健一 吉橋
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株式会社カネカ
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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
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a cured product, an article including the cured product, and a method for relieving internal stress in the cured product.
  • a curable composition containing a (meth)acrylic polymer and an epoxy compound is known as a prior art (for example, Patent Document 1).
  • One aspect of the present invention aims to provide a cured product with excellent impact resistance.
  • the cured product according to one embodiment of the present invention is A (meth)acrylic polymer (A) having an average of 0.8 or more groups represented by the general formula (1) per molecule at the end of the molecule; An epoxy compound and/or an oxetane compound (B), a photoradical initiator (C); A curable composition containing an epoxy curing agent (D) is cured, The film thickness is 200 ⁇ m or less.
  • a method for relieving internal stress of a cured product includes: A (meth)acrylic polymer (A) having an average of 0.8 or more groups represented by the general formula (1) per molecule at the end of the molecule, and an epoxy compound and/or an oxetane compound (B) , a photoradical initiator (C), and an epoxy curing agent (D).
  • the film thickness of the cured product obtained by curing is 200 ⁇ m or less.
  • -OC(O)C(R 1 ) CH 2 (1) (In the formula, R 1 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.)
  • a cured product with excellent impact resistance can be achieved.
  • FIG. 3 is a diagram showing the relationship between internal stress and thickness of cured products according to Examples 1 and 2 and Comparative Examples 1 to 3.
  • FIG. 7 is a diagram showing the relationship between internal stress and thickness of cured products according to Examples 3 to 6 and Comparative Examples 4 to 7.
  • curable compositions containing epoxy compounds contract during the curing and/or cooling process, generating large internal stress. Due to the internal stress, the cured product obtained by curing the curable composition has a problem in that it is easily broken by physical impact and/or cooling impact.
  • the present inventors discovered that by adding a (meth)acrylic polymer (A) to a curable composition, the internal stress of the cured product obtained was It has been discovered for the first time that the impact resistance of the cured product can be improved as a result.
  • the cured product according to one embodiment of the present invention contains a (meth)acrylic polymer (A), an epoxy compound and/or an oxetane compound (B), a photoradical initiator (C), and an epoxy curing agent (D). It is obtained by curing the curable composition contained therein. Examples of the curing method include photocuring and/or thermal curing.
  • Photocuring is not particularly limited, but includes photoradical curing.
  • Photo-radical curing is curing initiated by irradiation with active energy rays (UV or electron beams, etc.).
  • the source of active energy rays can be appropriately selected depending on the properties of the photoradical initiator (C).
  • Examples of active energy ray sources include high pressure mercury lamps, low pressure mercury lamps, LEDs, electron beam irradiators, halogen lamps, light emitting diodes, and semiconductor lasers.
  • Thermal curing is curing initiated by heating.
  • the thermosetting temperature is appropriately set depending on the types of the epoxy compound and/or oxetane compound (B), the epoxy curing agent (D), and other additives.
  • the thermosetting temperature is preferably 15 to 300°C, more preferably 15 to 250°C. Within the above temperature range, deterioration of the cured product due to heat can be prevented.
  • a heating furnace, an oven, a heating conveyor, etc. can be used for thermal curing.
  • the upper limit of the film thickness of the cured product is 200 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and still more preferably 50 ⁇ m or less. If the film thickness of the cured product is 200 ⁇ m or less, by adding a (meth)acrylic polymer (A) to the curable composition, the internal stress of the resulting cured product is alleviated and the impact resistance is improved. be able to.
  • the lower limit of the film thickness of the cured product is, for example, 5 ⁇ m or more from the viewpoint of impact resistance.
  • One embodiment of the present invention includes a (meth)acrylic polymer (A), an epoxy compound and/or an oxetane compound (B), a photoradical initiator (C), and an epoxy curing agent (D). Also included is a method for relaxing the internal stress of the cured product, which includes a step of curing the curable composition contained therein, and the film thickness of the cured product obtained by curing is 200 ⁇ m or less.
  • the (meth)acrylic polymer (A) has an average of 0.8 or more groups represented by the general formula (1) per molecule at the end of the molecule.
  • -OC(O)C(R 1 ) CH 2 (1)
  • R 1 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
  • R 1 is -H, -CH 3 , -CH 2 CH 3 , -(CH 2 ) n CH 3 (n represents an integer from 2 to 19), -C 6 H 5 (phenyl group), -CH Examples include 2OH , -CN, and the like. From the viewpoint of reactivity, R 1 is preferably -H or -CH 3 . That is, it is preferable that the group represented by general formula (1) is a (meth)acryloyl group.
  • the number of groups represented by general formula (1) per molecule of the (meth)acrylic polymer (A) is preferably 0.85 or more, and 1 or more, from the viewpoint of improving curability.
  • the number may be 1.5 or more.
  • the number of groups represented by general formula (1) is preferably 2.0 or less, more preferably less than 2.0.
  • the (meth)acrylic polymer (A) preferably has a group represented by general formula (1) at one end of the molecule.
  • the number of groups represented by general formula (1) per molecule of the (meth)acrylic polymer (A) is preferably 0.8 or more, and more preferably Preferably it is 0.85 or more.
  • the number is preferably 1.0 or less, and more preferably less than 1.0.
  • the number average molecular weight of the (meth)acrylic polymer (A) is preferably 3,000 to 100,000, more preferably 10,000 to 90, when measured by gel permeation chromatography (GPC). ,000, more preferably 30,000 to 80,000.
