TW202118809A - Photo-curing resin composition for electronic device having excellent coating characteristic and curability and low dielectric constant - Google Patents

Abstract

Disclosed is a photo-curing resin composition for electronic device with excellent coating characteristic and curability and low dielectric constant. The photo-curing resin composition for electronic device of the invention comprises a curable resin and a polymerization initiator. The curable resin contains a monofunctional cationic polymerizable compound and a polyfunctional cationic polymerizable compound, and the aforementioned monofunctional cationic polymerizable compound includes at least any one of a monofunctional aliphatic cationic polymerizable compound and a monofunctional cationic polymerizable compound with substituted phenoxy group. The photo-curing resin composition for electronic device has a dielectric constant of 3.5 or less when measured at 25 DEG C and 100 kHz.

Description

Light-curing resin composition for electronic devices

The present invention relates to a photocurable resin composition for electronic devices that has excellent coating properties and curability and has a low dielectric constant.

In recent years, curable resin compositions for electronic devices used as adhesives for touch panels, solder resists for circuit boards, etc. require materials that have moderate viscosity, are excellent in coatability, and have photocurability.

Touch panels are used in electronic devices such as mobile phones, smart phones, car navigation systems, and personal computers. Among them, electrostatic capacitive touch panels are rapidly spreading due to their excellent functionality. The electrostatic capacitive touch panel is generally composed of a cover plate, an adhesive layer, and a substrate stack. For the above-mentioned adhesive layer, transparency and excellent adhesion to the adherend are required. As such an adhesive layer, for example, Patent Document 1 discloses an adhesive layer containing a (meth)acrylic polymer obtained by polymerizing a specific monomer component.

On the other hand, a circuit board generally has a circuit formed by a wiring pattern formed on a substrate made of an insulating material, and the outermost surface is for the purpose of protecting the circuit and insulating the outside of the circuit. Covered by a protective film. In addition, by using solder resist, when installing parts or making connections with external wiring, etc., it is possible to prevent solder bridges that cause short circuits due to the adhesion of solder between the wirings. As the solder resist is disclosed in Patent Document 2, for example, a curable resin composition having photosensitivity is used for pattern formation. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2014-034655 Patent Document 2: Japanese Patent Laid-Open No. 08-259663

[The problem to be solved by the invention]

In recent years, with the thinning and larger size of capacitive touch panels, in order not to reduce the response speed of the touch panel, the curable resin composition used in the adhesive layer is further required to have a low dielectric constant , Low dielectric loss tangent and other dielectric properties. On the other hand, the curable resin used in the curable resin composition disclosed in Patent Document 2 has the following problem: since it has polar groups such as acid groups in order to impart photosensitivity, the dielectric constant and the dielectric loss tangent become high. As a result, when a high-frequency voltage is applied to the circuit, transmission delay or signal loss occurs. In addition, as a method for easily and efficiently forming a fine solder resist pattern, a method of forming a solder resist pattern by a printing method is implemented. However, conventional curable resin compositions have a printing method that is particularly suitable for inkjet methods and the like. In the case of the coating property, there is a problem that it becomes difficult to reduce the dielectric constant and the dielectric loss tangent. The object of the present invention is to provide a photocurable resin composition for electronic devices that is excellent in coating properties and curability and has a low dielectric constant. [Technical means to solve the problem]

The present invention is a photocurable resin composition for electronic devices, which contains a curable resin and a polymerization initiator, and the curable resin includes a monofunctional cationically polymerizable compound and a polyfunctional cationically polymerizable compound, and the above-mentioned monofunctional cation polymerizes The sexual compound includes at least any one of a monofunctional aliphatic cationic polymerizable compound and a monofunctional cationic polymerizable compound having a phenoxy group that can be substituted. The photocurable resin composition for electronic devices is heated at 25°C and 100°C. The dielectric constant measured under the condition of kHz is 3.5 or less. Hereinafter, the present invention will be described in detail.

The inventors of the present invention found that by using a combination of a monofunctional cationically polymerizable compound having a specific structure and a polyfunctional cationically polymerizable compound as a curable resin, electrons with excellent coating properties and curability and a low dielectric constant can be obtained. The photocurable resin composition for devices has completed the present invention.

The photocurable resin composition for electronic devices of the present invention contains a curable resin. The said curable resin contains a monofunctional cationically polymerizable compound. The monofunctional cationically polymerizable compound includes a monofunctional aliphatic cationically polymerizable compound and a monofunctional cationically polymerizable compound having a phenoxy group that can be substituted (hereinafter, also referred to as "phenoxy-containing monofunctional cationically polymerizable compound" Compound") at least any one of them. By containing at least any one of a monofunctional aliphatic cationic polymerizable compound and a phenoxy group-containing monofunctional cationic polymerizable compound as the monofunctional cationic polymerizable compound, the photocurable electronic device of the present invention The resin composition has excellent coatability and a low dielectric constant.

The monofunctional cationically polymerizable compound has one cationically polymerizable group in one molecule. Examples of the cationically polymerizable group possessed by the monofunctional cationically polymerizable compound include an epoxy group, an oxetanyl group, and a vinyl ether group. Among them, epoxy group and oxycyclobutyl group are preferred.

The above-mentioned monofunctional aliphatic cationically polymerizable compound has an aliphatic skeleton. The monofunctional aliphatic cationically polymerizable compound may have only a linear or branched aliphatic skeleton as the aliphatic skeleton, or may have a cyclic aliphatic skeleton as the aliphatic skeleton.

In the above-mentioned phenoxy-containing monofunctional cationically polymerizable compound, examples of the substituent when the above-mentioned phenoxy group is substituted include linear or branched alkyl groups having 1 to 18 carbon atoms, and straight Chain or branched alkenyl group with 2 or more and 18 or less carbon atoms, etc.

Specifically, the monofunctional cationically polymerizable compound preferably includes a compound selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and the following formula (1-3) The compound represented by the following formula (1-4), the compound represented by the following formula (1-5), the compound represented by the following formula (1-6), the compound represented by the following formula (1- 7) At least one of the compound represented by the compound represented by the following formula (1-8), and the compound represented by the following formula (1-9).

The lower limit of the content of the monofunctional cationically polymerizable compound in 100 parts by weight of the curable resin is preferably 20 parts by weight, and the upper limit is preferably 90 parts by weight. When the content of the monofunctional cationically polymerizable compound is in this range, the obtained photocurable resin composition for electronic devices maintains excellent curability, more excellent coatability, and a lower dielectric constant. The lower limit of the content of the monofunctional cationically polymerizable compound is more preferably 30 parts by weight, and the upper limit is more preferably 70 parts by weight.

The said curable resin contains a polyfunctional cationically polymerizable compound. By containing the above-mentioned polyfunctional cationically polymerizable compound, the photocurable resin composition for electronic devices of the present invention has excellent curability.

The above-mentioned polyfunctional cationically polymerizable compound has two or more cationically polymerizable groups in one molecule. The cationic polymerizable group possessed by the polyfunctional cationically polymerizable compound may be the same as the cationic polymerizable group possessed by the monofunctional cationically polymerizable compound. Among them, epoxy group and oxycyclobutyl group are preferred.

