Composition, adhesive, method for producing cured product, and cured product

Abstract

This composition contains a polyfunctional acrylic compound (A) having a fused ring, a monofunctional acrylate compound (B), an epoxy compound (C), an oxetane compound (D), a cationic polymerization initiator (E), and a radical polymerization initiator (F), and the epoxy compound (C) contains an epoxy compound (C1) having a fused ring, and the epoxy compound (C) contains an epoxy compound (C1) having a fused ring. The content of the epoxy compound (C1) is 1-30% by mass. The polyfunctional acrylic compound (A) having a fused ring is preferably a compound (A1) having a tricyclodecane skeleton.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition containing an acrylic compound, an epoxy compound, and a cationic polymerization initiator. BACKGROUND

[0002] A composition containing an acrylic compound and an epoxy compound and containing a cationic polymerization initiator is used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like. With respect to the improvement of such a curable composition, various reports have been made.

[0003] Patent Literature 1 describes a composition containing a radical polymerizable component (A) and a cationic polymerizable component (B), wherein the radical polymerizable component (A) contains 70 to 100 parts by mass of a radical polymerizable compound (A1) having a crosslinked condensed ring in 100 parts by mass of the radical polymerizable component (A), and the cationic polymerizable component (B) contains 10 to 50 parts by mass of a cationic polymerizable compound (B1) having a crosslinked condensed ring in 100 parts by mass of the cationic polymerizable component (B). Patent Literature 1 describes that the composition described in this document is excellent in adhesion, water resistance.

[0004] Prior Art Documents

[0005] Patent Literature

[0006] Patent Literature 1: International Publication No. 2020 / 045358 SUMMARY

[0007] However, the present inventors have conducted studies, and as a result, have found that the composition described in Patent Literature 1 has a high viscosity when it is desired to improve adhesion, moisture resistance of a cured product, and the like, and that the coatability is reduced, and that there is room for improvement in the balance between adhesion, moisture resistance, and viscosity.

[0008] Therefore, the present application has been achieved in order to solve the above-described problems, and it is an object of the present application to provide a composition which is excellent in adhesion and moisture resistance of a cured product, and which has a low viscosity.

[0009] The present inventors have conducted intensive studies, and as a result, have found that a composition containing a multifunctional acrylic compound (A) having a condensed ring, a monofunctional acrylate compound (B), an epoxy compound (C), an oxetane compound (D), a cationic polymerization initiator (E), and a radical polymerization initiator (F), and containing a prescribed amount of an epoxy compound (C1) having a condensed ring in the epoxy compound (C) is capable of solving the above-described problems.

[0010] The present application has been achieved based on the above-described insight, and provides the following technical solutions.

[0011] [1] A composition containing a multifunctional acrylic compound (A) having a condensed ring, a monofunctional acrylate compound (B), an epoxy compound (C), an oxetane compound (D), a cationic polymerization initiator (E), and a radical polymerization initiator (F),

[0012] The epoxy compound (C) contains an epoxy compound (C1) having a condensed ring,

[0013] The content of the epoxy compound (C1) is 1 to 30% by mass relative to the epoxy compound (C).

[0014] [2] The composition according to [1], wherein the multifunctional acrylic compound (A) having a condensed ring is a compound (A1) having a tricyclodecane skeleton.

[0015] [3] The composition according to [1] or [2], wherein the monofunctional acrylate compound (B) contains a monofunctional acrylate compound (B1) having a condensed ring.

[0016] [4] The composition according to any one of [1] to [3], containing a chain epoxy compound (C2).

[0017] [5] The composition according to any one of [1] to [4], wherein the oxetane compound (D) is a compound having two or more oxetanyl groups.

[0018] [6] The composition according to any one of [1] to [5], wherein the cationic polymerization initiator (E) is a photocationic polymerization initiator (E1).

[0019] [7] The composition according to any one of [1] to [6], wherein the radical polymerization initiator (F) is a photoradical polymerization initiator (F1).

[0020] [8] The composition according to any one of [1] to [7], wherein 95% by mass or more of components having a molecular weight of 2,000 or less are contained relative to the composition.

[0021] [9] The composition according to any one of [1] to [8], wherein 20 to 90% by mass of a compound having a condensed ring is contained relative to the composition.

[0022]

[10] An adhesive containing the composition according to any one of [1] to [9].

[0023]

[11] A method for producing a cured product, comprising at least one of a step of irradiating active energy rays to the composition according to any one of [1] to

[10] and a step of heating the composition according to any one of [1] to

[10] .

[0024]

[12] A cured product of the composition according to any one of [1] to

[10] . DETAILED DESCRIPTION

[0025] Hereinafter, preferred embodiments of the composition of the present application, an adhesive containing the same, a cured product thereof, and a method for producing the same will be described.

[0026] <Composition>

[0027] First, the composition of the present application will be described. The composition of the present application contains a multifunctional acrylic compound (A) having a condensed ring, a monofunctional acrylate compound (B), an epoxy compound (C), an oxetane compound (D), a cationic polymerization initiator (E), and a radical polymerization initiator (F), the epoxy compound (C) contains an epoxy compound (C1) having a condensed ring, and the content of the epoxy compound (C1) is 1 to 30 mass% with respect to the epoxy compound (C). It has been found in the present application that, by using the compound (A) and the compound (C) as specific polymerizable compounds, and using the two initiators (E) and (F), and using the oxetane compound (D) and the monofunctional acrylate compound (B), and using the epoxy compound (C1) having a condensed ring in such a small amount, it is possible to maintain high adhesiveness, heat resistance of the cured product (hereinafter, also simply referred to as "heat resistance"), and achieve low viscosity. In the present specification, as examples of excellent adhesiveness, as in the examples described later, it is possible to cite excellent curing properties such as initial curing properties, and excellent adhesiveness after a certain period of time after photocuring. The composition of the present application is low in viscosity.

[0028] In addition, as described in each of the examples described later, the composition of the present disclosure is also excellent in storage stability. As described in each of the examples described later, the composition of the present application is excellent in curing properties, and it is possible to set the amount of use of the polymerization initiator to an amount or less, and in addition thereto, by containing a certain amount of a compound having a condensed ring, the cured product is not easily heat-modified, and is also excellent in heat resistance.

[0029] <Multi-functional Acrylic Compound (A) Having a Condensed Ring>

[0030] The multifunctional acrylic compound (A) (hereinafter, also referred to as "compound (A)") having a condensed ring refers to a compound having 1 or more condensed rings and the sum of the number of acryloyl groups and methacryloyl groups is 2 or more in the molecule. However, a condensed ring that is opened to become a monocyclic ring at the time of becoming a cured product, like an alicyclic epoxy group, is not counted as a condensed ring. This is because a condensed ring that becomes a monocyclic ring after curing cannot be expected to improve the moisture resistance. As the condensed ring, a condensed ring containing a hetero atom is included, and a condensed ring not containing a hetero atom is also included (the same applies to the condensed rings of the compounds (B1), (C1) described later). Note that the alicyclic epoxy group is sometimes referred to as a cyclic olefin oxide structure.

[0031] In terms of improving moisture resistance, the condensed ring possessed by the compound (A) is preferably a cross-linking condensed ring. The cross-linking condensed ring refers to a condensed ring having a hydrocarbon group having 3 or more carbon atoms, and is preferably an aliphatic ring. As the cross-linking condensed ring, a cross-linking condensed ring having a structure represented by General Formula (I) or an adamantane ring and the like can be suitably given, and a cross-linking condensed ring having a structure represented by General Formula (I) is particularly preferred. The hydrogen atoms on these rings can be substituted with an arbitrary substituent. As the substituent, as a monovalent substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, -SO3H, an isocyanate group, or an alkyl group having 1 to 4 carbon atoms and the like can be given. Two hydrogen atoms on one carbon atom of the ring can be substituted with a divalent substituent, and as the divalent substituent at this time, =O, =CH2, =S and the like can be given.