  • GPC gel permeation chromatography
  • the number average molecular weight is 3,000 or more, sufficient flexibility and rubber elasticity can be obtained from the cured product.
  • the number average molecular weight is 100,000 or less, the viscosity of the polymer can be suppressed and handling is easy.
  • GPC measurements are performed using chloroform as a mobile phase using a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.
  • the (meth)acrylic monomer that constitutes the main chain of the (meth)acrylic polymer (A) is not particularly limited.
  • Examples of the (meth)acrylic monomer include (meth)acrylic acid and (meth)acrylic ester.
  • (Meth)acrylate esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate.
  • the (meth)acrylic polymer (A) preferably has a repeating unit derived from a (meth)acrylic acid ester having an alkoxy group having 1 to 3 carbon atoms.
  • Examples of the (meth)acrylic acid ester monomer having an alkoxy group having 1 to 3 carbon atoms include 2-methoxyethyl (meth)acrylate and 3-methoxybutyl (meth)acrylate.
  • the (meth)acrylic polymer (A) preferably has 1 to 35% by weight of repeating units derived from a (meth)acrylic acid ester having an alkoxy group having 1 to 3 carbon atoms in the total repeating units.
  • the (meth)acrylic polymer (A) includes a (meth)acrylic ester having an alkyl group having 3 to 5 carbon atoms, a (meth)acrylic ester having an alkyl group having 1 to 2 carbon atoms, and a (meth)acrylic ester having an alkyl group having 1 to 2 carbon atoms.
  • a polymer (A1) of (meth)acrylic acid ester having 3 alkoxy groups is preferable.
  • the monomers constituting the main chain of the (meth)acrylic polymer (A1) are not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-methoxy (meth)acrylate Examples include ethyl and 3-methoxybutyl (meth)acrylate.
  • the (meth)acrylic polymer (A1) has an acrylic ester having an alkyl group having 3 to 5 carbon atoms, an acrylic ester having an alkyl group having 1 to 2 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. It is preferable that the repeating unit derived from acrylic acid ester is 80% by weight or more, more preferably 90% by weight or more, and 95% by weight or more of the total repeating units constituting the (meth)acrylic polymer (A1). More preferably, the upper limit is 100% by weight or less.
  • the molecular weight distribution of the (meth)acrylic polymer (A) is preferably 1.8 or less, more preferably 1.7 or less, still more preferably 1.6 or less, even more preferably 1. It is 5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.
  • the theoretical lower limit of the molecular weight distribution is 1.
  • the molecular weight distribution is the ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by GPC. When the molecular weight distribution is 1.8 or less, the mechanical properties of the resulting cured product can be easily controlled.
  • the polymerization method for the (meth)acrylic polymer (A) is not particularly limited, but examples thereof include the polymerization methods described in JP-A No. 2005-232419, JP-A No. 2006-291073, and JP-A No. 2016-88944.
  • a method for introducing a group represented by general formula (1) to the terminal of the (meth)acrylic polymer (A) for example, the method described in paragraphs [0081] to [0087] of JP-A-2016-88944 is There are several methods.
  • Epoxy compound and/or oxetane compound (B) The curable composition contains an epoxy compound and/or an oxetane compound (B).
  • the epoxy compound and the oxetane compound play a role in improving the strength of the cured product.
  • the oxetane compound also plays the role of lowering the viscosity of the curable composition and improving workability.
  • the epoxy compound and/or oxetane compound (B) may be used alone or in combination of two or more.
  • Epoxy compound generally refers to a compound having an epoxy group.
  • examples of epoxy compounds include aromatic epoxy compounds and alicyclic epoxy compounds. From the viewpoint of increasing the hardness of the cured product, aromatic epoxy compounds are preferred.
  • the epoxy compound has a radically reactive group.
  • Such an epoxy compound forms a crosslink with the (meth)acryloyl functional group of the (meth)acrylic polymer. Therefore, a tough cured product with low elution into solvents can be obtained.
  • radically reactive groups include acryloyl, methacryloyl, and allyl groups. Epoxy compounds having radically reactive groups are available from Nippon Kayaku Co., Ltd., DIC Corporation, Showa Denko Materials Co., Ltd., and the like.
  • aromatic epoxy compounds include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol AD epoxy compounds, hydrogenated bisphenol A epoxy compounds, and hydrogenated bisphenol F epoxy compounds.
  • An example of an aromatic epoxy compound is 2,2-bis(4-glycidyloxyphenyl)propane.
  • alicyclic epoxy compounds include compounds having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. More specific examples of alicyclic epoxy compounds include vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2-(3, Examples include 4-epoxycyclohexyl 5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate, and bis(3,4-epoxycyclohexylmethylene) adipate.
  • oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1 -(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl ] Phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl)
  • the weight ratio of the (meth)acrylic polymer (A) to the epoxy compound and/or oxetane compound (B) in the curable composition is preferably 1:99 to 50:50, more preferably 2:98 to 40:60. Preferably, 3:97 to 30:70 is more preferable. If the blending ratio of both is within the above range, sufficient strength and elongation can be imparted to the cured product.
  • the curable composition contains a photoradical initiator (C).
  • the photoradical polymerization initiator (C) plays a role of curing the curable composition using light irradiation (UV irradiation, etc.) as a trigger. Only one type of photoradical polymerization initiator (C) may be used, or two or more types may be used in combination.
  • Examples of the photoradical polymerization initiator (C) include acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, and 3-pentyl.
  • radical photopolymerization initiator (C) examples include acylphosphine oxide photopolymerization initiators.