The above-mentioned polyfunctional cationically polymerizable compound is preferably selected from the group that does not have a polysiloxane skeleton in terms of the obtained photocurable resin composition for electronic devices that maintains a low dielectric constant and is more excellent in curability. Functional alicyclic epoxy compound, polyfunctional aliphatic glycidyl ether compound without polysiloxane skeleton, polyfunctional oxycyclobutane compound without polysiloxane skeleton, and having 2 or more cationic polymerizable groups At least one of the group consisting of polysiloxane compounds.

The above-mentioned polyfunctional alicyclic epoxy compound (hereinafter, also referred to simply as "multifunctional alicyclic epoxy compound") which does not have a polysiloxane skeleton has an alicyclic epoxy group. The above-mentioned polyfunctional alicyclic epoxy compound may have two or more of the above alicyclic epoxy groups in one molecule, or may have one of the above alicyclic epoxy groups and one or more non-alicyclic epoxy groups in one molecule Epoxy. As said alicyclic epoxy group, epoxycyclohexyl etc. are mentioned.

Specific examples of the polyfunctional alicyclic epoxy compound include: a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and the following formula (2) -3) The compound represented by the following formula (2-4), 1,2,8,9-diepoxylimonene, etc. Among them, it is preferably selected from a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), a compound represented by the following formula (2-3), and the following formula (2-4) At least one of the group consisting of the compound represented, more preferably the compound represented by the following formula (2-1), and still more preferably 3,4,3',4'-two Epoxy bicyclohexane.

In the formula (2-1), R ¹ to R ¹⁸ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each of which may be the same or may different. In the formula (2-2), R ¹⁹ to R ³⁰ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each of which may be the same or may different. In the formula (2-3), R ³¹ to R ⁴⁸ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each of which may be the same or may different. In the formula (2-4), R ⁴⁹ to R ⁶⁶ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each of which may be the same or may different.

The compound represented by the above formula (2-1), the compound represented by the above formula (2-2), the compound represented by the above formula (2-3), and the compound represented by the above formula (2-4) can be, for example It is manufactured by the method disclosed in Japanese Patent No. 5226162, Japanese Patent No. 5979631, etc.

Examples of commercially available compounds among the compounds represented by the above formula (2-1) include Celloxide 8000 (manufactured by Daicel). As a commercially available one among the compounds represented by the above formula (2-2), for example, THI-DE (manufactured by JXTG NIPPON OIL & ENERGY) and the like can be cited. As a commercially available one among the compounds represented by the above formula (2-3), for example, DE-102 (manufactured by JXTG NIPPON OIL & ENERGY) and the like can be cited. As a commercially available one among the compounds represented by the above formula (2-4), for example, DE-103 (manufactured by JXTG NIPPON OIL & ENERGY) and the like can be cited.

The above-mentioned polyfunctional aliphatic glycidyl ether compound (hereinafter, also referred to simply as "polyfunctional aliphatic glycidyl ether compound") which does not have a polysiloxane skeleton has an aliphatic skeleton. The polyfunctional aliphatic glycidyl ether compound may have only a linear or branched aliphatic skeleton as the aliphatic skeleton, or may have a cyclic aliphatic skeleton as the aliphatic skeleton.

As the above-mentioned polyfunctional aliphatic glycidyl ether compound, specifically, for example, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, Methanol Diglycidyl Ether, Tricyclodecanediol Diglycidyl Ether, etc.

As the above-mentioned polyfunctional oxycyclobutane compound having no polysiloxane skeleton (hereinafter, also simply referred to as "polyfunctional oxycyclobutane compound"), specifically, for example, 3-ethyl-3-(( (3-Ethyloxetane-3-yl)methoxy)methyl)oxetane, 1,4-bis(((3-ethyloxetane-3-yl)methoxy) ) Methyl)benzene, bis((3-ethyloxybutan-3-yl)methyl)isophthalate and the like.

Examples of the polysiloxane compound having two or more cationically polymerizable groups include: a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5) The compound and so on.

In formula (3), R ⁶⁷ each independently represents an alkyl group with a carbon number of 1 or more and 10 or less, R ⁶⁸ each independently represents a bonding bond or an alkylene group with a carbon number of 1 or more and 6 or less, and X represents an epoxy containing A group containing an oxocyclobutyl group, or a group containing a vinyl ether group, n represents an integer of 0 to 1000.

In formula (4), R ⁶⁹ each independently represents an alkyl group with a carbon number of 1 or more and 10 or less, R ⁷⁰ represents a bonding bond or an alkylene group with a carbon number of 1 or more and 6 or less, and R ⁷¹ each independently represents the carbon number 1 or more and 10 or less alkyl group, epoxy group-containing group, oxycyclobutyl group-containing group, or vinyl ether group-containing group, X represents epoxy group-containing group, oxcyclobutyl group-containing group, or Contains vinyl ether groups. l represents an integer from 0 to 1000, and m represents an integer from 1 to 100. However, when R ⁷¹ is an alkyl group having 1 or more and 10 or less carbon atoms, m represents an integer of 2 or more and 100 or less.

In formula (5), R ⁷² each independently represents an alkyl group having 1 or more and 10 or less carbon atoms, an epoxy group-containing group, an oxocyclobutyl group-containing group, or a vinyl ether group-containing group, 2k R ⁷² Among them, at least two R ⁷² represent an epoxy group-containing group, an oxocyclobutyl group-containing group, or a vinyl ether group-containing group. k represents an integer of 3 or more and 6 or less.

As X in the above formula (3), R ⁷¹ and X in the above formula (4), and the above ^{epoxy group-containing group in R 72} in the above formula (5), preferably the following formula (6 -1) or (6-2). As X in the above formula (3), R ⁷¹ and X in the above formula (4), and the above oxycyclobutyl group-containing group ^{in R 72} in the above formula (5), the following formula ( 7) The base expressed. As X in the above formula (3), R ⁷¹ and X in the above formula (4), and the above ^{vinyl ether group-containing group in R 72} in the above formula (5), preferably the following formula (8 ) Represents the base.

In the formulas (6-1) and (6-2), R ⁷³ represents a bonding bond or an alkylene group having a carbon number of 1 or more and 6 or less that may have an oxygen atom, and * represents a bonding position.

In the formula (7), R ⁷⁴ represents a bonding bond or an alkylene group with 1 to 6 carbon atoms that may have an oxygen atom, R ⁷⁵ represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and * represents Bond position.

In the formula (8), R ⁷⁶ represents a bonding bond or an alkylene group having a carbon number of 1 or more and 6 or less that may have an oxygen atom, and * represents a bonding position.

