CN112399978A

CN112399978A - Composition, adhesive containing same, cured product thereof, and method for producing same

Info

Publication number: CN112399978A
Application number: CN201980046766.4A
Authority: CN
Inventors: 板野和幸; 渡边智志
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2018-08-31
Filing date: 2019-08-26
Publication date: 2021-02-23
Also published as: JP7437306B2; WO2020045358A1; JPWO2020045358A1; TW202019985A; TWI814894B; KR20210053885A

Abstract

Provided are a composition which enables to obtain a cured product having excellent curing rate, excellent water resistance and excellent adhesion, an adhesive containing the same, a cured product thereof, and a method for producing the same. A composition comprising a radically polymerizable component (A) and a cationically polymerizable component (B), wherein the radically polymerizable component (A) contains 70 to 100 parts by mass of a radically polymerizable compound (A1) having a bridged condensed ring per 100 parts by mass of the radically polymerizable component (A), and the cationically polymerizable component (B) contains 10 to 50 parts by mass of a cationically polymerizable compound (B1) having a bridged condensed ring per 100 parts by mass of the cationically polymerizable component (B).

Description

Composition, adhesive containing same, cured product thereof, and method for producing same

Technical Field

The present invention relates to a composition, an adhesive containing the same, a cured product thereof, and a method for producing the same, and more particularly, to a composition capable of obtaining a cured product having excellent curing rate and water resistance and excellent adhesion, an adhesive containing the same, a cured product thereof, and a method for producing the same.

Background

The cationically curable composition is used in the fields of inks, coatings, various coating agents, adhesives, optical members, and the like. Various reports have been made on improvement of such a curable composition.

For example, patent document 1 proposes an active energy ray-curable adhesive composition for plastic films and the like, which has low viscosity and excellent curability, and which has excellent adhesion to various plastic films and sheets and excellent colorless transparency. Patent document 2 proposes an active energy ray-curable adhesive composition for plastic films and the like, which has low viscosity and excellent curability, has excellent adhesion to various plastic films and the like even when the atmospheric humidity during application and curing is high, and has excellent colorless transparency. Further, patent document 3 proposes a photocurable adhesive which has excellent curability even when the humidity of the application environment is high, and which has good adhesion after a certain period of time, good durability, good adhesion after the end of the wet heat resistance test, and low viscosity. Further, patent document 4 proposes a method for producing a laminate, which includes the steps of: a step of forming a curable resin composition layer by using a photo-and heat-curable resin composition containing a diacrylate having a dicyclopentadiene skeleton and a diglycidyl ether having a dicyclopentadiene skeleton; and a step of further irradiating the curable resin composition layer with active energy rays.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-034188

Patent document 2: japanese patent laid-open publication No. 2015-057467

Patent document 3: japanese patent laid-open publication No. 2015-143352

Patent document 4: japanese patent laid-open publication No. 2017-149135

Disclosure of Invention

Problems to be solved by the invention

However, the cationic curable compositions proposed in patent documents 1 to 4 have a problem that sufficient curability cannot be obtained and the water resistance of the resulting cured product is insufficient. For example, when used as an adhesive, the curing rate may be insufficient, and sufficient adhesive strength and water resistance may not be obtained.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a composition capable of obtaining a cured product excellent in curing speed and water resistance and excellent in adhesion, an adhesive containing the same, a cured product thereof, and a method for producing the same.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, the above object has been achieved. The present invention will be described in detail below.

That is, the composition of the present invention is a composition containing a radically polymerizable component (A) and a cationically polymerizable component (B), wherein the radically polymerizable component (A) contains 70 to 100 parts by mass of a radically polymerizable compound (A1) having a bridged condensed ring in 100 parts by mass of the radically polymerizable component (A),

the cationically polymerizable component (B) contains 10 to 50 parts by mass of a cationically polymerizable compound (B1) having a bridged condensed ring per 100 parts by mass of the cationically polymerizable component (B).