  • Acyl phosphine oxide photopolymerization initiators are preferable because they have excellent deep curing properties upon UV irradiation.
  • acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxy benzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,6-dimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-isobutylphosphine oxide, bis(2,6-dimethylbenzoyl)-isobutylphosphine oxide, -dimethoxybenzoyl)-isobutylphosphine oxide and bis(2,6-dimethoxybenzoyl)-phenylphosphine oxide.
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4, 4-trimethyl-pentylphosphine oxide is preferred.
  • photoradical polymerization initiators (C) mentioned above 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2, 2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred.
  • the compounding amount of the photoradical initiator (C) is 0.01 parts by weight to 5 parts by weight, based on 100 parts by weight of the total weight of the (meth)acrylic polymer (A) and the epoxy compound and/or oxetane compound (B). 1 part by weight, and more preferably 0.05 part by weight to 1 part by weight from the viewpoint of achieving both deep curability and light transmittance of the cured product.
  • Epoxy curing agent (D) The curable composition contains an epoxy curing agent (D).
  • the epoxy curing agent (D) a wide variety of conventionally known ones can be used.
  • the epoxy curing agent (D) include amine curing agents, imidazole curing agents, acid anhydride curing agents, and photocationic polymerization initiators. Only one type of epoxy curing agent (D) may be used, or two or more types may be used in combination.
  • Amine compounds can be used as the amine curing agent, and examples of amine compounds include aliphatic amines (diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamine).
  • aliphatic amines diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamine).
  • methylenediamine, guanidine, oleylamine, etc. alicyclic amines (mensendiamine, isophoronediamine, norbornanediamine, piperidine, N,N'-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis(4 -amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, polycyclohexylpolyamine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), etc.); amines having an ether bond ( 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylene diamine, polyoxypropylene triamine, Polyoxyethylenediamine, etc.
  • imidazole curing agents examples include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')] -ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')
  • acid anhydride curing agents examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and dodecyl.
  • acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and dodecyl.
  • succinic anhydride examples include succinic anhydride.
  • photocationic initiators include onium salt-based photoacid generators such as sulfonium salts, iodonium salts, diazonium salts, ammonium salts, pyridinium salts, phosnium salts, oxonium salts, and quinolinium salts, sulfonic acid derivatives, diazomethanes, and carboxylic acid generators. Examples include acid esters and iron arene complexes. More specific examples of photocationic initiators include those described in paragraphs [0074] to [0079] of JP-A No. 2012-144693.
  • epoxy curing agent (D) examples include polyamide amines (polyamides obtained by reacting dimer acid with polyamines (diethylenetriamine, triethylenetetramine, etc.), and polyamides obtained by reacting polycarboxylic acids other than dimer acid with polyamines).
  • Dicyandiamide Modified amines (epoxy-modified amines obtained by reacting amines with epoxy compounds, Mannich-modified amines obtained by reacting amines with formalin or phenol compounds, Michael addition-modified amines, ketimine, etc.) Can be mentioned.
  • an amine curing agent is preferable as the epoxy curing agent (D). Furthermore, considering the storage stability of the curable composition, a tertiary amine compound is preferable as the epoxy curing agent (D).
  • the blending amount of the epoxy curing agent (D) is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy compound and/or oxetane compound (B).
  • amount of the epoxy curing agent (D) is within the above range, the curability of the curable composition can be improved and the component elution from the cured product can be reduced.
  • a mixture of the epoxy compound and/or oxetane compound (B) and the epoxy curing agent (D) may be used.
  • an ultraviolet curable epoxy resin (TB3114, manufactured by ThreeBond) can be used.
  • the curable composition may contain a photosensitive resin (F).
  • a photosensitive resin (F) When the curable composition contains the photosensitive resin (F), it can be applied as a solder resist onto a printed wiring board, and a printed wiring board coated with the cured product can be obtained.
  • the photosensitive resin (F) is not particularly limited, but for example, a photosensitive resin containing a carboxyl group or a photosensitive resin containing a phenolic hydroxyl group can be used. Such photosensitive resins can also be referred to as alkali-soluble resins. From the viewpoint of excellent developability, photosensitive resins containing carboxyl groups are preferred. Further, from the viewpoint of photosensitivity, the molecule may have an ethylenically unsaturated group in addition to the carboxyl group. More specifically, examples of the photosensitive resin containing a carboxyl group include a resin containing a free carboxyl group and having one or more photosensitive unsaturated double bonds.
  • carboxyl group-containing photosensitive resins include polybasic acid-modified radically polymerizable unsaturated monocarboxylated epoxy resins such as polybasic acid-modified epoxy (meth)acrylate resins.
  • a polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxidized epoxy resin is produced by reacting a radically polymerizable unsaturated monocarboxylic acid with at least a portion of the epoxy groups of a polyfunctional epoxy resin having two or more epoxy groups in one molecule. By doing so, a radically polymerizable unsaturated monocarboxylated epoxy resin is obtained, and the hydroxyl groups generated in the resin are reacted with a polybasic acid and/or a polybasic acid anhydride.
  • the chemical structure of the polyfunctional epoxy resin is not particularly limited as long as it is a bifunctional or more functional epoxy resin.
  • the epoxy equivalent of the polyfunctional epoxy resin is not particularly limited, but its upper limit is preferably 2,000, more preferably 1,500, even more preferably 1,000, and particularly preferably 500.
  • the lower limit of the epoxy equivalent is preferably 100, particularly preferably 200.