The polyfunctional cationically polymerizable compound preferably includes a compound selected from the group consisting of the compound represented by the above formula (2-1), the compound represented by the above formula (2-2), the compound represented by the above formula (2-3), and the above At least one of the compound represented by the formula (2-4), the compound represented by the above formula (3), the compound represented by the above formula (4), and the compound represented by the above formula (5) . In particular, in terms of the obtained photocurable resin composition for electronic devices that can further reduce the dielectric constant and is more excellent in low outgassing properties, the above-mentioned polyfunctional cationically polymerizable compound preferably contains one selected from the above-mentioned formula (3) At least one of the group consisting of the compound represented by the above formula (4), and the compound represented by the above formula (5).

The lower limit of the content of the polyfunctional cationically polymerizable compound in 100 parts by weight of the curable resin is preferably 10 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the polyfunctional cationically polymerizable compound is in this range, the obtained photocurable resin composition for electronic devices maintains excellent coatability and low dielectric constant, and has more excellent curability. The lower limit of the content of the polyfunctional cationic polymerizable compound is more preferably 30 parts by weight, and the upper limit is more preferably 70 parts by weight.

The ratio of the monofunctional cationically polymerizable compound to the aforementioned polyfunctional cationically polymerizable compound (monofunctional cationically polymerizable compound: polyfunctional cationically polymerizable compound) is preferably 1:9 to 9:1 in terms of weight ratio. When the ratio of the above-mentioned monofunctional cationically polymerizable compound to the above-mentioned polyfunctional cationically polymerizable compound is in this range, the obtained resin composition for electronic devices maintains a low dielectric constant and suppresses damage or release to components, etc. Those with better reliability due to the generation of qi. The ratio of the monofunctional cationic polymerizable compound to the polyfunctional cationic polymerizable compound is more preferably 3:7 to 7:3.

The above-mentioned curable resin may be included in the range not impairing the purpose of the present invention for the purpose of improving coatability by viscosity adjustment, etc., in addition to the above-mentioned monofunctional cationically polymerizable compound and the above-mentioned polyfunctional cationically polymerizable compound, Other hardening resins. As said other curable resin, (meth)acrylic compound etc. are mentioned. In addition, in this specification, the above-mentioned "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and the "(meth)acrylic compound" refers to a compound having a (meth)acrylic acid group. The so-called "(form) "Acrylic)" refers to acryloyl or methacryloyl.

Examples of the (meth)acrylic compound include: glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth) Acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, benzyl (meth)acrylate, trimethylolpropane Tri(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, lauryl (meth)acrylate, (meth)acrylic modified silicone oil, etc. These (meth)acrylic compounds may be used alone or in combination of two or more kinds. In addition, in this specification, the said "(meth)acrylate" means acrylate or methacrylate.

The lower limit of the content of the other curable resin in 100 parts by weight of the curable resin is preferably 5 parts by weight, and the upper limit is preferably 30 parts by weight. When the content of the above-mentioned other curable resin is in this range, the obtained photocurable resin composition for electronic devices is more excellent in effects such as improvement of coating properties without deteriorating dielectric properties and the like. The lower limit of the content of the above-mentioned other curable resin is more preferably 10 parts by weight, and the upper limit is more preferably 20 parts by weight.

The photocurable resin composition for electronic devices of the present invention contains a polymerization initiator. As the above-mentioned polymerization initiator, a photocationic polymerization initiator can be suitably used. In addition, when the (meth)acrylic resin is contained as the other curable resin, the photocationic polymerization initiator and the photoradical polymerization initiator may be used in combination as the polymerization initiator. Furthermore, a thermal cationic polymerization initiator or a thermal radical polymerization initiator can also be used in the range which does not impair the objective of this invention.

The photocationic polymerization initiator is not particularly limited as long as it generates a protic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

Examples of the ionic photoacid generator type photo cationic polymerization initiator of the anionic moiety include, for _{^{example: BF 4 -, PF 6 -}} , SbF 6 -, (BX 4) - ( wherein, X represents at least two of the above via Fluorine or trifluoromethyl substituted phenyl) etc. And, as the anionic moiety, may include _{PF m (C n F 2n +} 1) 6-m - ( wherein, m is an integer of 0 or more and 5 or less of, n-1 or more and an integer of 6 or less) and the like. As the ionic photoacid generating type photocationic polymerization initiator, for example, aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4- Cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt and the like.

As the above-mentioned aromatic sulfide salt, for example, bis(4-(diphenylaunyl)phenyl) sulfide bishexafluorophosphate, bis(4-(diphenylaunyl)phenyl) sulfide bis Hexafluoroantimonate, bis(4-(diphenylarunyl)phenyl) sulfide bistetrafluoroborate, bis(4-(diphenylarunyl)phenyl) sulfide tetrakis(pentafluorophenyl) )Borate, 4-(phenylthio)phenyl diphenyl hexafluorophosphate, 4-(phenylthio) phenyl diphenyl hexafluoroantimonate, 4-(phenylthio) phenyl Diphenyl alumium tetrafluoroborate, 4-(phenylthio)phenyl diphenyl alumium tetrakis (pentafluorophenyl) borate, triphenyl alumium hexafluorophosphate, triphenyl alumium hexafluoroantimonate , Triphenyl arunnium tetrafluoroborate, triphenyl arunnium tetrakis (pentafluorophenyl) borate, bis(4-(bis(4-(2-hydroxyethoxy))phenylarunnyl)phenyl) Sulfide bishexafluorophosphate, bis(4-(bis(4-(2-hydroxyethoxy))phenylaunyl)phenyl)thioether bishexafluoroantimonate, bis(4-(bis( 4-(2-Hydroxyethoxy))Phenylalanyl)phenyl)sulfide bistetrafluoroborate, Bis(4-(Bis(4-(2-hydroxyethoxy))phenylalanyl) Phenyl) sulfide tetrakis(pentafluorophenyl) borate, tris(4-(4-acetylphenyl)thienyl) sulfide tetrakis(pentafluorophenyl) borate and the like.

As the above-mentioned aromatic iodonium salt, for example, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrakis (pentafluorophenyl) Borate, bis(dodecylphenyl) hexafluorophosphate, bis(dodecylphenyl) hexafluoroantimonate, bis(dodecylphenyl) tetrafluoroborate, double (Dodecylphenyl) tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4-(1-methylethyl)phenyl hexafluorophosphate, 4-methylphenyl -4-(1-Methylethyl)phenylphosphonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenylphosphonium tetrafluoroborate, 4-methylbenzene 4-(1-methylethyl)phenylphosphonium tetrakis(pentafluorophenyl)borate and the like.

Examples of the above-mentioned aromatic diazonium salt include: phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrafluoroborate. (Pentafluorophenyl) borate and the like.

As the above-mentioned aromatic ammonium salt, for example, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2 -Cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl) borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate , 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate and the like.

As the above-mentioned (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (2,4-cyclopentadien-1-yl)( (1-methylethyl)benzene)-Fe(II)hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) Hexafluoroantimonate, (2,4-cyclopentadien-1-yl) ((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadiene) -1-yl)((1-methylethyl)benzene)-Fe(II)tetra(pentafluorophenyl)borate and the like.

Examples of the nonionic photo-acid-generating photocationic polymerization initiator include: nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonate, diazonaphthoquinone, and N-hydroxyimide sulfonate Acid esters and so on.