In the composition of the present invention, it is preferable that: further comprising a radical polymerizable initiator (C) and a cation polymerizable initiator (D),

the composition contains 40 to 60 parts by mass of the radical polymerizable component (A), 30 to 50 parts by mass of the cation polymerizable component (B), 1 to 10 parts by mass of the radical polymerizable initiator (C) and 1 to 10 parts by mass of the cation polymerizable initiator (D) per 100 parts by mass of the total amount of the radical polymerizable component (A), the cation polymerizable component (B), the radical polymerizable initiator (C) and the cation polymerizable initiator (D). The composition has excellent initial curability.

In the composition of the present invention, it is preferable that: the bridged condensed ring included in the radically polymerizable compound (a1) and the cationically polymerizable compound (B1) is a bridged condensed ring having a structure represented by the following formula (I). A cured product obtained from the composition has excellent water resistance.

Further, in the composition of the present invention, it is preferable that: the cationically polymerizable component (B) includes a cationically polymerizable compound (B2) having a weight average molecular weight of 1000 or more and less than 30000 and having no bridged fused ring. A cured product having excellent water resistance is obtained from the composition.

In the composition of the present invention, it is preferable that: the cationically polymerizable component (B) includes a cationically polymerizable compound (B3) having a weight average molecular weight of 200 or more and less than 1000 and no bridged fused ring. A cured product having excellent coatability and water resistance is obtained from the composition.

In the composition of the present invention, it is preferable that: the cationically polymerizable compound (B3) includes a compound having an oxetanyl group. A cured product having excellent water resistance is obtained from the composition.

Further, in the composition of the present invention, it is preferable that: the radically polymerizable component (a) includes a radically polymerizable compound (a2) having a cationically polymerizable group and having no isocyanurate ring or bridged condensed ring. The composition is excellent in coatability and initial adhesiveness.

In the composition of the present invention, it is preferable that: the radically polymerizable component (a) includes a radically polymerizable compound (a3) having an isocyanurate ring and no bridged condensed ring. A cured product having excellent water resistance is obtained from the composition.

The adhesive of the present invention is characterized by comprising the composition of the present invention. The adhesive containing the composition of the present invention can provide a cured product having excellent curing speed and excellent adhesion and water resistance.

The cured product of the present invention is characterized by being a cured product of the composition of the present invention. By using the composition of the present invention, a cured product having excellent adhesion and water resistance can be formed.

The method for producing a cured product of the present invention is characterized by comprising: a step of irradiating or heating the composition of the present invention with an active energy ray. The composition of the present invention contains the above components, and therefore, a cured product having excellent adhesion and water resistance can be easily obtained.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a composition capable of providing a cured product having excellent curing rate and water resistance and excellent adhesion, an adhesive containing the same, a cured product thereof, and a method for producing the same.

Detailed Description

The composition of the present invention, an adhesive containing the same, a cured product thereof, and a method for producing the same will be described in detail below.

< composition >

First, the composition of the present invention will be described. The composition of the present invention contains a radically polymerizable component (a) (hereinafter also referred to as "component (a)") and a cationically polymerizable component (B) (hereinafter also referred to as "component (B)"). The composition of the present invention contains 70 to 100 parts by mass of the radically polymerizable compound (a1) (hereinafter also referred to as "compound (a 1)") having a bridged fused ring in 100 parts by mass of the component (a), and contains 10 to 50 parts by mass of the cationically polymerizable compound (B1) (hereinafter also referred to as "compound (B1)") having a bridged fused ring in 100 parts by mass of the component (B). That is, by containing the compound (a1) and the compound (B1) in an appropriate ratio as described above, a cured product having excellent curing speed and excellent adhesive strength and water resistance can be obtained.

The composition of the present invention is preferably a composition having high curability because it contains a radical polymerization initiator (C) (hereinafter also referred to as "component (C)") and a cationic polymerization initiator (D) (hereinafter also referred to as "component (D)") in addition to the compound (a1) and the compound (B1). The preferred proportions of the component (A), the component (B), the component (C) and the component (D) in the composition of the present invention are 40 to 60 parts by mass of the component (A), 30 to 50 parts by mass of the component (B), 1 to 10 parts by mass of the component (C) and 1 to 10 parts by mass of the component (D), respectively, based on 100 parts by mass of the total amount of the component (A), the component (B), the component (C) and the component (D). By setting the ratio to this value, a composition that can give a cured product having excellent curing speed and excellent adhesion and water resistance can be obtained.