  • polyfunctional epoxy resins examples include biphenyl-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, rubber-modified epoxy resins such as silicone-modified epoxy resins, ⁇ -caprolactone-modified epoxy resins, bisphenol A-type epoxy resins, Phenol novolak type epoxy resins such as bisphenol F type epoxy resin and bisphenol AD type epoxy resin, cresol novolac type epoxy resin such as 4.000-cresol novolak type, bisphenol A novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin , glycidylamine type epoxy resin, heterocyclic epoxy resin, bisphenol modified novolac type epoxy resin, polyfunctional modified novolac type epoxy resin, condensate type epoxy resin of phenols and aromatic aldehyde having a phenolic hydroxyl group, etc. Can be done. Furthermore, epoxy resins obtained by introducing halogen atoms such as Br and Cl into
  • the radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include (meth)acrylic acid, crotonic acid, cinnamic acid, tiglic acid, and angelic acid. Among these, (meth)acrylic acid is preferred from the viewpoint of easy availability. These may be used alone or in combination of two or more.
  • the radically polymerizable unsaturated monocarboxylic acid reacts with the epoxy group of the polyfunctional epoxy resin, a photosensitive unsaturated double bond is introduced into the epoxy resin, thereby imparting photosensitivity to the epoxy resin.
  • the reaction method of the polyfunctional epoxy resin and the radically polymerizable unsaturated monocarboxylic acid is not particularly limited.
  • An example of this method is heating in an organic solvent).
  • polybasic acid and/or polybasic acid anhydride reacts with the hydroxyl group generated in the radically polymerizable unsaturated monocarboxylated epoxy resin by the reaction between the polyfunctional epoxy resin and the radically polymerizable unsaturated monocarboxylic acid, A free carboxyl group is further introduced into the resin into which the photosensitive unsaturated double bond has been introduced. This imparts alkaline developability to the resin.
  • the polybasic acid and polybasic acid anhydride are not particularly limited, and both saturated and unsaturated types can be used.
  • polybasic acids examples include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, and phthalic acid derivatives (e.g., tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyl Tetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid
  • examples of the polybasic acid anhydride include anhydrides
  • the method for reacting the radically polymerizable unsaturated monocarboxylated epoxy resin with the polybasic acid and/or polybasic acid anhydride is not particularly limited.
  • a method of heating the mixture and/or polybasic acid anhydride in a suitable diluent for example, an inert organic solvent
  • a suitable diluent for example, an inert organic solvent
  • a compound having one or more radically polymerizable unsaturated groups and an epoxy group for example, A carboxyl group-containing photosensitive resin whose photosensitivity is further improved by further introducing a radically polymerizable unsaturated group into the side chain of the resin by reacting a glycidyl compound may also be used.
  • the carboxyl group-containing photosensitive resin with further improved photosensitivity is produced by adding a glycidyl compound to a polybasic acid-modified radically polymerizable unsaturated monocarboxylated epoxy resin, so that the radically polymerizable unsaturated group becomes a polybasic acid-modified radical. Since it is bonded to the side chain of the polymerizable unsaturated monocarboxylated epoxy resin skeleton, the photopolymerization reactivity, that is, the photocurability is further improved, and more excellent photosensitive characteristics are exhibited.
  • glycidyl compound examples include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, and pentaerythritol trimethacrylate monoglycidyl ether. These may be used alone or in combination of two or more.
  • the acid value of the carboxyl group-containing photosensitive resin is not particularly limited, but its lower limit is preferably 30 mgKOH/g, particularly preferably 40 mgKOH/g, from the viewpoint of obtaining reliable alkali developability.
  • the upper limit of the acid value of the carboxyl group-containing photosensitive resin is preferably 200 mgKOH/g from the viewpoint of preventing dissolution of the exposed area (photocured area) by an alkaline developer, and improves the moisture resistance and insulation of the photocured product. From the viewpoint of reliably preventing a decrease in reliability, 150 mgKOH/g is particularly preferable.
  • the mass average molecular weight (Mw) of the carboxyl group-containing photosensitive resin is not particularly limited, but the lower limit thereof is preferably 6,000, more preferably 7,000, and more preferably 8,000 from the viewpoint of toughness and dryness to the touch of the photocured product. is particularly preferred.
  • the upper limit of the mass average molecular weight (Mw) of the carboxyl group-containing photosensitive resin is preferably 200,000, more preferably 100,000, and particularly preferably 50,000 from the viewpoint of reliably preventing a decrease in alkali developability.
  • the mass average molecular weight (Mw) means the molecular weight measured by GPC measurement.
  • the curable composition according to one embodiment of the present invention may contain various additives depending on the purpose.
  • additives include polymerizable monomers and/or oligomers, fillers, microhollow particles, plasticizers, solvents, thixotropic agents (anti-sagging agents), antioxidants (anti-aging agents), compatibilizers, etc. agent, hardening modifier, radical inhibitor, metal deactivator, ozone deterioration inhibitor, phosphorus peroxide decomposer, lubricant, pigment, antifoaming agent, foaming agent, termiticide, fungicide, ultraviolet rays
  • absorbers and light stabilizers include absorbers and light stabilizers.
  • the additives include paragraphs [0110] to [0124] of JP-A No. 2006-274085, paragraphs [0134] to [0151] of JP-A No. 2006-291073, and paragraphs of JP-A No. 2007-308692. [0232] to [0235], paragraphs [0089] to [0093] of International Publication No. 05/116134, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 63-254149, It is described in JP-A-64-22904, JP-A-2001-72854, etc.