Examples of commercially available photo-cationic polymerization initiators include: the photo-cationic polymerization initiator manufactured by Green Chemical Company, the photo-cationic polymerization initiator manufactured by Union Carbon, and the photo-cationic polymerization initiator manufactured by ADEKA. Initiator, photo-cationic polymerization initiator manufactured by 3M, photo-cationic polymerization initiator manufactured by BASF, photo-cationic polymerization initiator manufactured by Rhodia, etc. As the photocationic polymerization initiator manufactured by the aforementioned Green Chemical Company, for example, DTS-200 and the like can be cited. As the photocationic polymerization initiator manufactured by the above-mentioned Union Carbon Compounds, for example, UVI6990, UVI6974, etc. can be cited. Examples of the photocationic polymerization initiator manufactured by ADEKA include SP-150 and SP-170. As the photocationic polymerization initiator manufactured by 3M, for example, FC-508, FC-512, etc. can be cited. Examples of the photocationic polymerization initiator manufactured by BASF include IRGACURE261, IRGACURE290 and the like. As the photocationic polymerization initiator manufactured by Rhodia, for example, PI2074 and the like can be cited.

系化合物等。Examples of the aforementioned photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, phosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, Diphenyl ethylenedione, 9-oxysulfur

Department of compounds and so on.

Examples of commercially available photo-radical polymerization initiators include: a photo-radical polymerization initiator manufactured by BASF Corporation, a photo-radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd., and the like. Examples of the photoradical polymerization initiator manufactured by BASF include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, Lucirin TPO, and the like. As the photo-radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd., for example, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like can be cited.

As the thermal cationic polymerization initiator, the anionic moiety include _{^{BF 4 -, PF 6 -,}} SbF 6 -, or (BX ₄₎ ^- (wherein, X is substituted by at least two of fluoro or trifluoromethyl Phenyl) sulfonium salt, phosphonium salt, ammonium salt, etc. Among them, sulfonium salt and ammonium salt are preferred.

Examples of the above-mentioned sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and the like.

As said phosphonium salt, ethyl triphenyl phosphonium hexafluoroantimonate, tetrabutyl phosphonium hexafluoroantimonate, etc. are mentioned.

As the above-mentioned ammonium salt, for example, dimethylphenyl(4-methoxybenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methoxybenzyl)ammonium hexafluoroantimonate, Dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl)borate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorophosphate, dimethylphenyl( 4-methylbenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorotetra(pentafluorophenyl)borate, methylphenyldibenzylammonium hexafluoro Phosphate, methyl phenyl dibenzyl ammonium hexafluoroantimonate, methyl phenyl dibenzyl ammonium tetra (pentafluorophenyl) borate, phenyl tribenzyl ammonium tetra (pentafluorophenyl) borate , Dimethylphenyl(3,4-dimethylbenzyl)ammonium tetra(pentafluorophenyl)borate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzylpyridine Onium trifluoromethanesulfonic acid and so on.

As a commercially available one among the above-mentioned thermal cationic polymerization initiators, for example, a thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd., a thermal cationic polymerization initiator manufactured by King Industries, etc. can be cited. As the thermal cationic polymerization initiator manufactured by Sanxin Chemical Industry Co., Ltd., for example, San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, San-Aid Aid SI-B4 and so on. As the thermal cationic polymerization initiator manufactured by the above-mentioned King Industries, for example, CXC1612, CXC1821, and the like can be cited.

Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides, and the like. As said azo compound, 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, etc. are mentioned, for example. Examples of the above-mentioned organic peroxide include: benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxide Oxidized dicarbonate and so on.

Examples of commercially available thermal radical polymerization initiators include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, V-501 (all of which are from FUJIFILM WAKO PURE CHEMICAL) Manufacturing) and so on.

The content of the polymerization initiator relative to 100 parts by weight of the curable resin has a preferred lower limit of 0.01 parts by weight and a preferred upper limit of 10 parts by weight. When the content of the polymerization initiator is 0.01 parts by weight or more, the obtained photocurable resin composition for electronic devices is more excellent in curability. The content of the polymerization initiator is 10 parts by weight or less, so that the curing reaction of the obtained photocurable resin composition for electronic devices does not become too fast, and the workability is more excellent, and the cured product can be changed. To be more even. The lower limit of the content of the polymerization initiator is more preferably 0.05 parts by weight, and the upper limit is more preferably 5 parts by weight.

The photocurable resin composition for electronic devices of the present invention may contain a sensitizer. The above-mentioned sensitizer has the effect of further improving the polymerization initiation efficiency of the above-mentioned polymerization initiator and further promoting the curing reaction of the photocurable resin composition for electronic devices of the present invention.

系化合物、或2,2-二甲氧基-1,2-二苯乙烷-1-酮、二苯甲酮、2,4-二氯二苯甲酮、鄰苯甲醯苯甲酸甲酯、4,4'-雙(二甲胺基)二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚等。 作為上述9-氧硫

系化合物，例如可列舉：2,4-二乙基9-氧硫

等。Examples of the above-mentioned sensitizer include: 9-oxysulfur

Series compounds, or 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl phthalate , 4,4'-bis(dimethylamino)benzophenone, 4-benzyl-4'-methyl diphenyl sulfide, etc. As the above 9-oxysulfur

Compounds, for example, 2,4-diethyl 9-oxysulfur

Wait.

The content of the sensitizer is preferably 0.01 parts by weight in the lower limit and 3 parts by weight in the upper limit with respect to 100 parts by weight of the curable resin. When the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is further exhibited. When the content of the sensitizer is 3 parts by weight or less, the absorption does not become too large and light can be transmitted to the deep part. The lower limit of the content of the sensitizer is more preferably 0.1 part by weight, and the upper limit is more preferably 1 part by weight.

、N,N'-雙(2-甲基-1-咪唑基乙基)脲、N,N'-(2-甲基-1-咪唑基乙基)-己二醯胺、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4,5-二羥基甲基咪唑等。作為上述酸酐，例如可列舉：四氫鄰苯二甲酸酐、乙二醇雙(脫水偏苯三酸酯)（ethylene glycol bis(anhydrotrimellitate)）等。 該等熱硬化劑可單獨使用，亦可組合2種以上使用。The photocurable resin composition for electronic devices of the present invention may contain a thermosetting agent within a range that does not impair the purpose of the present invention. Examples of the thermosetting agent include hydrazine compounds, imidazole derivatives, acid anhydrides, dicyandiamine, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins. As the above-mentioned hydrazine compound, for example, 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, sebacic acid dihydrazide (sebacic acid dihydrazide), isophthalic acid dihydrazide Dihydrazide (isophthalic acid dihydrazide), adipic acid dihydrazide (adipic acid dihydrazide), malonic acid dihydrazide (malonic acid dihydrazide), etc. Examples of the imidazole derivatives include 1-cyanoethyl-2-benzimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, and 2,4-diamino -6-(2'-Methylimidazolyl-(1'))-ethyl-symmetric three

, N,N'-bis(2-methyl-1-imidazolylethyl)urea, N,N'-(2-methyl-1-imidazolylethyl)-hexamethylenediamide, 2-phenyl -4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. As said acid anhydride, tetrahydrophthalic anhydride, ethylene glycol bis (anhydrotrimellitate), etc. are mentioned, for example. These thermosetting agents may be used alone or in combination of two or more kinds.