In the composition of the present invention, the ratio of the component (a) to the component (B) is preferably 50 to 130 parts by mass per 100 parts by mass of the component (a). When the ratio of the component (a) to the component (B) is in the above range, a cured product having excellent adhesion and water resistance can be obtained, which is preferable. Hereinafter, each component will be described in detail.

< radically polymerizable component (A) >

The component (A) is a compound having a radical polymerizable group. The radical polymerizable group is a group capable of polymerizing in the presence of a radical, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, and a thiol group. The component (a) is composed of a compound (a1), a radically polymerizable compound (a2) (hereinafter also referred to as "compound (a 2)") having a cationically polymerizable group and having no isocyanurate ring and no bridged condensed ring, a radically polymerizable compound (A3) (hereinafter also referred to as "compound (A3)") having an isocyanurate ring and no bridged condensed ring, and other radically polymerizable compounds not belonging to the compounds (a1) to (A3). These compounds may be used alone or in combination of two or more.

From the viewpoints of ease of application, curing speed, and the like of the composition of the present invention, the component (a) preferably contains a low molecular weight compound. This is because: since the low-molecular-weight compound is excellent in dispersibility, solubility, and the like in the composition, a cured product having excellent transparency can be obtained. On the other hand, the radical polymerizable compound preferably contains a high molecular weight compound from the viewpoint of the adhesive strength of the composition of the present invention and the like. From the viewpoint of the balance among ease of application, curing speed, and adhesive force of the composition, the radical polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound. Further, by using a high molecular weight compound together with a low molecular weight compound, the dispersion or solubility in the composition of the present invention can be improved, and a cured product having excellent transparency can be obtained.

The molecular weight of the low-molecular weight compound may be, for example, 1000 or less, preferably 50 or more and 500 or less, and particularly preferably 50 or more and 300 or less, as long as the desired coating properties and the like can be obtained. The molecular weight of the high-molecular weight compound may be, for example, greater than 1000, preferably 1000 or more and 50000 or less, and particularly preferably 5000 or more and 20000 or less, as long as the desired ease of adhesion can be obtained. In the following, when the compound is a polymer, the molecular weight indicates a weight average molecular weight (Mw).

Here, the weight average molecular weight can be determined as a standard polystyrene equivalent value by Gel Permeation Chromatography (GPC). The weight average molecular weight Mw can be obtained as follows: for example, the measurement can be carried out using GPC (LC-2000plus series) manufactured by Nippon spectral Co., Ltd., tetrahydrofuran as a dissolution solvent, polystyrene standards for calibration curves Mw1110000, 707000, 397000, 189000, 98900, 37200, 13700, 9490, 5430, 3120, 1010, 589 (TSKgel standard polystyrene manufactured by Tosoh Co., Ltd.), and KF-804, KF-803, KF-802 (manufactured by Showa Denko K.K.) as a measurement column. The measurement temperature may be set to 40 ℃ and the flow rate may be set to 1.0 mL/min.

The content of the component (a) in the composition of the present invention is preferably 40 to 60 parts by mass, and particularly preferably 45 to 55 parts by mass, per 100 parts by mass of the composition, from the viewpoint of excellent water resistance.

< Compound (A1) >

The compound (a1) is a radically polymerizable compound having a bridged fused ring. The bridged fused ring of the compound (a1) is a fused ring sharing 3 or more carbon atoms, and preferably includes a bridged fused ring having a structure represented by the general formula (I).

Examples of the bridged condensed rings having such a structure include those shown below.

Among the bridged condensed rings exemplified, adhesives containing the compound (a1) having bridged condensed rings nos. 6, 7 and 8 are preferable because they have high adhesion and water resistance. The bridged condensed ring No.6 is particularly preferable because of its structural stability and high productivity.

The compound (A1) having 1 to 4 radically polymerizable groups is preferable because the balance between the adhesive strength and the coating properties is good, and the compound (A1) having 1 to 3 radically polymerizable groups is particularly preferable.

Examples of the compound (A1) include tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dimethylol dicyclopentanyl di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, adamantyl (meth) acrylate, and 2-isopropyl-2-adamantyl (meth) acrylate.