  • the curable composition according to one embodiment of the present invention may further contain a reactive diluent, if necessary.
  • the curable composition contains a reactive diluent to ensure sufficient photocuring and obtain a cured product having acid resistance, alkali resistance, etc. Can be done.
  • the reactive diluent is not particularly limited, it is possible to use a compound that is a photopolymerizable monomer and has at least one polymerizable double bond per molecule, preferably at least two polymerizable double bonds per molecule.
  • the compound include monofunctional (meth)acrylate monomers, bifunctional (meth)acrylate monomers, trifunctional or more functional (meth)acrylate monomers, and the like.
  • the curable composition according to one embodiment of the present invention may further contain silica if necessary.
  • silica By containing silica, a cured product with excellent solder heat resistance and thermal shock resistance can be obtained without impairing basic properties such as alkali developability and coating appearance.
  • silica for example, scaly silica and/or spherical (for example, true spherical) silica having a main surface and end surfaces can be used.
  • the scaly silica having a surface and an end face is a flaky silica, unlike an amorphous silica powder formed by crushing large particles of silica. Further, a plurality of flaky silica particles are interconnected to form a thin film-like connected aggregate.
  • spherical silica has a spherical external shape (for example, a true spherical shape), unlike amorphous silica powder formed by pulverizing large particles of silica.
  • Spherical silica is, for example, an aggregate of primary particles. Note that the silica has not been subjected to surface treatment such as hydrophobic treatment. Therefore, it is different from silica, which can be used as a matting agent described below.
  • the curable composition according to one embodiment of the present invention may further contain an inorganic filler.
  • an inorganic filler solder heat resistance can be improved.
  • the inorganic filler include, but are not limited to, talc, barium sulfate, alumina, aluminum hydroxide, mica, silica other than flaky silica and spherical silica having a main surface and end faces, and the like.
  • the curable composition according to one embodiment of the present invention may further include a matting agent.
  • a matting agent By including a matting agent, it is possible to obtain a cured product with excellent soldering heat resistance and thermal shock resistance while reducing glossiness without impairing basic properties such as alkali developability and coating appearance. . Further, by including the matting agent, the surface shape of the coating film becomes uneven and roughened (mattized), thereby reducing glossiness and providing a matte appearance.
  • Matting agents include inorganic matting agents and organic matting agents.
  • inorganic matting agents include: spherical silica whose surface has been treated with a hydrophobic compound, etc.; hydrophilic porous silica whose surface has not been subjected to a hydrophobic treatment with a hydrophobic compound, etc.; magnesium oxide , spherical metal oxides such as calcium oxide and zinc oxide; spherical metal carbonates such as calcium carbonate and magnesium carbonate; spherical silicon carbide; and clay particles.
  • the organic matting agent include polyolefins such as urethane resins, phenol resins, silicone resins, fluororesins, polyamides, and polypropylene.
  • thermosetting component The curable composition according to one embodiment of the present invention may contain a thermosetting component.
  • the thermosetting component is not particularly limited, but includes amine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like.
  • the thermosetting components may be used alone or in combination of two or more.
  • the curable composition according to one embodiment of the present invention may contain an organic acid.
  • an organic acid By containing an organic acid, the contact angle of the dried coating film can be easily adjusted to a constant value, so the components contained in the dissolved photosensitive resin composition will not precipitate at the bottom of the developer, and as a result, the This is effective in that it can suppress contamination of the developer and clogging of the developing device due to sediment.
  • the organic acid is not particularly limited, but includes carboxylic acids, mono- or diesters of phosphorous acid, mono- or diesters of phosphoric acid, and the like.
  • the organic acid does not have an aromatic ring. By blending an organic acid that does not have an aromatic ring, the light absorption of the organic acid itself is suppressed, the photoreactivity of the photosensitive component is relatively improved, and excellent resolution can be obtained.
  • the curable composition according to one embodiment of the present invention may contain a dispersant.
  • a dispersant By including a dispersant, the dispersibility and settling properties of the curable composition can be improved.
  • the dispersant include DISPERBYK-191 (manufactured by BYK Chemie Japan).
  • the curable composition according to one embodiment of the present invention may contain a photopolymerization inhibitor.
  • a photopolymerization inhibitor By adding a photopolymerization inhibitor, a certain amount of radical polymerization that occurs inside the curable composition due to exposure to light can be suppressed depending on the type of polymerization inhibitor and the amount added.
  • thermosetting catalyst The curable composition according to one embodiment of the present invention may include a thermosetting catalyst.
  • thermosetting catalyst include imidazole derivatives, amine compounds, hydrazine compounds, phosphorus compounds, and S-triazine derivatives.
  • the curable composition according to one embodiment of the present invention may contain a thermal polymerization inhibitor. By including a thermal polymerization inhibitor, thermal polymerization or polymerization over time of the curable composition can be prevented.
  • the curable composition according to one embodiment of the present invention may contain a chain transfer agent.
  • a chain transfer agent By including a chain transfer agent, the sensitivity of the curable composition can be improved.
  • Known chain transfer agents can be used, such as N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like.
  • the curable composition according to one embodiment of the present invention may contain an organic solvent.
  • organic solvent include, but are not particularly limited to, ketones, aromatic hydrocarbons, glycol ethers, esters, aliphatic hydrocarbons, petroleum solvents, and the like. These solvents may be used alone or in combination of two or more.
  • the curable composition according to one embodiment of the present invention may contain a curing agent.