[0032] [Chemical Formula 1]

[0033]

[0034] In the case where the condensed ring possessed by the compound (A) is a cross-linking condensed ring, as the cross-linking condensed ring, for example, the cross-linking condensed rings No. 1 to 12 shown below can be suitably given.

[0035] [Chemical Formula 2]

[0036]

[0037] Among the exemplified cross-linking condensed rings, the composition containing the compound (A1) having at least one condensed ring selected from cross-linking condensed rings No. 2 and No. 3 is preferred in terms of obtaining low viscosity and storage stability while obtaining adhesion and moisture resistance.

[0038] Among them, the composition in which the compound (A) contains the compound (A1) having a tricyclodecane skeleton (hereinafter, also referred to as compound (A1)) is excellent in moisture resistance, and is therefore preferred. Having a tricyclodecane skeleton means having a tricyclodecane ring in the structure, and for example, having a cross-linking condensed ring No. 2.

[0039] The number of condensed rings in the compound (A) is preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and most preferably 1 from the viewpoint of low viscosity and adhesiveness. For example, the number of condensed rings in the following formula (II) is 1.

[0040] The sum of the number of acryloyl groups and methacryloyl groups in the compound (A) can be preferably 2 to 5, more preferably 2 to 4, further preferably 2 to 3, and most preferably 2 from the viewpoint of low viscosity and adhesiveness.

[0041] The compound (A) is preferably represented by the following formula (II) from the viewpoint of easily achieving moisture resistance, low viscosity, and adhesiveness.

[0042] [Chemical Formula 3]

[0043]

[0044] In the formula, ring A is any one of the above cross-linking condensed rings No. 1 to 12, L 1 and L 2 each independently is a direct bond or an alkylene group having 1 to 3 carbon atoms. R 1 and R 2 each independently is a hydrogen atom or a methyl group.

[0045] The molecular weight of the compound (A) can be preferably 150 or more and less than 600, more preferably 200 or more and 400 or less, and further preferably 250 or more and 350 or less from the viewpoint of low viscosity and adhesiveness.

[0046] As the compound (A), tricyclodecane dimethanol di(meth)acrylate and the like can be given.

[0047] The (meth)acrylate described in the present specification means both the corresponding methacrylate and acrylate. For example, if it is tricyclodecane dimethanol di(meth)acrylate, it means both tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate.

[0048] As the compound (A1), commercially available products can also be used. As the commercially available products, KAYARAD R-684 (manufactured by Nippon Shokubai), A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like can be given.

[0049] The content of the compound (A) is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and particularly preferably 15 to 50 parts by mass, relative to 100 parts by mass of the solid content of the composition. This is because, when the content of the compound (A) is within the above range, a composition having a good balance between moisture heat resistance and adhesiveness can be obtained. The solid content of the composition in the description of the present application means the content excluding the solvent contained in the composition.

[0050] The content of the compound (A1) is preferably 30 to 100 parts by mass, more preferably 40 to 100 parts by mass, and particularly preferably 50 to 100 parts by mass, relative to 100 parts by mass of the compound (A). This is because, when the content of the compound (A1) is within the above range, a composition having a good balance between moisture heat resistance and adhesiveness can be obtained.

[0051] The composition of the present application can contain a polyfunctional acrylic compound having no condensed ring (hereinafter also referred to as compound (A')). As the compound (A'), aliphatic polyfunctional acrylic compounds, polyfunctional acrylic compounds having an isocyanurate ring, and the like can be given.

[0052] As the aliphatic polyfunctional acrylic compound, a compound having no aromatic ring and heterocycle and having a total number of acryloyl groups and methacryloyl groups of 2 or more can be exemplified by esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol diacrylate, neopentyl glycol diacrylate, trimethylol ethane tri(meth)acrylate, trimethylol propane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polyester (meth)acrylate oligomers. In addition, as the aliphatic polyfunctional acrylic compound, a polyfunctional urethane (meth)acrylate can be given.

[0053] As the above polyfunctional acrylic compound having an isocyanurate ring, ε-caprolactone-modified tris[2-(meth)acryloyloxyethyl] isocyanurate, tris[(meth)acryloyl ethyl] isocyanurate, tris[3-(meth)acryloyloxypropyl] isocyanurate and the like tris[(meth)acryloyloxyalkyl] isocyanurate, di[(meth)acryloyl ethyl]-2-hydroxyethyl isocyanurate, and tris(acryloyl ethyl) isocyanurate can be given.

[0054] As commercially available products of the aliphatic multifunctional acrylic compound, KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Shokubai Co., Ltd.), NK Ester A-DOD-N, A-DPH, A-TMPT, A-HD-N, TMPT, A-NPG, and A-HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Oligo U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U-122A, U-340A, U-324A, UA-53H, UA-100, AH-600 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.), Art Resin UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH-500, SH-9832, UN-901T, UN-904, UN-905, UN-906, UN-906S, UN-907, UN-952, UN-953, UN-954, H-91, H-135 (manufactured by Konishi Co., Ltd.), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (manufactured by Sartomer Company), EBECRYL 8810 (manufactured by Daicel Corporation), and the like can be mentioned.

[0055] As commercially available products of the multifunctional acrylic compound having an isocyanurate ring and not having a condensed ring, ARONIX M-215, M-315 (manufactured by Toagosei Co., Ltd.), NK Ester A-9300, A-9300-1CL, A-9300-3CL (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), TAIC (manufactured by Mitsubishi Chemical), and the like can be mentioned.

[0056] In particular, from the viewpoint of obtaining a composition having improved initial curability, the content of the compound (A') is preferably 50% by mass or less, more preferably 20% by mass or less, and can be 3% by mass or less, in the solid content of the composition.

[0057] From the viewpoint of obtaining a low viscosity and particularly improving the adhesive force, the proportion of the compound (A) in the entire multifunctional acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more.

[0058] <Monofunctional acrylate compound (B)>

[0059] The monofunctional acrylate compound (B) (hereinafter, also referred to as compound (B)) refers to a compound having one acryloyl group or methacryloyl group. As the compound (B), a monofunctional acrylate compound (B1) having a fused ring (hereinafter, also referred to as compound (B1)), a monofunctional acrylate compound (B2) having a hydroxyl group (hereinafter, also referred to as compound (B2)), and other monofunctional acrylate compounds (B3) (hereinafter, also referred to as compound (B3)) can be exemplified. The composition of the present application can exhibit adhesiveness, moisture and heat resistance, and low tackiness in a case where the composition contains the monofunctional acrylate compound (B) in a case where the compounds (A), (C) to (F) are contained and the ratio of (C1) / (C) is a specific ratio.

[0060] The above-mentioned compound (B1) refers to all monofunctional acrylate compounds having a fused ring, the above-mentioned compound (B2) refers to a monofunctional acrylate compound having a hydroxyl group without having a fused ring, and the above-mentioned compound (B3) refers to a monofunctional acrylate compound which does not belong to the compound (B1) or the compound (B2).

[0061] The composition containing the compound (B1) is excellent in moisture and heat resistance, and is thus preferred. The compound (B1) refers to a compound having one or more fused rings in the molecule and having one acryloyl group or methacryloyl group. However, a fused ring which is opened to become a monocyclic ring at the time of becoming a cured product, such as an alicyclic epoxy group, is not counted as a fused ring. This is because the moisture and heat resistance of the cured product cannot be expected to be improved in the case of a fused ring which becomes a monocyclic ring after curing.