As the compound (A1), a commercially available compound can also be used. Examples of commercially available products include KAYARAD R-684 (manufactured by Nippon Kagaku K.K.); A-DCP and DCP (manufactured by Ninghamun chemical industries, Ltd.); FA-511AS, FA-512AS, FA-513AS, FA-512M, FA-512MT, and FA-513M (manufactured by Hitachi chemical Co., Ltd.).

< Compound (A2) >

The compound (a2) is not particularly limited as long as it is a radically polymerizable compound having a cationically polymerizable group and having no isocyanurate ring or bridged condensed ring.

The cationically polymerizable group is a group capable of being polymerized in the presence of an acid, and examples thereof include a hydroxyl group, an epoxy group, an alicyclic epoxy group, an oxetanyl group, a vinyl ether group and the like. The cationically polymerizable group contained in the compound (a2) is preferably a hydroxyl group from the viewpoint of adhesion to a substrate. From the viewpoint of initial curability and adhesion, an epoxy group is preferable.

Examples of the compound (a2) include hydroxyl group-containing acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol tri (meth) acrylate; hydroxyl group-containing acrylamides such as N-2-hydroxyethyl (meth) acrylamide and N-vinylformamide; vinyl alcohols such as vinylphenol, allyl alcohol, and crotyl alcohol; epoxy (meth) acrylates such as ethylene glycol diglycidyl ether epoxy (meth) acrylate, diethylene glycol diglycidyl ether mono (meth) acrylate, triethylene glycol diglycidyl ether mono (meth) acrylate, polyethylene glycol diglycidyl ether mono (meth) acrylate, propylene glycol diglycidyl ether mono (meth) acrylate, tripropylene glycol diglycidyl ether mono (meth) acrylate, polypropylene glycol diglycidyl ether mono (meth) acrylate, neopentyl glycol diglycidyl ether mono (meth) acrylate, and the like obtained by reacting a hydroxyl group-containing vinyl monomer, an epoxy compound, and (meth) acrylic acid; glycidyl (meth) acrylate, and the following compounds (A2) Nos. 1 to 4, (3-ethyloxetan-3-yl) methacrylate, and the like.

The radical polymerizable group of the compound (a2) is preferably an acryloyl group, from the viewpoint of excellent curability. In addition, from the viewpoint of low viscosity and excellent coatability, it is preferable to have 1 or 2 radical polymerizable groups.

When the radically polymerizable component (a) contains the radically polymerizable compound (a2), the content of the radically polymerizable compound (a2) is preferably 0 to 20 parts by mass, and particularly preferably 5 to 10 parts by mass, per 100 parts by mass of the radically polymerizable component (a), from the viewpoint of excellent adhesiveness, water resistance, and fluidity.

< Compound (A3) >

The compound (a3) is not particularly limited as long as it is a radically polymerizable compound containing an isocyanurate ring and having no bridged condensed ring.

Examples of the compound (a3) include tris [ (meth) acryloyloxyalkyl ] isocyanurate such as e-caprolactone-modified tris [2- (meth) acryloyloxyethyl ] isocyanurate, tris [ (meth) acryloylethyl ] isocyanurate, and tris [3- (meth) acryloyloxypropyl ] isocyanurate; and bis [ (meth) acryloylethyl ] -2-hydroxyethyl isocyanurate, monoallyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, the following compound (A3) No.1, and the like.

As the compound (A3), a commercially available compound can also be used. Examples of commercially available products include ARONIX M-215 and M-315 (described above by Toyo Synthesis Co.); NK ESTER A-9300, A-9300-1CL and A-9300-3CL (manufactured by Xinzhongcun chemical industry Co., Ltd.); TMAIC (manufactured by Mitsubishi chemical corporation), and the like.

The radical polymerizable group of the compound (a3) is preferably an acryloyl group, from the viewpoint of excellent curability. Further, from the viewpoint of excellent curability, it preferably has a plurality of radical polymerizable groups, and particularly preferably 2 to 3.

When the radically polymerizable component (a) contains the radically polymerizable compound (A3), the content of the radically polymerizable compound (A3) is preferably 0 to 20 parts by mass, and particularly preferably 5 to 10 parts by mass, per 100 parts by mass of the radically polymerizable component (a), from the viewpoint of excellent water resistance and fluidity.