As a commercially available one among the above-mentioned thermosetting agents, for example, thermosetting agents manufactured by Otsuka Chemical Co., Ltd., thermosetting agents manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like can be cited. Examples of the thermosetting agent manufactured by the above-mentioned Otsuka Chemical Company include SDH, ADH, and the like. Examples of the thermosetting agent manufactured by Ajinomoto Fine-Techno include Amicure VDH, Amicure VDH-J, and Amicure UDH.

The content of the thermosetting agent relative to 100 parts by weight of the curable resin has a preferred lower limit of 0.5 parts by weight, and a preferred upper limit of 30 parts by weight. When the content of the thermosetting agent is in this range, the obtained photocurable resin composition for electronic devices has more excellent thermosetting properties while maintaining excellent storage stability. The lower limit of the content of the thermal hardening agent is more preferably 1 part by weight, and the upper limit is more preferably 15 parts by weight.

The photocurable resin composition for electronic devices of the present invention may further contain a silane coupling agent. The above-mentioned silane coupling agent has the effect of improving the adhesion of the photocurable resin composition for electronic devices of the present invention to a substrate or the like.

Examples of the silane coupling agent include: 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanate Group propyl trimethoxysilane and so on. These silane compounds may be used alone or in combination of two or more kinds.

The content of the silane coupling agent relative to 100 parts by weight of the curable resin has a preferred lower limit of 0.1 parts by weight and a preferred upper limit of 10 parts by weight. When the content of the silane coupling agent is in this range, the exudation caused by the remaining silane coupling agent is suppressed, and the effect of improving the adhesiveness of the obtained photocurable resin composition for electronic devices is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.5 parts by weight, and the upper limit is more preferably 5 parts by weight.

The photocurable resin composition for electronic devices of the present invention may contain a curing retarder. By containing the above-mentioned curing retarder, the pot life of the obtained photocurable resin composition for electronic devices can be prolonged.

As said hardening retarder, a polyether compound etc. are mentioned, for example. As said polyether compound, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a crown ether compound, etc. are mentioned, for example. Among them, a crown ether compound is preferred.

With respect to 100 parts by weight of the curable resin, the content of the hardening retarder preferably has a lower limit of 0.05 parts by weight, and a preferable upper limit of 5.0 parts by weight. When the content of the curing retarder is within this range, it is possible to suppress outgassing when the obtained photocurable resin composition for electronic devices is cured, and to further exhibit the retardation effect. The lower limit of the content of the hardening retarder is more preferably 0.1 parts by weight, and the upper limit is more preferably 3.0 parts by weight.

The photocurable resin composition for electronic devices of the present invention may further contain a surface modifier within a range that does not impair the purpose of the present invention. By containing the above-mentioned surface modifier, the flatness of the coating film can be imparted to the photocurable resin composition for electronic devices of the present invention. As said surface modifier, surfactant, a leveling agent, etc. are mentioned, for example.

Examples of the above-mentioned surface modifier include surface modifiers such as polysiloxane-based, acrylic-based, and fluorine-based surface modifiers. As a commercially available one among the above-mentioned surface modifiers, for example, a surface modifier manufactured by BYK-Chemie Japan, a surface modifier manufactured by AGC SEIMI CHEMICAL, etc. can be cited. Examples of surface modifiers manufactured by BYK-Chemie Japan include BYK-340, BYK-345, and the like. As the surface modifier manufactured by the aforementioned AGC SEIMI CHEMICAL company, for example, Surflon S-611 and the like can be cited.

The photocurable resin composition for electronic devices of the present invention may also contain a compound or ion exchange resin that reacts with the acid generated in the composition within a range that does not impair the purpose of the present invention.

Examples of the compound that reacts with the acid generated in the composition include acid-neutralized substances, such as carbonates or bicarbonates of alkali metals or alkaline earth metals. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, etc. can be used.

As the ion exchange resin, any of a cation exchange type, an anion exchange type, and an amphoteric ion exchange type can be used, and it is particularly preferably a cation exchange type or an amphoteric ion exchange type capable of adsorbing chloride ions.

Furthermore, the photocurable resin composition for electronic devices of the present invention may optionally contain various known additives such as reinforcing agents, softeners, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants.

As a method of manufacturing the photocurable resin composition for electronic devices of the present invention, for example, the use of a homogenous disperser, homomixer, universal mixer, planetary mixer, kneader, three-roll mill, etc., is used to harden the resin composition. The method of mixing additives such as flexible resin, polymerization initiator and optionally silane coupling agent.

The upper limit of the dielectric constant of the photocurable resin composition for electronic devices of the present invention measured under the conditions of 25° C. and 100 kHz is 3.5. With the above-mentioned dielectric constant being 3.5 or less, the photocurable resin composition for electronic devices of the present invention can be suitably used in adhesives for electronic devices, such as adhesives for touch panels or solder resists for circuit boards, or electronic devices Use coating agent, etc. The preferable upper limit of the above-mentioned dielectric constant is 3.3, and the more preferable upper limit is 3.0. In addition, the above-mentioned dielectric constant has no particularly preferable lower limit, and the substantial lower limit is 2.2. In addition, the above-mentioned "dielectric constant" can be measured using a dielectric constant measuring device.

The photocurable resin composition for electronic devices of the present invention can be suitably used for coating by an inkjet method. The inkjet method may be a non-heated inkjet method or a heated inkjet method. Furthermore, in this specification, the above-mentioned "non-heated inkjet method" is a method for inkjet coating at a coating head temperature of less than 28°C, and the above-mentioned "heated inkjet method" is a method for coating at a temperature above 28°C. Method of inkjet coating at cloth head temperature.

The above-mentioned heating inkjet method uses an inkjet coating head equipped with a heating mechanism. By mounting the inkjet coating head with a heating mechanism, the viscosity and surface tension can be reduced when the photocurable resin composition for electronic devices is ejected.

As the above-mentioned inkjet coating head equipped with a heating mechanism, for example, KM1024 series manufactured by KONICA MINOLTA, or SG1024 series manufactured by FUJIFILM Dimatix, etc. can be cited.

When the photocurable resin composition for electronic devices of the present invention is used for coating by the above-mentioned thermal inkjet method, the heating temperature of the coating head is preferably in the range of 28°C to 80°C. When the heating temperature of the coating head is in this range, the time-dependent viscosity increase of the photocurable resin composition for electronic devices is further suppressed, and the ejection stability is more excellent.