[0062] The fused ring possessed by the compound (B1) is preferably a crosslinking fused ring in terms of low viscosity and achievement of a balance between moisture and heat resistance and adhesiveness. As the crosslinking fused ring, a crosslinking fused ring having a structure represented by the above general formula (I) can be preferably exemplified.

[0063] As examples of the compound (B1), dicyclopentyl oxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, adamantyl (meth) acrylate, 2-isopropyl-2-adamantyl (meth) acrylate, and the like can be exemplified.

[0064] As the compound (B1), a commercially available product can also be used. As the commercially available product, for example, DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-511AS, FA-512AS, FA-513AS, FA-512M, FA-512MT, FA-513M (manufactured by Hitachi Chemical Co., Ltd.), and the like can be exemplified.

[0065] The fused ring contained in the compound (B1) can be the same as or different from the compound (A). In the different case, a compound having a smaller number of rings constituting the fused ring than the compound (A) can be used. The number of rings constituting the fused ring herein means the number of rings contained in the fused ring, and is 3 in the case of the crosslinked fused ring No. 1 and 4 in the case of the crosslinked fused ring No. 2.

[0066] In the present application, the fused ring contained in the compound (B1) is preferably a norbornyl skeleton or a tricyclodecane skeleton from the viewpoint of improving the curability and making the properties as an adhesive particularly excellent, and is particularly preferably at least one selected from the crosslinked fused ring No. 1 and No. 2, and is especially preferably a compound having at least one selected from the crosslinked fused ring No. 1 and No. 2, and is especially preferably the crosslinked fused ring No. 1, and is most preferably an isobornyl ring.

[0067] In terms of the curability, the compound (B1) preferably has an acryloyl group among acryloyl group and methacryloyl group.

[0068] The composition containing the compound (B2) as the monofunctional acrylate compound (B) is excellent in heat resistance, and is therefore preferred. The compound (B2) means a compound having no fused ring in the molecule, having one acryloyl group or methacryloyl group, and having one or more hydroxyl groups. The number of hydroxyl groups is preferably one from the viewpoint of low viscosity and good coatability.

[0069] As examples of the compound (B2), there can be mentioned hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like hydroxyl group-containing acrylates; N-2-hydroxyethyl (meth) acrylamide, and the like hydroxyl group-containing acrylamides; mono (meth) acrylates of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like epoxy (meth) acrylates obtained by reacting an epoxy compound with (meth) acrylate.

[0070] As the composition of the present application, the compound (B3) can be contained as the compound (B).

[0071] As the compound (B3), glycidyl (meth)acrylate, and the following compounds No. 1 to No. 4, (3- ethyloxetan-3-yl)methyl acrylate, and the like can be exemplified.

[0072] [Chemical Formula 4]

[0073]

[0074] As other compounds (B3), for example, the following can be exemplified: (meth)acrylic acid; unsaturated succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2- (meth)acryloyloxyethyl] ester; methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butyloxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, and the like esters of unsaturated monoacids and monohydric or monophenolic alcohols; zinc (meth)acrylate, magnesium (meth)acrylate, and the like metal salts of unsaturated monoacids, and the like.

[0075] As other compounds B3, commercially available products can also be used. As the commercially available products, for example, the following can be exemplified: NK Ester AM-90G, AM-90G, AM-130G, AM-230G, AMP-20GY (all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.), β-CEA, EBECRYL 110, EBECRYL 110 (all of which are manufactured by Daicel-allnex), THFA (manufactured by Osaka Organic Chemical Industry), and the like.

[0076] As the compound (B), it is preferable to contain at least one selected from the group consisting of the compound (B1) and the compound (B2).

[0077] As the content of the compound (B), it is preferable to be 3 to 70 parts by mass, more preferable to be 5 to 60 parts by mass, and particularly preferable to be 8 to 50 parts by mass, with respect to 100 parts by mass of the solid content of the composition. This is because, in the case where the content of the compound (B) is in the above range, a composition having a good balance between moisture heat resistance and adhesiveness can be obtained. The solid content of the composition in the description of the present application means the content excluding the solvent contained in the composition.

[0078] The content of the compound (B1) is preferably 30 to 100 parts by mass, more preferably 40 to 90 parts by mass, and particularly preferably 50 to 80 parts by mass, relative to 100 parts by mass of the compound (B). This is because, when the content of the compound (B1) is within the above range, a composition having a good balance between moisture resistance and adhesiveness can be obtained.

[0079] The mass ratio of the content of the compound (A) to the content of the compound (B1) is preferably 2 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the compound (A), from the viewpoint of a balance between low viscosity, storage stability, adhesiveness, moisture resistance, and particularly from the viewpoint of excellent curability and particularly excellent adhesiveness, more preferably 3 parts by mass or more and 80 parts by mass or less, and further preferably 5 parts by mass or more and 30 parts by mass or less.

[0080] The content of the compound (B2) is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 30 to 60 parts by mass, relative to 100 parts by mass of the compound (B). This is because, when the content of the compound (B2) is within the above range, a composition having a good balance between low viscosity, moisture resistance, and adhesiveness can be obtained.

[0081] From the viewpoint of low viscosity and storage stability, the total amount of monofunctional acrylate compounds and difunctional acrylate compounds is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and more further preferably 95% by mass or more, in the acrylic compound. The acrylic compound is a compound having an acryloyl group or a methacryloyl group, and the difunctional acrylate compound is a compound having a total of two acryloyl groups or methacryloyl groups.

[0082] <epoxy compound (C)>

[0083] The epoxy compound (C) (hereinafter, also referred to as the compound (C)) refers to a compound having one or more epoxy groups, and not having an acryloyl group and a methacryloyl group.

[0084] The present application is a composition in which the compound (C) contains an epoxy compound (C1) having a condensed ring (hereinafter, also referred to as the compound (C1)), and thus a composition having a good balance between moisture resistance and adhesiveness can be obtained.

[0085] <epoxy compound (C1) having a condensed ring>

[0086] The compound (C1) is an epoxy compound having a condensed ring. Among the condensed rings, a crosslinked condensed ring having a structure represented by the above general formula (I) can be given from the viewpoint of excellent moisture resistance.

[0087] As the compound (C1), a compound represented by any one of the following formulae (IV-1) to (IV-3) is preferred.

[0088] [Chemical Formula 5]

[0089]

[0090] In the formula, ring C is any one of the above crosslinking condensed rings No. 1 to 12, L 4 and L 5 Each independently is a direct bond or an alkylene group having 1 to 3 carbon atoms.

[0091] [Chemical Formula 6]

[0092]

[0093] In the formula, ring D is any one of the above crosslinking condensed rings No. 1 to 12, L 6 is a direct bond or an alkylene group having 1 to 3 carbon atoms.

[0094] In the present specification, as the alkylene group having 1 to 3 carbon atoms, methylene group, ethylene group, propylene group can be mentioned.

[0095] [Chemical Formula 7]

[0096]

[0097] In the formula, ring E is any one of the above crosslinking condensed rings No. 1 to 12.

[0098] As the specific examples of the compound (C1) represented by any one of the formulae (IV-1) to (IV-3), the following compounds (C1) No. 1 to No. 14, etc. can be mentioned.

[0099] [Chemical Formula 8]

[0100]

[0101] As the compound (C1), commercially available products can also be used. As the commercially available products, the following can be mentioned, for example: ADEKA RESIN EP-4088L, 4088S (manufactured by ADEKA); XD-1000 (manufactured by Nippon Kayaku), HP-7200 (manufactured by DIC), KRM-408 (manufactured by ADEKA), etc.