< other radically polymerizable Compound >

Examples of the other radical polymerizable compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene fluoride, and tetrafluoroethylene; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as (meth) acrylic acid, α -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, HIMIC acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl ] ester, phthalic acid mono [2- (meth) acryloyloxyethyl ] ester, and ω -carboxy polycaprolactone mono (meth) acrylate; an unsaturated polybasic acid such as a polyfunctional (meth) acrylate having 1 carboxyl group and 2 or more (meth) acryloyl groups; 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, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, n-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth), Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 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, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, and polyester (meth) acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adducts, dodecenylsuccinic anhydride, and methylhimic anhydride; amides of unsaturated monobasic and polyamine such as (meth) acrylamide, methylenebis (meth) acrylamide, diethylenetriamine tri (meth) acrylamide, xylylenebis (meth) acrylamide, and α -chloroacrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth) acrylonitrile, α -chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphite, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, and vinyl carbamate compounds of vinyl pyridine and polyisocyanate compounds, and the like.

As other radical polymerizable compounds, commercially available products can be used. Examples of commercially available products include KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA and PET30 (manufactured by Nippon Kagaku Co., Ltd.); NK ESTER A-DOD-N, A-DPH, A-TMPT, A-HD-N, TMPT, NPG and HD-N (manufactured by Xinzhongcun chemical industry Co., Ltd.); SPC-1000, SPC-3000 (available from Showa Denko K.K.); 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 shinkamura chemical Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (manufactured by shinkayako chemical Co., Ltd.), ARTRESIN UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH-500, SH-9832, UN-901T, UN-904, UN-905, UN-906S, UN-907, UN-906-907, UN-952, UN-953, UN-954, H-91, H-135 (manufactured by Kokai Co., Ltd.), SARTOMER CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (manufactured by SARTOMER Co., Ltd.), EBECRYL 8810 (manufactured by DAICEL Co., Ltd.), and the like.

< cationically polymerizable component (B) >

The cationically polymerizable component (B) contained in the composition of the present invention is a compound having a cationically polymerizable group and no radically polymerizable group. The component (B) is composed of the following compounds: a compound (B1), a cationically polymerizable compound (B2) (hereinafter also referred to as "compound (B2)") having a cationically polymerizable group and having no bridged fused ring and a weight average molecular weight of 1000 or more and less than 30000, a cationically polymerizable compound (B3) (hereinafter also referred to as "compound (B3)") having no bridged fused ring and a weight average molecular weight of 200 or more and less than 1000, and other cationically polymerizable compounds not belonging to the compounds (B1) to (B3). In the composition of the present invention, two or more components (B) may be used alone or in combination. In addition, in the case where the compound is a polymer, the molecular weight means a weight average molecular weight (Mw).

The content of the component (B) in the composition of the present invention is preferably 30 to 50 parts by mass, and particularly preferably 40 to 50 parts by mass, per 100 parts by mass of the composition, from the viewpoint of excellent water resistance.

From the viewpoints of ease of application, curing speed, and the like of the composition of the present invention, the component (B) preferably contains a low molecular weight compound. This is because: since the low-molecular-weight compound is excellent in dispersibility, solubility, and the like in the composition, a cured product having excellent transparency can be obtained. On the other hand, the cationically polymerizable compound preferably contains a high molecular weight compound from the viewpoint of the adhesive strength of the composition of the present invention and the like. In addition, from the viewpoint of the balance of ease of application, curing speed, and adhesive force of the composition, the cationically polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound. Further, by using a high molecular weight compound together with a low molecular weight compound, the dispersion or solubility in the composition of the present invention can be improved, and a cured product having excellent transparency can be obtained.

The content of the high molecular weight compound is not particularly limited as long as a desired curing rate and adhesive strength can be obtained, and can be appropriately adjusted from the viewpoint of, for example, balance between adhesive strength and transparency. Specifically, the content of the high-molecular weight compound may be 0 part by mass or more and 20 parts by mass or less, preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less, in 100 parts by mass of the solid content of the composition of the present invention. This is because: by making the content within this range, the curing speed and the adhesive force of the composition of the present invention become excellent, particularly because: a cured product having excellent adhesion and excellent transparency can be formed.