The preferred lower limit of the viscosity of the photocurable resin composition for electronic devices of the present invention at 25°C is 5 mPa·s, and the preferred upper limit is 50 mPa·s. Since the above-mentioned viscosity at 25°C is in this range, coating can be suitably performed by an inkjet method. The lower limit of the viscosity of the photocurable resin composition for electronic devices of the present invention at 25°C is more preferably 8 mPa·s, and even more preferably the lower limit is 10 mPa·s. In addition, the more preferable upper limit of the viscosity of the photocurable resin composition for electronic devices of the present invention at 25°C is 40 mPa·s, and the more preferable upper limit is 30 mPa·s. Furthermore, in this specification, the above-mentioned "viscosity" means the value measured under the conditions of 25°C and 100 rpm using an E-type viscometer. As the E-type viscometer, for example, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.), etc., can be used, and a CP1 type cone plate can be used.

The preferred lower limit of the surface tension of the photocurable resin composition for electronic devices of the present invention at 25°C is 15 mN/m, and the preferred upper limit is 35 mN/m. When the surface tension at 25°C is in this range, coating can be suitably performed by the inkjet method. The lower limit of the surface tension at 25°C is more preferably 20 mN/m, the upper limit is more preferably 30 mN/m, and the lower limit is still 22 mN/m, and the upper limit is 28 mN/m. Furthermore, the above-mentioned surface tension refers to the value measured by the Wilhelmy method using a dynamic wettability tester. As the above-mentioned dynamic wettability tester, for example, WET-6100 type (manufactured by Liske Corporation) and the like can be cited.

The photocurable resin composition for electronic devices of the present invention can be suitably cured by irradiating light with a wavelength of 300 nm or more and 400 nm or less and a cumulative light quantity of ^{300 mJ/cm 2} or more and 3000 mJ/cm ^{2 or less.}

Examples of the light source used for the above light irradiation include: low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, excimer laser, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, sodium lamp, halogen lamp , Xenon lamp, LED lamp, fluorescent lamp, sunlight, electron beam irradiation device, etc. These light sources may be used alone, or two or more types may be used in combination. The light sources are appropriately selected according to the absorption wavelength of the photocationic polymerization initiator or the photoradical polymerization initiator.

As the irradiation means for irradiating light to the photocurable resin composition for electronic devices of the present invention, for example, simultaneous irradiation of various light sources, sequential irradiation with an interval time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. can be used. A means of irradiation.

The photocurable resin composition for electronic devices of the present invention can be suitably used as an adhesive for electronic devices or a coating agent for electronic devices such as an adhesive for touch panels or a solder resist for circuit boards. In addition, the photocurable resin composition for electronic devices of the present invention can also be suitably used as a sealing agent for display elements such as organic EL display elements. [Effects of Invention]

According to the present invention, it is possible to provide a photocurable resin composition for electronic devices that is excellent in coatability and curability and has a low dielectric constant.

Hereinafter, examples are disclosed, and the present invention is further described in detail, but the present invention is not limited to these examples.

(Examples 1 to 22, Comparative Examples 1 to 5) According to the blending ratios described in Tables 1 to 4, a homogeneous dispersion type stirring mixer was used to uniformly stir and mix the materials at a stirring speed of 3000 rpm. In this way, the photocurable resin compositions for electronic devices of Examples 1-22 and Comparative Examples 1-5 were produced. As a homogeneous dispersing type stirring mixer, a homogeneous dispersing machine type L (manufactured by Primix) is used. In Tables 1 to 4, "X-22-169" means that in the above formula (3), R ⁶⁷ is a methyl group, R ⁶⁸ is a bonding bond, and X is a group represented by the above formula (6-2) (R ⁷³ Is ethylene) and n is 0 (average value). In Tables 1 to 4, "X-22-163" means that in the above formula (3), R ⁶⁷ is a methyl group, R ⁶⁸ is a n-propylidene group, and X is a group represented by the above formula (6-1) (R ⁷³ It is a formaldehyde-based) compound. In the Table 1 to 4, "X-40-2678" is the above formula (5) R ⁷² 2 R ⁷² th group is represented by the above formula (6-2) (R ⁷³ is ethyl stretched), the other R ⁷² is a methyl group and k is a compound of 4 (average value).

The obtained photo-curable resin composition for electronic devices was coated on a PET film with a thickness of 100 μm, and an LED UV lamp was used to ^{irradiate 395 nm ultraviolet rays at 3000 mJ/cm 2 to} make the photo-curable resin composition The thing hardens. As the LED UV lamp, SQ series (manufactured by QUARK TECHNOLOGY) is used. After that, gold electrodes were vacuum vapor-deposited on both sides of the cured film in an opposing manner to make it into a circle with a diameter of 2 cm and a thickness of 0.1 μm to prepare a test piece for dielectric constant measurement. For the obtained test piece, the dielectric constant was measured under the conditions of 25°C and 100 MHz using a dielectric constant measuring device. As the dielectric constant measuring device, a 1260 impedance analyzer (manufactured by Solartron) and a 1296 dielectric constant measuring interface (manufactured by Solartron) were used. The results are shown in Tables 1 to 4.

＜Evaluation＞ The following evaluations were performed for each of the photocurable resin compositions for electronic devices obtained in the examples and comparative examples. The results are shown in Tables 1 to 4.

(Viscosity) For each of the photocurable resin compositions for electronic devices obtained in the Examples and Comparative Examples, an E-type viscometer was used to measure the viscosity under the conditions of 25° C. and 100 rpm using a CP1 type cone plate. As the E-type viscometer, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) was used.

(Coatability) The following coating test was carried out, that is, using an inkjet printer, the photocurable resin compositions for electronic devices obtained in the Examples and Comparative Examples were placed in a grid with a droplet volume of 10 microliters and a pitch of 25 μm. The shape is printed on alkali-washed alkali-free glass. As the inkjet printer, Materials Printer DMP-2831 (manufactured by FUJIFILM Corporation) was used; as the alkali-free glass, AN100 (manufactured by AGC Corporation) was used. Set the case where there is no uncoated part and unevenness in the printing area and print uniformly as "○", and set the case where there is no uncoated part but the unevenness of the stripes is set to "Δ", and set When there is an uncoated part, set it as "×" to evaluate the coatability.

(Curability) For the photocurable resin compositions for electronic devices obtained in the examples and comparative examples, use LED UV lamps to irradiate 395 nm of ultraviolet rays ^{at 3000 mJ/cm 2 to make the photocurable resin compositions} hardening. As the LED UV lamp, SQ series (manufactured by QUARK TECHNOLOGY) is used. For the composition and hardened product before hardening, FT-IR analysis was performed using a Fourier transform infrared spectrophotometer. As a Fourier transform infrared spectrophotometer, iS-5 (manufactured by Nicolet) was used. In the case of epoxy group, calculate ^{the reduction rate of the peak of 915 cm -1} after hardening, and in the case of oxcyclobutyl, calculate the reduction rate of the peak of ^{980 cm -1 after hardening, respectively as the hardening} Rate (reaction rate of cationic polymerizable group). Set the case where the curing rate is 90% or more to "○", the case where the curing rate is more than 70% and less than 90% is set to "Δ", and the case where the curing rate is less than 70% is set to "×". Evaluation.