[0102] As the epoxy group of the compound (C1), a glycidyl ether group is preferred from the viewpoint of high curability and excellent adhesion. In addition, from the viewpoint of excellent adhesion, it is preferred to have a plurality of epoxy groups, and from the viewpoint of low viscosity of the composition and excellent coatability, it is particularly preferred to have 2 to 3, and most preferably 2. Therefore, a compound represented by formula (IV-1) is preferred.

[0103] The composition containing the compound (C1) having the crosslinked condensed ring No. 2 or No. 3 described above has low viscosity, high adhesion, and moisture resistance, and is therefore preferred, and a composition containing the compound (C1) having the crosslinked condensed ring No. 2 is preferred.

[0104] The composition containing the chain-type epoxy compound (C2) (hereinafter, also referred to as the compound (C2)) as the compound (C) has excellent coatability, and is therefore preferred. The compound (C2) is a compound having a glycidyl ether group, and having no cyclic structure other than an epoxy group and no acryloyl group and methacryloyl group in the molecule.

[0105] As specific examples of the compound (C2), monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols, glycidyl esters of alkyl carboxylic acids, polyglycidyl ethers of aliphatic polyols or epoxy alkyl adducts thereof, and polyfunctional epoxy compounds such as polyglycidyl esters of aliphatic long-chain polybasic acids can be given.

[0106] As representative compounds of the chain-type epoxy compound, 1,4-butanediol diglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polyglycidyl ethers of polyols such as glycidyl ethers of polyhydric alcohols, and polyglycidyl ether adducts of polyether polyols obtained by adding one or two or more kinds of epoxy alkyl to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerol, and di-glycidyl esters of aliphatic long-chain dibasic acids can be given. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, epoxidized polybutadiene, and the like can be given.

[0107] As the compound (C2), commercially available compounds such as Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (all of which are manufactured by Nagase Chemtex), DY-022 (manufactured by Nagase Chemtex), Epolite M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (all of which are manufactured by Kowa Chemical Industry), ADEKA Glycirol ED-503, ADEKA Glycirol ED-503G, ADEKA Glycirol ED-506, ADEKA Glycirol ED-523T (all of which are manufactured by ADEKA), 2EH (manufactured by Yashima Chemical), and the like can be used.

[0108] In the present application, from the viewpoint of producing a composition having excellent adhesiveness, moisture and heat resistance, and heat resistance, the chain of the compound (C2) is preferably branched. For example, the compound (C2) is preferably a compound having a structure in which a branched chain alcohol is glycidyl etherified.

[0109] In the case where the chain-type epoxy compound (C2) is a compound having a structure in which a chain-type alcohol is glycidyl etherified, as the chain-type alcohol, a chain-type alcohol having 3 to 10 carbon atoms can be suitably given, and more preferably 3 to 8. As the compound (C2), a compound having a structure in which a branched chain-type alcohol having the above number of carbon atoms is glycidyl etherified is particularly preferred.

[0110] As the epoxy group of the compound (C2), a glycidyl ether group is preferred from the viewpoint of high curability and excellent adhesion. In addition, from the aspect of excellent adhesion, it is preferred to have a plurality of epoxy groups, and from the aspect of low viscosity of the composition and excellent coatability, 2 to 3, and most preferably 2 are particularly preferred.

[0111] The compound (C) can also use other epoxy compounds in addition to the compound (C1) and the compound (C2). As the other epoxy compound, an aromatic epoxy compound can be given. The aromatic epoxy compound refers to a compound having an aromatic ring and not having an alicyclic epoxy group. As examples of the aromatic epoxy compound, the compounds described in International Publication No. 2020 / 045358, a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, a bisphenol E-type epoxy compound, or a phenol novolak-type epoxy compound are preferred because of excellent adhesion.

[0112] As the compound (C), it is preferred not to contain an epoxy compound having an alicyclic epoxy group because of good adhesion. As the epoxy compound having an alicyclic epoxy group, the epoxy compounds exemplified in International Publication No. 2020 / 045358 can be given. The content of the epoxy compound having an alicyclic epoxy group in the compound (C) is preferably 1% by mass or less.

[0113] Note that in the present specification, in the case where the molecular weight of the epoxy compound exceeds 2,000, the compound is handled as an epoxy polymer not belonging to any one of the compound (C1), the compound (C2), the aromatic epoxy compound, and the alicyclic epoxy compound. The molecular weight referred to here is the weight average molecular weight, which will be described later.

[0114] The content of the above epoxy polymer in the composition is preferably less than 5% by mass, more preferably less than 4% by mass, and particularly preferably less than 3% by mass, as the epoxy compound (C).

[0115] The content of the compound (C) is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and particularly preferably 20 to 50 parts by mass, with respect to 100 parts by mass of the solid content of the composition. This is because in the case where the content of the compound (C) is in the above range, a composition having a good balance between moisture resistance and adhesion can be obtained.

[0116] The content of the compound (C1) is 1 to 30% by mass relative to the compound (C). As described above, in the present application, by using all of the compounds (A) to (F) and setting the compound (C1) to the above prescribed amount, a composition excellent in moisture heat resistance, low viscosity, storage stability, and adhesiveness can be obtained. From this viewpoint, the content of the compound (C1) is more preferably 5 to 30% by mass and particularly preferably 10 to 30% by mass relative to the compound (C).

[0117] From the viewpoint of the balance between low viscosity and adhesiveness, and particularly the viewpoint of making the adhesiveness including curability more excellent, the mass ratio of the content of the compound (A) and the compound (C1) relative to 100 parts by mass of the compound (A) can be suitably cited as 2 parts by mass or more and 200 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and particularly preferably 5 parts by mass or more and 30 parts by mass or less.

[0118] From the aspect of further improving the above effects, the content of the compound (C1) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass relative to 100 parts by mass of the solid content of the composition.

[0119] The content of the compound (C2) is preferably 15 to 90 parts by mass, more preferably 30 to 80 parts by mass, and particularly preferably 50 to 70 parts by mass relative to 100 parts by mass of the compound (C). This is because, when the content of the compound (C2) is in the above range, a composition excellent in the balance between moisture heat resistance and adhesiveness can be obtained.

[0120] The content of the compound (C2) is preferably 180 to 1200 parts by mass, more preferably 200 to 1000 parts by mass, and particularly preferably 250 to 900 parts by mass relative to 100 parts by mass of the compound (C1). This is because, by making the content of the compound (C2) in the above range, a composition excellent in the balance between low viscosity and adhesiveness can be obtained.

[0121] <OXETANE COMPOUND (D)>

[0122] The oxetane compound (D) (hereinafter also referred to as the compound (D)) is a compound having an oxetanyl group in the molecule without having an acryloyl group, a methacryloyl group, or an epoxy group. The composition of the present application contains the oxetane compound (D) under the condition that the compounds (A) to (C), (E), and (F) and (C1) / (C) are in a specific ratio, and the initial curability is improved, and the balance between low viscosity and adhesiveness and moisture heat resistance becomes good.

[0123] As the oxetane compound, 3,3'-[oxybis(methylene)]bis(3-ethyloxetane), (3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-(3-ethyl-3-oxetanylmethyloxymethyl)oxetane, xylylene bisoxetane, and the like difunctional oxetane compounds, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, and the like monofunctional oxetane compounds can be exemplified.

[0124] As the oxetane compound, commercially available products such as ARON OXETANE OXT-121, OXT-101, OXT-221, EXOH, POX, PHO, OXA, XDO, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), ETANACOL OXBP, OXTP (manufactured by Ube Industries, Ltd.), and the like can be used.