  • the curing agent include phenol resins, polycarboxylic acids and their acid anhydrides, cyanate ester resins, active ester resins, maleimide compounds, alicyclic olefin polymers, and the like.
  • One type of curing agent may be used alone, or two or more types may be used in combination.
  • the curable composition according to one embodiment of the present invention may contain a colorant.
  • Colorants include, but are not limited to, pigments, dyes, pigments, and the like.
  • the curable composition according to one embodiment of the present invention may contain a photopolymerizable monomer.
  • the photopolymerizable monomer may be a monomer having an ethylenically unsaturated double bond.
  • Examples of the photopolymerizable monomer include polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, carbonate (meth)acrylate, and epoxy (meth)acrylate.
  • thermosetting resin The curable composition according to one embodiment of the present invention may contain a thermosetting resin.
  • Thermosetting resins are not particularly limited, but include, for example, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, episulfide resins, and the like.
  • the curable composition according to one embodiment of the present invention may contain a sensitizer.
  • the sensitizer may be an anthracene compound, and commercially available products can be used.
  • Commercially available products include, for example, UVS-107 (molecular weight 410) and UVS-581 (molecular weight 434) manufactured by Kawasaki Chemical Industries, Ltd.
  • the curable composition according to one embodiment of the present invention may contain a silane coupling agent.
  • a silane coupling agent for example, a silane coupling agent having an imidazole ring can be used.
  • the curable composition according to one embodiment of the present invention may include an elastomer.
  • an elastomer By including an elastomer, the elastic modulus can be lowered, so stress during curing can be relaxed and crack resistance can be further improved.
  • the elastomer is not particularly limited, but examples include polyester elastomer, styrene elastomer, polyurethane elastomer, polyester urethane elastomer, polyamide elastomer, polyesteramide elastomer, acrylic elastomer, olefin elastomer, silicone elastomer, etc. It will be done.
  • resins in which part or all of the epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can also be used.
  • epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, block copolymers, etc. can also be used.
  • the curable composition according to one embodiment of the present invention may contain a photopolymerization initiation aid in combination with the photoradical initiator (C).
  • the photopolymerization initiation aid is not particularly limited, examples thereof include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.
  • the article including the cured product according to an embodiment of the present invention is not particularly limited, but may be an article obtained by, for example, coating a curable composition on a base material, etc., and then curing it. .
  • Examples of such articles include printed wiring boards coated with solder resist.
  • known methods can be used to apply the curable composition to the substrate, such as screen printing, bar coater, spray coating, applicator, blade coater, knife coater, roll coater, gravure coater, etc. can be mentioned.
  • the cured product according to one embodiment of the present invention has good electrical insulation, it can be suitably used for electrical/electronic parts, resist materials, and the like. However, it is not limited to these uses, and can be used in various other uses.
  • electrical/electronic parts include electrical insulation materials (insulating coating materials for wires and cables, etc.), sealing materials, adhesives, pressure-sensitive adhesives, conformal coating agents, electrical and electronic potting agents, packing, O-rings, and belts. Can be mentioned. More specific examples include high voltage thick film resistors, hybrid IC circuit elements, HICs, electrical insulation parts, semiconducting parts, conductive parts, modules, printed circuits, ceramic substrates, diodes, transistors, and bonding wires.
  • buffer materials such as optical fibers for optical communication, transformer high voltage circuits, printed circuit boards, high voltage transformers with variable resistance parts, electrical insulation parts, solar cells (crystalline silicon solar cells, amorphous silicon solar cells, CI (G)S solar cells, perovskite solar cells, organic thin film solar cells, dye-sensitized solar cells, GaAs solar cells, etc.), potting materials for flyback transformers for TVs, heavy electrical parts, light electrical parts, back sealing of solar cells. Examples include sealing materials for circuits and boards of electrical and electronic equipment.
  • resist materials include peripheral members of semiconductors and conductors. More specific examples include photomasks, photoresists, semiconductor surface protection tapes, dicing tapes, die bonding tapes, die bonding materials, interlayer insulation materials (buildup materials), photosensitive dry film resists, and liquid photosensitive resin materials. , interporter materials, package substrate materials, solder resists, semiconductor sealing resins, underfill materials, side fill materials, printed circuit board materials, and modifiers for these materials.
  • Examples of further suitable applications include components that allow light (ultraviolet, visible, infrared, X-ray, laser, etc.) to pass through.
  • Examples include display peripheral members and UV ink for 3D printing. More specific examples include flat panel displays and their sealing materials; peripheral materials for liquid crystal display devices (light guide plates, prism sheets, polarizing plates, retardation plates, viewing angle correction films, front glass protective films in the liquid crystal display field) (polarizer protective film or adhesive, adhesive or filler between panels or films, liquid crystal film, etc.); encapsulant for color PDP (plasma display), antireflection film, optical correction film, front glass protective film or adhesives, adhesives or fillers between panels or films; molding materials for light-emitting elements used in light-emitting diode display devices, encapsulants for light-emitting diodes (LEDs), protective films or adhesives for front glass, panels or Adhesives or fillers between films; light guide plates, prism sheets, polarizing plates, retardation viewing angle correction films, polar
  • One embodiment of the present invention may include the following configuration.
  • a (meth)acrylic polymer (A) having an average of 0.8 or more groups represented by the general formula (1) per molecule at the end of the molecule, and an epoxy compound and/or an oxetane compound A cured product obtained by curing a curable composition containing (B), a photoradical initiator (C), and an epoxy curing agent (D), and having a film thickness of 200 ⁇ m or less.