(Low outgassing properties) For the photocurable resin compositions for electronic devices obtained in the Examples and Comparative Examples, the gas chromatograph using the headspace method as shown below was used to measure the heat-cured material. Outgassing produced. First, use an applicator to coat 100 mg of the photocurable resin composition for each electronic device with a thickness of 300 μm, and then use an LED lamp to irradiate ultraviolet rays with a wavelength of 365 nm ^{at 3000 mJ/cm 2 to make the electronic device use} The photocurable resin composition is cured. Then, the obtained hardened product was put into a vial for headspace, the vial was sealed, and the vial was heated at 100°C for 30 minutes, and the gas generated was measured by the headspace method. Set the case where the generated gas is less than 400 ppm to "◎", the case where the gas generated is more than 400 ppm and less than 600 ppm is set to "○", and the case where the gas generated is greater than 600 ppm and less than 800 ppm is set to "Δ" is set to "×" for the case of 800 ppm or more to evaluate low outgassing.

[Table 1] Example 1 2 3 4 5 6 Composition (parts by weight) Monofunctional cationic polymerizable compound Monofunctional aliphatic cationic polymerizable compound The compound represented by formula (1-1) (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-212") 70 30 - - - - Compound represented by formula (1-2) (manufactured by Mitsubishi Chemical Corporation, "YED-188") - - 70 - - - Monofunctional cationic polymerizable compound containing phenoxy group Compound represented by formula (1-4) (manufactured by Mitsubishi Chemical Corporation, "YED-122") - - - 70 30 - Compound represented by formula (1-5) (manufactured by ADEKA, "ED-509E") - - - - - 70 Multifunctional cationic polymerizable compound Multifunctional alicyclic epoxy compound 3,4,3',4'-Diepoxybicyclohexane (manufactured by Daicel, "Celloxide 8000") 30 70 30 30 70 30 Compound represented by formula (2-2) (manufactured by JXTG NIPPON OIL & ENERGY, "THI-DE") - - - - - - Compound represented by formula (2-3) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-102") - - - - - - Compound represented by formula (2-4) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-103") - - - - - - Multifunctional aliphatic glycidyl ether compound Neopentyl glycol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., "SR-NPG") - - - - - - Multifunctional Oxycyclobutane Compounds 1,4-Bis(((3-ethyloxycyclobutan-3-yl)methoxy)methyl)benzene (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-121") - - - - - - Polysiloxane compound with more than 2 cationic polymerizable groups The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-169") - - - - - - The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-163") - - - - - - The compound represented by formula (5) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-40-2678") - - - - - - Photocationic polymerization initiator IRGACURE290 (manufactured by BASF) 1 1 1 1 1 1 Dielectric constant 3.1 3.4 2.9 3.0 3.4 3.0 Evaluation Viscosity (mPa·s) 18 30 12 25 40 30 Coatability ○ ○ ○ ○ Δ ○ Hardening ○ ○ ○ ○ ○ ○ Low outgassing Δ ◎ Δ Δ ◎ Δ

[Table 2] Example 7 8 9 10 11 12 Composition (parts by weight) Monofunctional cationic polymerizable compound Monofunctional aliphatic cationic polymerizable compound The compound represented by formula (1-1) (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-212") - - - 70 70 70 Compound represented by formula (1-2) (manufactured by Mitsubishi Chemical Corporation, "YED-188") - - 70 - - - Monofunctional cationic polymerizable compound containing phenoxy group Compound represented by formula (1-4) (manufactured by Mitsubishi Chemical Corporation, "YED-122") 70 70 - - - - Compound represented by formula (1-5) (manufactured by ADEKA, "ED-509E") - - - - - - Multifunctional cationic polymerizable compound Multifunctional alicyclic epoxy compound 3,4,3',4'-Diepoxybicyclohexane (manufactured by Daicel, "Celloxide 8000") - - - - - - Compound represented by formula (2-2) (manufactured by JXTG NIPPON OIL & ENERGY, "THI-DE") - - - 30 - - Compound represented by formula (2-3) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-102") - - - - 30 - Compound represented by formula (2-4) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-103") - - - - - 30 Multifunctional aliphatic glycidyl ether compound Neopentyl glycol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., "SR-NPG") 30 - - - - - Multifunctional Oxycyclobutane Compounds 1,4-Bis(((3-ethyloxycyclobutan-3-yl)methoxy)methyl)benzene (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-121") - 30 30 - - - Polysiloxane compound with more than 2 cationic polymerizable groups The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-169") - - - - - - The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-163") - - - - - - The compound represented by formula (5) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-40-2678") - - - - - - Photocationic polymerization initiator IRGACURE290 (manufactured by BASF) 1 1 1 1 1 1 Dielectric constant 2.9 3.1 3.0 3.0 2.9 2.9 Evaluation Viscosity (mPa·s) 15 40 20 15 19 twenty two Coatability ○ Δ ○ ○ ○ ○ Hardening ○ ○ ○ ○ ○ ○ Low outgassing Δ Δ Δ Δ Δ Δ

[table 3] Example 13 14 15 16 17 18 19 20 twenty one twenty two Composition (parts by weight) Monofunctional cationic polymerizable compound Monofunctional aliphatic cationic polymerizable compound The compound represented by formula (1-1) (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-212") 70 30 - - - 70 70 50 50 50 Compound represented by formula (1-2) (manufactured by Mitsubishi Chemical Corporation, "YED-188") - - 70 - - - - - - - Monofunctional cationic polymerizable compound containing phenoxy group Compound represented by formula (1-4) (manufactured by Mitsubishi Chemical Corporation, "YED-122") - - - 70 - - - - - - Compound represented by formula (1-5) (manufactured by ADEKA, "ED-509E") - - - - 70 - - - - - Multifunctional cationic polymerizable compound Multifunctional alicyclic epoxy compound 3,4,3',4'-Diepoxybicyclohexane (manufactured by Daicel, "Celloxide 8000") - - - - - - - - - - Compound represented by formula (2-2) (manufactured by JXTG NIPPON OIL & ENERGY, "THI-DE") - - - - - - - - - - Compound represented by formula (2-3) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-102") - - - - - - - - - - Compound represented by formula (2-4) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-103") - - - - - - - - - - Multifunctional aliphatic glycidyl ether compound Neopentyl glycol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., "SR-NPG") - - - - - - - - - - Multifunctional Oxycyclobutane Compounds 1,4-Bis(((3-ethyloxycyclobutan-3-yl)methoxy)methyl)benzene (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-121") - - - - - - - - - - Polysiloxane compound with more than 2 cationic polymerizable groups The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-169") 30 70 30 30 30 - - 50 - - The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-163") - - - - - 30 - - 50 - The compound represented by formula (5) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-40-2678") - - - - - - 30 - - 50 Photocationic polymerization initiator IRGACURE290 (manufactured by BASF) 1 1 1 1 1 1 1 1 1 1 Dielectric constant 2.6 2.7 2.8 2.9 2.8 2.6 2.7 2.7 2.7 2.7 Evaluation Viscosity (mPa·s) 14 20 20 25 25 12 26 16 14 29 Coatability ○ ○ ○ ○ ○ ○ ○ ○ ○ Δ Hardening ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Low outgassing Δ ◎ Δ Δ Δ Δ Δ ○ ○ ○