[0125] As the compound (D), a compound containing a hydroxyl group or a compound not containing a hydroxyl group can be used. In addition, a compound having an aromatic ring or a compound not having an aromatic ring can be used. The compound (D) is preferably a compound in which a hydrogen atom in an aliphatic hydrocarbon compound having an oxygen atom in a group is substituted with an oxetanyl group. The molecular weight of the compound (D) is preferably 100 or more and less than 1,000, and more preferably 150 or more and 400 or less.

[0126] The number of the oxetanyl groups of the compound (D) is usually 1 to 3, and particularly, a composition in which the compound (D) is a compound having two or more oxetanyl groups is preferred because of excellent adhesiveness.

[0127] The content of the compound (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass, relative to 100 parts by mass of the solid content of the composition. This is because, when the content of the compound (D) is within the above range, a composition having a good balance between moisture heat resistance and adhesive force can be obtained.

[0128] From the viewpoint of producing a composition having more excellent moisture heat resistance, low viscosity, and adhesive force, the content of the compound (D) is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 50 parts by mass or more and 150 parts by mass or less, relative to 100 parts by mass of the compound (C1).

[0129] <Photocationic polymerization initiator (E)>

[0130] The cationic polymerization initiator (E) (hereinafter also referred to as component (E)) is a material that generates an acid by active energy rays or heat. Component (E) can use any one of a photocationic polymerization initiator and a thermal cationic polymerization initiator. The photocationic polymerization initiator (E1) is preferred because it has a short curing time for the composition and can be patterned. The photocationic polymerization initiator (E1) is a material that generates an acid by active energy rays such as ultraviolet rays.

[0131] In the composition of the present application, component (E) preferably contains a compound having an aromatic ring and the number of aromatic rings is 3 or more.

[0132] As the photocationic polymerization initiator, a double salt or a derivative thereof as an onium salt, or an oxime sulfonate compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a diazomethane compound, a nitrobenzyl compound, a benzoin tosylate compound, an iron arene complex, a phenylethanone derivative compound, and the like can be used, of which a double salt or a derivative thereof as an onium salt is preferred. This is because the curing speed and adhesive force of the composition of the present application are excellent by using the above photocationic polymerization initiator.

[0133] As the double salt or a derivative thereof as an onium salt, a salt of a cation and an anion represented by the following general formula (1) can be mentioned as a compound having 3 or more aromatic rings.

[0134] [A] m+ [B] m- (1)

[0135] Here, the cation [A] m+ is preferably an onium, and its structure can be represented by the following general formula (2), for example.

[0136] [(R 10 ) a Q] m+ (2)

[0137] Here, R 10 is an organic group having 1 to 60 carbon atoms, which can contain several atoms other than carbon atoms.

[0138] a is an integer of 1 to 5.

[0139] a R 10 each independently can be the same or different.

[0140] a R 10 at least one of which is the above organic group having an aromatic ring, and the number of aromatic rings contained in a R 10 is 3 or more. Q is an atom or an atomic group selected from S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, and F. In addition, when the valence of Q in the cation [A] m+ is q, the relationship m = a - q needs to be satisfied.

[0141] In addition, the anion [B] m- is preferably a halide complex, the structure of which can be represented by the following general formula (3), for example.

[0142] [LX b ] m- (3)

[0143] Here, L is a metal or a metalloid (Metalloid) that is a central atom of the halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, or the like. X is a halogen atom. b is an integer of 3 to 7. In addition, when the valence of L in the anion [B] m- is p, the relationship m = b - p needs to be satisfied.

[0144] As a specific example of the anion [LX b ] m- of the general formula (3), tetra(pentafluorophenyl)borate [(C6F5)4B] - , tetrafluoroborate (BF4) - , hexafluorophosphate (PF6) - , hexafluoroantimonate (SbF6) - , hexafluoroarsenate (AsF6) - , hexachloroantimonate (SbCl6) - , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion), and the like can be given.

[0145] In addition, the anion [B] m- may also preferably use an anion having the structure represented by the following general formula (4).

[0146] [LX b-1 (OH)] m- (4)

[0147] Here, L, X, b are the same as described above. In addition, as other anions that can be used, perchlorate ions (CIO4) - , trifluoromethylsulfite ions (CF3SO3) - , fluorosulfonic acid ions (FSO3) - , toluenesulfonic acid ions, trinitrobenzenesulfonic acid ions, camphorsulfonic acid ions, nonafluorobutanesulfonic acid ions, hexadecafluorooctanesulfonic acid ions, tetraarylboric acid ions, tetra(pentafluorophenyl)boric acid ions, and the like.

[0148] In the composition of the present application, among such onium salts, from the aspect of excellent adhesiveness, an aromatic iodonium salt-based compound or an aromatic sulfonium salt-based compound is preferably used, and an aromatic sulfonium salt-based compound is particularly preferable. As the aromatic iodonium salt-based compound, a diaryliodonium salt having a structure in which two aryl groups are bonded to an iodine atom can be given. As the aromatic sulfonium salt-based compound, a triarylsulfonium salt having a structure in which three aryl groups are bonded to a sulfur atom can be given. As the aromatic iodonium salt-based compound and the aromatic sulfonium salt-based compound, the compounds described in Japanese Patent Application Publication No. 2019-070106, Japanese Patent Application Publication No. 2018-165330, and Japanese Patent Application Publication No. 2016-038569 can be given.

[0149] The content of the cationic polymerization initiator (E) is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 3 to 10 parts by mass, relative to 100 parts by mass of the solid content of the composition, from the aspect of optical properties, particularly the aspect of allowing the optical properties of the cured product to be good.

[0150] <Free radical polymerization initiator (F)>

[0151] The composition in which the free radical polymerization initiator (F) is a photoradical polymerization initiator (Fl) is preferable because the curing time is short and the composition can be patterned.

[0152] The free radical polymerization initiator (F) is a material that generates a radical by active energy rays or the like. The photoradical polymerization initiator (Fl) is a material that generates a radical by light such as ultraviolet rays.

[0153] As the photoradical polymerization initiator (F1), there is no particular limitation as long as it is a photoradical polymerization initiator that generates radicals by light irradiation, and a conventionally known compound can be used, and as a preferable photoradical polymerization initiator, for example, a benzophenone compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, and an oxime ester compound, and the like can be exemplified.

[0154] As the benzophenone compound, for example, as a hydroxyacetophenone compound, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, benzoin; as an alkoxyacetophenone compound, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one; as another acetophenone compound, p-dimethylaminophenylacetophenone, p-t-butyldichloroacetophenone, p-t-butytrichloroacetophenone, p-azidobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1-one, and the like can be exemplified.

[0155] The above hydroxyacetophenone compound refers to an acetophenone compound having a hydroxyl group bonded to a carbon atom adjacent to a carbonyl group, the alkoxyacetophenone compound refers to an acetophenone compound having an alkoxy group bonded to a carbon atom adjacent to a carbonyl group, the aminoacetophenone compound refers to an acetophenone compound having an amino group bonded to a carbon atom adjacent to a carbonyl group, and the other acetophenone compound refers to an acetophenone compound not classified as the hydroxyacetophenone compound, the alkoxyacetophenone compound, and the aminoacetophenone compound.

[0156] As the benzoin compound, benzoin and the like can be exemplified.

[0157] As the benzophenone compound, for example, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyl diphenyl sulfide, and the like can be exemplified.

[0158] As the thioxanthone compound, thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like can be exemplified.

[0159] The oxime ester compound refers to a compound having an oxime ester group, and the compound described in International Publication No. 2020 / 045358 can be exemplified.

[0160] As other photoradical polymerization initiators (F1), there are mentioned phosphine oxide-based compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-isobutylphosphine oxide, bis(2,6-dimethoxybenzoyl)-isobutylphosphine oxide, bis(2,6-dimethoxybenzoyl)-phenylphosphine oxide, and titanocene-based compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyrrol-1-yl)]titanium, and the like.