  • R 1 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
  • R 1 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
  • the (meth)acrylic polymer (A) has an average of 0.8 to 1 group represented by the general formula (1) per molecule at one end of the molecule (meth)
  • ⁇ 4> The cured product according to any one of ⁇ 1> to ⁇ 3>, wherein the epoxy compound and/or oxetane compound (B) is an aromatic epoxy compound.
  • ⁇ 5> The cured product according to any one of ⁇ 1> to ⁇ 4>, wherein the epoxy curing agent (D) is an amine compound.
  • the epoxy curing agent (D) is an amine compound.
  • An article comprising the cured product according to any one of ⁇ 1> to ⁇ 5>.
  • ⁇ 7> A printed wiring board coated with the cured product according to any one of ⁇ 1> to ⁇ 5>.
  • the film thickness of the cured product obtained by curing is 200 ⁇ m or less, A method of relieving internal stress in the cured product.
  • -OC(O)C(R 1 ) CH 2 (1) (In the formula, R 1 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.)
  • an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel.
  • the reaction solution was heated and stirred for several hours while maintaining the system temperature at about 80 to about 90° C. to bring the polymerization catalyst into contact with oxygen.
  • Acetonitrile and unreacted monomers were removed by devolatilization under reduced pressure to obtain a (meth)acrylic polymer.
  • the obtained (meth)acrylic polymer was colored dark green.
  • the (meth)acrylic polymer obtained in the polymerization step was diluted with butyl acetate (approximately 100 parts by weight per 100 parts by weight of the (meth)acrylic polymer).
  • a filter aid was added to the diluted solution, heat treated, and filtered.
  • Adsorbents (Kyoward(R) 700SEN and Kyoward(R) 500SH) were added to the filtrate and filtered again to obtain a clear liquid. This clear liquid was concentrated to obtain an almost colorless and transparent purified product.
  • (Acryloyl group introduction step) The (meth)acrylic polymer obtained as a purified product was dissolved in N,N-dimethylacetamide (approximately 100 parts by weight per 100 parts by weight of the (meth)acrylic polymer). Potassium acrylate (approximately 2 molar equivalents relative to the Br group at the end of the polymer), a heat stabilizer (4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl), and an adsorbent (Kyoward). (registered trademark) 700SEN) was added thereto, and the mixture was heated and stirred at about 70°C for several hours.
  • the number average molecular weight of the (meth)acrylic polymer (A-1) was approximately 23,000, and the molecular weight distribution was 1.1.
  • the average number of acryloyl groups introduced into the polymer was about 1.9 per molecule.
  • the number of functional groups introduced per molecule of the (meth)acrylic polymer was calculated based on the concentration analysis by 1 H-NMR and the number average molecular weight determined by GPC.
  • 1 H-NMR was measured using Bruker ASX-400 at 23° C. using deuterated chloroform as a solvent. The same applies to Synthesis Examples 2 and 3.
  • the reaction solution was heated and stirred for several hours while maintaining the system temperature at about 80 to about 90° C. to bring the polymerization catalyst into contact with oxygen.
  • Acetonitrile and unreacted monomers were removed by devolatilization under reduced pressure to obtain a (meth)acrylic polymer.
  • the (meth)acrylic polymer was colored dark green.
  • the (meth)acrylic polymer obtained in the polymerization step was diluted with butyl acetate (approximately 100 parts by weight per 100 parts by weight of the (meth)acrylic polymer).
  • a filter aid was added to the diluted solution, heat treated, and filtered.
  • Adsorbents (Kyoward(R) 700SEN and Kyoward(R) 500SH) were added to the filtrate and filtered again to obtain a clear liquid. This clear liquid was concentrated to obtain an almost colorless and transparent purified product.
  • (Acryloyl group introduction step) The (meth)acrylic polymer obtained as a purified product was dissolved in N,N-dimethylacetamide (approximately 100 parts by weight per 100 parts by weight of the (meth)acrylic polymer). Potassium acrylate (approximately 2 molar equivalents relative to the terminal Br group of the (meth)acrylic polymer), a heat stabilizer (4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl), and An adsorbent (Kyoward (registered trademark) 700SEN) was added, and the mixture was heated and stirred at about 70°C for several hours.
  • the number average molecular weight of the (meth)acrylic polymer (A-2) was approximately 16,000, and the molecular weight distribution was 1.1.
  • the average number of acryloyl groups introduced into the polymer was about 1.9 per molecule.
  • n-butyl acrylate During the dropwise addition of n-butyl acrylate, 0.68 parts by weight of pentamethyldiethylenetriamine was added in portions. When the polymerization reaction rate reaches 96%, acetonitrile and unreacted monomers are removed by devolatilization at 80°C, and a polyester having a bromine group at one end with a number average molecular weight of 11,800 and a molecular weight distribution of 1.08 is produced. (n-butyl acrylate) (polymer (P-1)) was obtained.
  • polymer (P-1) 100 parts by weight of polymer (P-1)
  • a filter aid Radiolite 900, manufactured by Showa Kagaku Kogyo Co., Ltd.
  • methylcyclohexane 100 parts by weight of methylcyclohexane
  • the (meth)acrylic polymer (A-3) had a number average molecular weight of 12,200 and a molecular weight distribution of 1.18.
  • the average number of acryloyl groups introduced into the (meth)acrylic polymer (A-3) was 0.87 per molecule.
  • Samples for physical property evaluation were prepared by the following method.
  • Each component blended into the curable composition is as follows.