[Table 4] Comparative example 1 2 3 4 5 Composition (parts by weight) Monofunctional cationic polymerizable compound Monofunctional aliphatic cationic polymerizable compound The compound represented by formula (1-1) (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-212") - - - - 5 Compound represented by formula (1-2) (manufactured by Mitsubishi Chemical Corporation, "YED-188") - - - - - Monofunctional cationic polymerizable compound containing phenoxy group Compound represented by formula (1-4) (manufactured by Mitsubishi Chemical Corporation, "YED-122") - 100 - - - Compound represented by formula (1-5) (manufactured by ADEKA, "ED-509E") - - 5 - - Multifunctional cationic polymerizable compound Multifunctional alicyclic epoxy compound 3,4,3',4'-Diepoxybicyclohexane (manufactured by Daicel, "Celloxide 8000") 100 - - - - Compound represented by formula (2-2) (manufactured by JXTG NIPPON OIL & ENERGY, "THI-DE") - - - - - Compound represented by formula (2-3) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-102") - - - - - Compound represented by formula (2-4) (manufactured by JXTG NIPPON OIL & ENERGY, "DE-103") - - - - - Multifunctional aliphatic glycidyl ether compound Neopentyl glycol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., "SR-NPG") - - - - - Multifunctional Oxycyclobutane Compounds 1,4-Bis(((3-ethyloxycyclobutan-3-yl)methoxy)methyl)benzene (manufactured by Toagosei Co., Ltd., "ARONE OXETANE OXT-121") - - 95 - - Polysiloxane compound with more than 2 cationic polymerizable groups The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-169") - - - 100 95 The compound represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-163") - - - - - The compound represented by formula (5) (manufactured by Shin-Etsu Chemical Co., Ltd., "X-40-2678") - - - - - Photocationic polymerization initiator IRGACURE290 (manufactured by BASF) 1 1 1 1 1 Dielectric constant 3.7 2.7 4.0 2.9 2.9 Evaluation Viscosity (mPa·s) 65 15 85 35 32 Coatability X ○ X X X Hardening ○ X ○ ○ ○ Low outgassing ◎ X ◎ ◎ ◎ [Industrial availability]

According to the present invention, it is possible to provide a photocurable resin composition for electronic devices that is excellent in coatability and curability and has a low dielectric constant.

no

no

Claims (7)

A photocurable resin composition for electronic devices, which contains a curable resin and a polymerization initiator, and is characterized in that: The curable resin includes a monofunctional cationically polymerizable compound and a polyfunctional cationically polymerizable compound, The monofunctional cationically polymerizable compound includes at least any one of a monofunctional aliphatic cationically polymerizable compound and a monofunctional cationically polymerizable compound having a phenoxy group that can be substituted, and The photocurable resin composition for electronic devices has a dielectric constant of 3.5 or less when measured under the conditions of 25°C and 100 kHz. The photocurable resin composition for an electronic device according to claim 1, wherein the monofunctional cationically polymerizable compound includes a compound selected from the group consisting of the following formula (1-1) and the following formula (1-2) The compound represented by the following formula (1-3), the compound represented by the following formula (1-4), the compound represented by the following formula (1-5), the compound represented by the following formula (1- 6) The group consisting of the compound represented by the following formula (1-7), the compound represented by the following formula (1-8), and the compound represented by the following formula (1-9) At least one of them,

. The photocurable resin composition for an electronic device according to claim 1 or 2, wherein the polyfunctional cationically polymerizable compound includes a polyfunctional alicyclic epoxy compound that does not have a silicone skeleton, and that does not have a polysiloxane skeleton. One of the group consisting of polyfunctional aliphatic glycidyl ether compounds with a silicone skeleton, a polyfunctional oxycyclobutane compound without a silicone skeleton, and a polysiloxane compound with two or more cationic polymerizable groups At least one. The photocurable resin composition for an electronic device according to claim 3, wherein the polyfunctional cationically polymerizable compound includes a compound selected from the group consisting of the following formula (2-1) and the following formula (2-2) The compound represented, the compound represented by the following formula (2-3), the compound represented by the following formula (2-4), the compound represented by the following formula (3), and the compound represented by the following formula (4) At least one of the group consisting of the compound and the compound represented by the following formula (5),

In the formula (2-1), R ¹ to R ¹⁸ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each of which may be the same or may Different; In the formula (2-2), R ¹⁹ to R ³⁰ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each of which may be the same, It may be different; in formula (2-3), R ³¹ to R ⁴⁸ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each of which may be The same or different; In the formula (2-4), R ⁴⁹ to R ⁶⁶ represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, each They can be the same or different;

In formula (3), R ⁶⁷ each independently represents an alkyl group with a carbon number of 1 or more and 10 or less, R ⁶⁸ each independently represents a bonding bond or an alkylene group with a carbon number of 1 or more and 6 or less, and X represents an epoxy containing A group containing an oxetanyl group, or a group containing a vinyl ether group, n represents an integer from 0 to 1000;

In formula (4), R ⁶⁹ each independently represents an alkyl group with a carbon number of 1 or more and 10 or less, R ⁷⁰ represents a bonding bond or an alkylene group with a carbon number of 1 or more and 6 or less, and R ⁷¹ each independently represents the carbon number 1 or more and 10 or less alkyl group, epoxy group-containing group, oxocyclobutyl group, or vinyl ether group-containing group, X represents an epoxy group-containing group, oxocyclobutyl group-containing group, or A vinyl ether group-containing group, l represents an integer from 0 to 1000, and m represents an integer from 1 to 100. However, when R ⁷¹ is an alkyl group with a carbon number of 1 or more and 10 or less, m represents Integer between 2 and 100;

In formula (5), R ⁷² each independently represents an alkyl group having 1 or more and 10 or less carbon atoms, an epoxy group-containing group, an oxocyclobutyl group-containing group, or a vinyl ether group-containing group, 2k R ⁷² Among them, at least two R ⁷² represent an epoxy group-containing group, an oxocyclobutyl group-containing group, or a vinyl ether group-containing group, and k represents an integer of 3 or more and 6 or less. The photocurable resin composition for electronic devices according to claim 4, wherein the polyfunctional cationically polymerizable compound includes a compound selected from the group consisting of the compound represented by the above formula (3), the compound represented by the above formula (4), and At least one of the group consisting of the compound represented by the above formula (5). The photocurable resin composition for electronic devices according to 2, 3, 4, or 5, wherein the ratio of the monofunctional cationically polymerizable compound to the polyfunctional cationically polymerizable compound (monofunctional cationically polymerizable compound: polyfunctional cation The polymerizable compound) is 1:9 to 9:1 by weight ratio. The photocurable resin composition for electronic devices described in 2, 3, 4, 5, or 6 has a viscosity at 25°C of 5 mPa·s or more and 50 mPa·s or less.