[0161] Phosphine oxide-based compounds have absorption in the long wavelength region, and are thus preferred in terms of high curability.

[0162] As commercially available photoradical polymerization initiators (F1), there are mentioned ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831, NCI-930 (all of which are manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (all of which are manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all of which are manufactured by Tronly); and the like.

[0163] From the viewpoint of small inhibition of cationic polymerization of the epoxy compound, a photoradical polymerization initiator not containing an amino group is preferred.

[0164] From the viewpoint of excellent transparency of the obtained cured product, a phenylacetone-based compound is preferred, from the viewpoint of not inhibiting cationic polymerization of the epoxy compound, a hydroxyphenylacetone-based compound and an alkoxyphenylacetone-based compound in which an oxygen atom is adjacent to a carbon atom adjacent to a carbonyl group are more preferred, and from the viewpoint of excellent curability, a hydroxyphenylacetone-based compound is particularly preferred.

[0165] The above-described radical polymerization initiator (F) can be used alone or in combination of two or more.

[0166] As the content of the radical polymerization initiator (F), 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass, relative to 100 parts by mass of the solid content of the composition, is preferred.

[0167] This is because when the content of the radical polymerization initiator (F) is within the above range, a composition having excellent optical properties, which can provide a cured product having good optical properties and a good balance between heat and humidity resistance and adhesion, can be obtained.

[0168] The composition of the present application can further add a solvent (G). As the solvent (G), a compound which is liquid at 25°C, 1 atm, and does not belong to the above components. Generally, a solvent capable of dissolving or dispersing the above components can be used as needed. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; cellusolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol-based solvents such as methanol, ethanol, isopropyl or n-propyl alcohol, isobutyl or n-butyl alcohol, and amyl alcohol; ether ester-based solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX-based solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene, and pinene; paraffin-based solvents such as mineral spirits, Swasol #310 (manufactured by Cosmo Matsuyama Seiyu), and Solvesso #100 (manufactured by Exxon Chemical); halogenated aliphatic hydrocarbon-based solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, and 1,2-dichloroethane; halogenated aromatic hydrocarbon-based solvents such as chlorobenzene; carbonyl-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water can be used, and these solvents can be used alone or as a mixed solvent of two or more. Among these, alcohol-based solvents which can undergo cationic polymerization with the epoxy compound are preferred because of their excellent curability, and solvents having a low volatility and a boiling point of 200°C or higher are preferred because of their excellent moldability (dimensional stability, less likely to form bubbles) of the cured product. A composition in which no solvent is added is particularly preferred.

[0169] The content of the solvent is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, relative to 100 parts by mass of the composition. In the case where the solvent is contained, the content is preferably 0.1 parts by mass or more, relative to 100 parts by mass of the composition. This is because when the content of the solvent is within the above range, a composition having a good balance between heat and humidity resistance and adhesion can be obtained.

[0170] In the composition of the present application, the content of the multifunctional acrylic compound (A) and the monofunctional acrylate compound (B) (hereinafter, also referred to as radical polymerizable compound) is preferably in the range of 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, and particularly preferably 40 to 70 parts by mass, with respect to 100 parts by mass of the total of the multifunctional acrylic compound (A), the monofunctional acrylate compound (B), the epoxy compound (C), and the oxetane compound (D) (hereinafter, also referred to as polymerizable compound). This is because the adhesion is excellent when the content of the radical polymerizable compound is in the above range.

[0171] In the composition of the present application, the content of the epoxy compound (C) and the oxetane compound (D) (hereinafter, also referred to as cationic polymerizable compound) is preferably in the range of 10 to 80 parts by mass, more preferably 20 to 70 parts by mass, and particularly preferably 30 to 60 parts by mass, with respect to 100 parts by mass of the total of the polymerizable compound. This is because the adhesion and the moisture resistance are excellent when the content of the cationic polymerizable compound is in the above range.

[0172] The composition in which the composition contains 95% by mass or more of a component having a molecular weight of 2,000 or less is preferred because the viscosity is low and the coatability is excellent, and particularly, the composition preferably contains 96% by mass or more of a component having a molecular weight of 2,000 or less, and more preferably contains 97% by mass or more. Note that the molecular weight referred to here can be measured as the weight average molecular weight in the case of a high molecular compound. The weight average molecular weight can be found by gel permeation chromatography (GPC) in the form of a standard polystyrene conversion value. The weight average molecular weight Mw can be measured, for example, using GPC (LC-2000 plus series) manufactured by Japan Spectroscopic Co., Ltd., with tetrahydrofuran as the elution solvent, with polystyrene standards of Mw 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation) as the calibration curve, and KF-804, KF-803, KF-802 (manufactured by Showa Denko K.K.) as the measurement column. In addition, the measurement temperature can be set to 40°C, and the flow rate can be set to 1.0 mL / minute.

[0173] The composition of the present application is preferably 40 mPa s or less in viscosity from the viewpoint of low viscosity and excellent workability. The viscosity is measured at 25°C by the method described in the Examples below. The lower the viscosity of the composition, the more preferred it is, and is generally 10 mPa s or more.

[0174] The composition containing 20 to 90 mass% of the compound having a condensed ring is preferred because of excellent moisture resistance, low viscosity, excellent balance of adhesiveness, and good heat resistance, and more preferably contains 30 to 75 mass%, and further preferably contains 40 to 60 mass%. As the condensed ring described here, the condensed rings described in the description of the compound (A) can be exemplified.

[0175] <Other components>

[0176] The composition of the present application can contain other components as needed in addition to the above components. The other components can include, as needed, inorganic fillers, organic fillers, pigments, silane coupling agents, colorants such as dyes, photosensitizers, antifoaming agents, thickening agents, thixotropic agents, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, and adhesion promoters, and the like. The total content of the other components is preferably 30 mass% or less in the solid components of the composition of the present application.

[0177] As the method of producing the composition of the present application, there is no particular limitation as long as it is a method capable of uniformly mixing the above components. Note that, as the mixing method, a method using a publicly known mixing device can be employed, and for example, a method using a three-roll mill, a sand mill, a ball mill, or the like can be exemplified.

[0178] As the curing method of the composition of the present application, it is appropriately set depending on the types of the component (E) and the component (F). As the curing method, in the case where the component (E) and the component (F) are a photocationically polymerizable initiator (E1) and a photoradical polymerization initiator (F1), respectively, a method of performing active energy ray irradiation treatment by irradiating the composition of the present application with active energy rays can be used.

[0179] As the active energy rays, visible light, ultraviolet rays, electron beams, X-rays, radioactive rays, high-frequency waves, and the like can be exemplified, and ultraviolet rays are most preferred in terms of economy. As the light source of the ultraviolet rays, ultraviolet laser, mercury lamps, xenon lasers, metal halide lamps, and the like can be exemplified. In addition, the composition of the present application can be cured by irradiation with an LED light source. As the active energy rays from the LED light source, ultraviolet rays can be exemplified. As the wavelength of the active energy rays from the LED light source, 350 nm to 405 nm can be exemplified. The composition of the present application can be cured to a touch-dry state or a solvent-insoluble state by active energy ray irradiation, typically after 0.1 seconds to several minutes, in the case where the cationically polymerizable initiator is a photocationically polymerizable initiator.