  • Example 1 The aluminum base material cut above was exposed to the atmosphere using a UV irradiation device (manufactured by Fusion UV System, model: LIGHT HAMMER 6, light source: mercury lamp, peak illuminance: 250 mW/cm 2 , integrated light amount: 2,000 mJ/cm 2 ). irradiated with UV light at the bottom. Next, the mixture was heated in an oven at 120° C. for 60 minutes, and then sufficiently cooled to obtain a cured product.
  • a UV irradiation device manufactured by Fusion UV System, model: LIGHT HAMMER 6, light source: mercury lamp, peak illuminance: 250 mW/cm 2 , integrated light amount: 2,000 mJ/cm 2 .
  • Examples 3 to 6, Comparative Examples 4 to 7 The aluminum base material cut above was heated in an oven at 80° C. for 20 minutes. Next, after irradiating with UV light under the same conditions as in Example 1, heating was performed in an oven at 120° C. for 60 minutes, and the product was sufficiently cooled to obtain a cured product.
  • Example 2 Comparative Examples 2 and 3
  • the aluminum base material cut above was irradiated with UV light in the atmosphere using a UV irradiation device (peak illuminance: 250 mW/cm 2 , cumulative light amount: 2,000 mJ/cm 2 ).
  • Example 1 had a lower internal stress. That is, it was confirmed that the cured product according to one embodiment of the present invention alleviates the internal stress of the cured product. Furthermore, from Comparative Example 1, it was confirmed that the smaller the sample thickness, the larger the internal stress.
  • Example 2 and Comparative Example 3 when comparing Example 2 and Comparative Example 3 with a sample thickness of 90 ⁇ m, it was confirmed that the internal stress of Example 2 was reduced. Further, Comparative Example 2, in which the sample thickness was more than 200 ⁇ m, had an internal stress at the same level as Comparative Example 3, which had a sample thickness of 193 ⁇ m. That is, it was confirmed that when the sample thickness exceeded 200 ⁇ m, the internal stress did not decrease even when the (meth)acrylic polymer (A) was added. Therefore, it was suggested that when the film thickness of the cured product is 200 ⁇ m or less, the addition of the (meth)acrylic polymer (A) relieves the internal stress of the cured product and improves the impact resistance of the cured product. .
  • test piece for three-point bending test The curable composition was poured into a Teflon (registered trademark) mold having a width of 10 mm, a length of 100 mm, and a depth of 2 mm, and heated in an oven at 80° C. for 20 minutes. Next, UV light was irradiated in the atmosphere using a UV irradiation device (peak illuminance: 250 mW/cm 2 , cumulative light amount: 2,000 mJ/cm 2 ). Thereafter, a test piece for a three-point bending test was obtained by heating at 150° C. for 60 minutes in an oven.
  • a Teflon registered trademark
  • Table 8 shows the compositions of Reference Examples 1 to 3 and Comparative Example 8, and the evaluation results of the three-point bending test.
  • Table 8 shows that Reference Examples 1 to 3 are superior to Comparative Example 8 in flexural modulus, maximum stress, and strain at break. Among them, it can be seen that a cured product using a (meth)acrylic polymer having a group represented by the above general formula (1) at one end of the molecule (Reference Example 3) exhibits more excellent physical properties.
  • the bending elastic modulus, maximum point stress, and breaking point strain are calculated using calculation formulas that take into account the film thickness of the sample, and such calculation methods are common in the technical field. Therefore, it is thought that comparable calculation results can be obtained even when measuring samples with different film thicknesses.
  • the film thickness is about 2 mm, but even when the film thickness is 200 ⁇ m or less, calculation results comparable to those when the film thickness is about 2 mm can be obtained. It is presumed that the reference example is superior to the comparative example in flexural modulus, maximum stress, and strain at break.
  • One embodiment of the present invention can be utilized in the field of cured products.

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Abstract

Le but de la présente invention est de fournir un produit durci ayant une excellente résistance aux chocs. Un produit durci selon un mode de réalisation de la présente invention est obtenu par durcissement d'une composition durcissable contenant un polymère (méth)acrylique (A) ayant, aux bornes de la molécule, un groupe de formule générale (1) en nombre moyen d'au moins 0,8 par molécule, un composé époxy et/ou un composé oxétane (B), un initiateur photo-radical (C), et un agent de durcissement époxy (D), et présente une épaisseur inférieure ou égale à 200 μm. (1) : -OC(O)C(R1)=CH2 (dans la formule, R1 représente un atome d'hydrogène ou un groupe organique présentant de 1 à 20 atomes de carbone).
PCT/JP2023/028212 2022-08-16 2023-08-02 Produit durci, article pourvu d'un produit durci et procédé de diminution de la contrainte interne d'un produit durci WO2024038761A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005092981A1 (fr) * 2004-03-26 2005-10-06 Kaneka Corporation Composition vulcanisable à la fois par photocuisson radicalaire et photocuisson cationique
WO2007077888A1 (fr) * 2005-12-28 2007-07-12 Kaneka Corporation Composition durcissable
JP2023073098A (ja) * 2021-11-15 2023-05-25 株式会社カネカ 硬化性組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005092981A1 (fr) * 2004-03-26 2005-10-06 Kaneka Corporation Composition vulcanisable à la fois par photocuisson radicalaire et photocuisson cationique
WO2007077888A1 (fr) * 2005-12-28 2007-07-12 Kaneka Corporation Composition durcissable
JP2023073098A (ja) * 2021-11-15 2023-05-25 株式会社カネカ 硬化性組成物

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