[0180] As the curing method of the composition of the present application, in the case where component (F) is a thermal radical polymerization initiator, or in the case where component (E) is a thermal cationic polymerization initiator, a method of performing a heat treatment on the composition of the present application can be used. The conditions when the composition of the present application is cured by heating can be set to 1 to 100 minutes at 70°C to 250°C. The pressure can be applied after pre-baking (PAB) is performed, post-exposure baking (PEB) can also be performed, or baking can be performed at different temperatures in different stages. The heating conditions differ depending on the kind and blending ratio of each component, and can be set to 70°C to 180°C, 5 minutes to 15 minutes if an oven is used, and 1 to 5 minutes if a hot plate is used, for example. Then, in order to cure the coating film, heating treatment is performed at 180°C to 250°C, preferably 200°C to 250°C, for 30 minutes to 90 minutes if an oven is used, and for 5 minutes to 30 minutes if a hot plate is used, whereby a cured film can be obtained.

[0181] As the use of the composition of the present application, there is no particular limitation as long as it is a use for forming a cured product, and optical materials represented by optical films, adhesives, eyeglasses, lenses for photography, paints, coating agents, undercoating agents, inks, high-refractive materials, water-soluble materials, resists for semiconductors / displayers / MEMS / medical devices, liquid resists, printing plates, insulating varnishes, insulating sheets, laminated boards, printed circuit boards, encapsulants for semiconductor devices / LED packaging / liquid crystal injection ports / organic ELs / optical elements / electrical insulation / electronic components / separation films, and the like, molding materials, putty, glass fiber impregnants, caulking agents, passivation films for semiconductors / solar cells, interlayer insulating films, protective films, protective films for color filters, spacers, DNA separation chips, microreactors, nanobiodevices, recording materials for hard disks, solid-state imaging elements, light-emitting diodes, organic light-emitting devices, light-emitting films, fluorescent films, actuators, holograms, plasma devices, polarizing plates, polarizing films, phase difference films, prism sheets used in backlights of liquid crystal display devices, lens sheets such as Fresnel lens sheets used in screens of projection televisions and the like, lens portions of lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, injection molding agents for optical molding, and the like can be given.

[0182] From the viewpoint of excellent moisture resistance, adhesiveness, coatability due to low viscosity, and storage stability, the composition of the present application is preferably used for an adhesive. As specific uses of the adhesive, it can be used for various uses such as optical materials typified by eyeglasses and camera lenses, electronic materials typified by laminated boards and printed circuit boards, in-vehicle devices typified by head-up displays and car navigation systems, and display panels typified by organic EL and liquid crystals. Among them, it is preferably used for uses requiring transparency, and particularly preferably used for optical materials, in-vehicle devices, display panels, and the like.

[0183] When the composition of the present application is used as an adhesive, the adherend to be adhered by the adhesive of the present application can use any of inorganic materials and organic materials.

[0184] As the organic material, for example, cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, and nitrocellulose; polyamides; polyimides; polyurethanes; epoxy compounds; polycarbonates; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-l,4-cyclohexane dimethanol terephthalate, polyethylene-1,2-phenyleneoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate; polystyrenes; polyolefins such as polyethylene, polypropylene, polymethylpentene, polytetrafluoroethylene, and cyclic olefin polymers; vinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonates; polysulfones; polyethersulfones; polyetherketones; polyetherimides; polyethylene oxides; norbornene resins; and the like can be exemplified. In addition, as the inorganic material, for example, glasses such as soda glass and quartz glass, metals, metal oxides, and the like can be exemplified.

[0185] <Adhesive>

[0186] The adhesive of the present application contains the composition of the present application. By containing the composition of the present application, the adhesive of the present application is excellent in curing speed, adhesion, and moisture resistance.

[0187] The adhesive of the present application can be manufactured using the composition of the present application. The adhesive of the present application can be composed only of the composition of the present application, or can be manufactured by mixing the composition of the present application with various additives and the like known to be used in the manufacture of an adhesive using a publicly known mixing device. Note that, as for the use of the composition and the adhesive of the present application, the same content as that described in the item of the composition can be applied, and thus the description thereof is omitted here.

[0188] <Cured product>

[0189] Next, the cured product of the present application is described.

[0190] The cured product of the present application is a cured product of the composition of the present application. The cured product of the present application can be used as an adhesive layer, for example, which is excellent in curing speed and adhesive force. In addition, the composition of the present application can be set to be the same as the content described in the item of "composition", and thus the description thereof is omitted here.

[0191] The cured product of the present application is a cured product of the composition of the present application, and contains the polymer of the composition of the present application. That is, the cured product of the present application has a crosslinked condensed ring.

[0192] As for the planar shape, thickness, and the like of the cured product of the present application, they can be appropriately set according to the use and the like of the cured product.

[0193] The cured product of the present application is obtained by forming the composition of the present application into a desired shape and curing it, and the manufacturing method is not particularly limited. As such a manufacturing method, it can be the same as the content described in the item of the manufacturing method of the cured product described later, and thus the description thereof is omitted here.

[0194] As for the use and the like of the cured product of the present application, it can be the same as the content described in the item of the composition.

[0195] <Manufacturing method of cured product>

[0196] Next, the manufacturing method of the cured product of the present application will be described.

[0197] The manufacturing method of the cured product of the present application has a curing step of curing the composition of the present application. Hereinafter, each step of the manufacturing method of the cured product of the present application will be described in detail.

[0198] 1. Curing step

[0199] The curing step is a step of curing the composition of the present application, and includes a step of irradiating active energy rays or heating. As for such a curing method, it can be the same as the content described in the item of "A. Composition".

[0200] 2. Other steps

[0201] The manufacturing method of the cured product of the present application can have other steps as needed. As such a step, a step of applying the composition of the present application before the step of curing the composition of the present application, and the like can be given.

[0202] As a method of applying the composition of the present application, a publicly known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, and the like can be used. The procedure of application can apply the composition of the present application to a substrate. As the substrate, a substrate including soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, and the like can be appropriately set according to the use of the cured product and the like. In addition, the cured product can be used after being peeled from the substrate or transferred from the substrate to another adherend.

[0203] Examples

[0204] Hereinafter, the present application is described in detail further based on examples, but the present application is not limited to these examples. Comparative Examples 1 to 3 are comparative examples corresponding to Patent Literature 1.

[0205] [Examples and Comparative Examples]

[0206] The compositions of Examples 1 to 19 and Comparative Examples 1 to 11 were prepared by thoroughly mixing the components in accordance with the formulations shown in Tables 1 to 5 below. The symbols in the tables indicate the following components. In addition, the values of the components in the tables are in parts by mass.

[0207] (Multi-functional acrylic compound (A))

[0208] [Chemical Formula 9]

[0209]

[0210] A'-2: Tris(acryloyl ethyl) isocyanurate

[0211] [Chemical Formula 10]

[0212]

[0213] (Single-functional acrylic ester compound (B))

[0214] [Chemical Formula 11]

[0215]

[0216] B1-3: Dicyclopentyl acrylate

[0217] [Chemical Formula 12]

[0218]

[0219] (Epoxy compound (C))

[0220] [Chemical Formula 13]

[0221]

[0222] C-1: copolymer of methyl methacrylate and glycidyl methacrylate, weight average molecular weight 8,000, epoxy equivalent weight 500-600

[0223] C2-1: 1,4-butanediol diglycidyl ether

[0224] (Oxetane compound (D))

[0225] [Chemical Formula 14]

[0226]

[0227] (Cationic polymerization initiator (E))

[0228] [Chemical Formula 15]

[0229]

[0230] (Radical polymerization initiator (F))

[0231] [Chemical Formula 16]

[0232]

[0233] (Evaluation method)

[0234] (Adhesive test piece production method)

[0235] The composition obtained in the examples and comparative examples was coated on one piece of TAC film (FUJITAC TD80, manufactured by FUJIFILM Corporation) so that the film thickness after curing became 3 μm, and then, using a laminator, the other piece of COP (cycloolefin polymer, ZEONOR film 14-060, manufactured by ZEON Corporation) film on which corona discharge treatment was performed was attached, and using an electrodeless ultraviolet light lamp, light equivalent to 1000 mJ / cm

[0236] was irradiated through the COP film to perform adhesion, and a test piece was obtained. 2

[0237] (Initial curing property)

[0238] The adhesive test piece obtained was left to stand for 3 minutes from the time of exposure under conditions of 30°C, 50% RH, and atmospheric pressure, and then, cut into a width of 2.0 cm to obtain an evaluation sample. Using the evaluation sample, a 90° peeling test was performed at a load speed of 300 mm / min, and evaluation was performed in accordance with the following criteria.

[0239] S: more than 1.0 N / 2 cm or substrate destruction

[0240] ​A: more than 0.5 N / 2 cm and 1.0 N / 2 cm or less

[0241] B: more than 0.2 N / 2 cm and 0.5 N / 2 cm or less

[0242] C: 0.2 N / 2 cm or less

[0243] The higher the value of the initial curability, the more excellent the curability.

[0244] (adhesion)

[0245] The obtained adhesion test piece was left to stand for 12 hours from exposure under the conditions of 30°C, 50% RH, and atmospheric pressure, cut into a width of 2.0 cm, and an adhesion evaluation sample was obtained. The obtained sample was subjected to a 90-degree peeling test under the above conditions, and evaluated in accordance with the following criteria.

[0246] S: more than 3.0 N / 2 cm or substrate failure

[0247] A: more than 1.5 N / 2 cm and 3.0 N / 2 cm or less

[0248] B: more than 0.5 N / 2 cm and 1.5 N / 2 cm or less

[0249] C: 0.5 N / 2 cm or less

[0250] The higher the adhesion, the more excellent the adhesion as an adhesive.

[0251] (hydrothermal resistance)

[0252] The above adhesion test piece was left in an environment of 85°C x 85% Rh for 500 hours. Then, after the temperature of the test piece was decreased to room temperature, a 90-degree peeling test was performed under the above conditions, and evaluated in accordance with the following criteria.

[0253] S: more than 1.5 N / 2 cm

[0254] A: more than 1.0 N / 2 cm and 1.5 N / 2 cm or less

[0255] B: more than 0.5 N / 2 cm and 1.0 N / 2 cm or less

[0256] C: 0.5 N / 2 cm or less

[0257] The higher the adhesion, the more excellent the hydrothermal resistance.

[0258] (thermal resistance)

[0259] The composition obtained in the examples and comparative examples was coated on a glass plate at a thickness of 50 μm, another glass plate was attached, and irradiated with a high-pressure Hg lamp at 1000 mJ / cm2 The active energy rays were heated at 150°C for 1 hour to obtain a test piece. The b* (hereinafter referred to as "b*") in the L*a*b* color space of the test piece was measured using a V-670 UV-Vis-NIR spectrophotometer (manufactured by Japan Spectrophotometer Co., Ltd.). S Then, after placing the obtained test piece in an environment of 85℃× for 500 hours, the b* value was determined (hereinafter referred to as "b*"). H Find Δb*(=|b*). H -b* S The value of |) is evaluated according to the following evaluation criteria.

[0260] S: Δb* is less than 3

[0261] A: Δb* is 3 or more but less than 5

[0262] B: Δb* is 5 or more but less than 10

[0263] C: Δb* is 10 or higher

[0264] The smaller the Δb*, the better the heat resistance.

[0265] (Optical properties)

[0266] Based on the b* measured in the above (heat resistance) evaluation S The value is evaluated according to the following evaluation criteria.

[0267] S: b* of the cured product S 3 or below

[0268] A: b* of the cured product S More than 3 and less than 5

[0269] B: b* of the solidified product S More than 5 and less than 10

[0270] C: b* of the cured product S More than 10

[0271] b* S The smaller the size, the better the optical properties.

[0272] (Viscosity)

[0273] The viscosity of the compositions of the examples and comparative examples immediately after manufacture (hereinafter also referred to as "viscosity V1") was measured using a viscometer (cone-plate viscometer (Toki Sangyo TVE-22L)) at 25°C, and evaluated according to the following evaluation criteria.

[0274] A: Viscosity V1 is below 40 mPa·s

[0275] B: viscosity Vl is more than 40 mPa-s and is 100 mPa-s or less

[0276] C: viscosity Vl is 100 mPa-s or more

[0277] The lower the viscosity, the more excellent the handleability, and thus is preferred.

[0278] (Storage stability)

[0279] After the above composition was manufactured, it was put in a brown-colored spiral tube (manufactured by Maruemu Co., Ltd.), capped and sealed, and left to stand at ordinary temperature for 3 months, after which the viscosity was measured again using the above method (hereinafter referred to as viscosity "V2"). The tackiness rate (%) = (V2-Vl) Vl x 100 (%) was calculated, and evaluated according to the following criteria.

[0280] A: tackiness rate is less than 10%

[0281] B: tackiness rate is 10% or more

[0282]

[0283]

[0284]

[0285]

[0286]

[0287] As shown in Tables 1 to 5, the adhesiveness, moisture heat resistance, and viscosity of the composition of each example were all evaluated as "A" or more. In comparison with each example, Comparative Examples 1 to 3, which correspond to Patent Document 1, had poor initial curing properties, and thus had insufficient adhesiveness, and also had room for improvement in terms of high viscosity. Comparative Examples 4, 5, and 11, which did not contain compound (A) or compound (Cl), had poor moisture heat resistance, and Comparative Examples 6 to 10, which did not contain compounds (B) to (D), component (E), or component (F), had poor adhesiveness and moisture heat resistance.

[0288] Industrial applicability

[0289] According to the present application, a composition having excellent adhesiveness and moisture heat resistance of a cured product, and low viscosity, can be provided.

Claims

1. A composition containing a multifunctional acrylic compound (A) having a condensed ring, a monofunctional acrylate compound (B), an epoxy compound (C), an oxetane compound (D), a cationic polymerization initiator (E), and a radical polymerization initiator (F), the epoxy compound (C) contains an epoxy compound (C1) having a condensed ring, the content of the epoxy compound (C1) having a condensed ring is 1 to 30 mass% relative to the epoxy compound (C).

2. The composition of claim 1, wherein, the multifunctional acrylic compound (A) having a condensed ring is a compound (Al) having a tricyclodecane skeleton.

3. The composition according to claim 1 or 2, wherein, the monofunctional acrylate compound (B) contains a monofunctional acrylate compound (Bl) having a condensed ring.

4. The composition according to claim 1 or 2, wherein, the composition contains a chain epoxy compound (C2).

5. The composition of claim 1 or 2, wherein, the oxetane compound (D) is a compound having two or more oxetanyl groups.

6. The composition of claim 1 or 2, wherein, the cationic polymerization initiator (E) is a photocationic polymerization initiator (El).

7. The composition of claim 1 or 2, wherein, the radical polymerization initiator (F) is a photoradical polymerization initiator (Fl).

8. The composition of claim 1 or 2, wherein, contains 95 mass% or more of a component having a molecular weight of 2,000 or less relative to the composition.

9. The composition of claim 1 or 2, wherein, contains 20 to 90 mass% of a compound having a condensed ring relative to the composition.

10. An adhesive containing the composition according to claim 1 or 2.

11. A method for producing a cured product, which includes at least one of a step of irradiating the composition according to claim 1 or 2 with active energy rays and a step of heating the composition according to claim 1 or 2.

12. A cured product of the composition according to claim 1 or 2.

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