< Compound (B1) >

The compound (B1) is a cationically polymerizable compound having a bridged fused ring. Among the bridged condensed rings, the bridged condensed ring having the structure represented by the general formula (I) is preferable from the viewpoint of excellent water resistance, and particularly, an adhesive containing the compound (B1) having the bridged condensed rings nos. 6, 7 and 8 is preferable because it has high adhesion and water resistance. The bridged fused ring No.6 is particularly preferable because it is stable in structure and high in productivity.

Examples of the compound (B1) include the following compounds (B1) nos. 1 to 22.

As the compound (B1), a commercially available compound can also be used. Examples of commercially available products include ADEKA RESIN EP-4088L and 4088S (manufactured by ADEKA corporation); XD-1000 (manufactured by Nippon Kagaku K.K.) HP-7200 (manufactured by DIC Co., Ltd.), and the like.

The cationically polymerizable group of the compound (B1) is preferably an epoxy group, and particularly preferably a glycidyl ether group, from the viewpoint of high curability and excellent adhesion. Further, from the viewpoint of excellent curability, the resin composition preferably has a plurality of cationically polymerizable groups, and particularly preferably 2 to 3 cationically polymerizable groups.

< Compound (B2) >

The compound (B2) is not particularly limited as long as it is a cationically polymerizable compound having a weight average molecular weight of 1000 or more and less than 30000 and not having a bridged condensed ring. The weight average molecular weight can be measured by the above-mentioned measurement method. The composition containing the compound (B2) is preferable because it has improved water resistance.

Examples of the compound (B2) include a copolymer of glycidyl methacrylate such as a polymer of glycidyl methacrylate and a copolymer of glycidyl methacrylate and methyl methacrylate, and a product obtained by modifying a part of these, and examples of the glycidyl methacrylate include glycidyl methacrylate, 2-methylglycidyl methacrylate, 4-hydroxybutyl methacrylate, diglycidyl ether of bisphenol a, and diglycidyl ether of bisphenol F. In addition, polymers such as novolak-type epoxy resins, 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether, and copolymers thereof, and the like can be cited.

As the compound (B2), a commercially available compound can also be used. Examples of commercially available products include G-0130M (manufactured by Nichiku corporation, supra) and EOCN-104S (manufactured by Nippon chemical Co., Ltd.).

The compound (B2) preferably has an epoxy equivalent of 200 to 600 because it has excellent curability when the epoxy equivalent is 1000 or less.

The cationically polymerizable group contained in the compound (B2) is preferably an epoxy group, and particularly preferably a glycidyl ether group, from the viewpoint that a composition having high curability and high adhesive strength can be obtained.

From the viewpoint of excellent water resistance and fluidity, the preferable content of the cationically polymerizable compound (B2) optionally contained in the cationically polymerizable component (B) is 0 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass, in 100 parts by mass of the cationically polymerizable component (B).

< Compound (B3) >

The compound (B3) is not particularly limited as long as it is a cationically polymerizable compound having a weight average molecular weight of 200 or more and less than 1000 without a bridged fused ring. The composition containing the compound (B3) is preferable because it can achieve both adhesion and coatability. Examples of the compound (B3) include an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, and an oxetane compound. Among them, a compound having an epoxy group and an oxetanyl group in the same molecule is classified as an oxetane compound.

A composition containing a compound (B3) having an epoxy equivalent of 500 or less is preferable because it is excellent in curability, and a composition containing a compound (B3) having an epoxy equivalent of 200 or less is particularly preferable.

The cationically polymerizable group contained in the compound (B3) is preferably an epoxy group, and particularly preferably a glycidyl ether group, from the viewpoint that a composition having high curability and high adhesive strength can be obtained. Further, as the compound (B3), a compound having an oxetanyl group is also preferable in that a composition having excellent water resistance can be obtained.

When the cationically polymerizable component (B) contains the cationically polymerizable compound (B3), the content is preferably 0 to 90 parts by mass, and particularly preferably 35 to 80 parts by mass, per 100 parts by mass of the cationically polymerizable component (B), from the viewpoint of excellent water resistance and fluidity.

The composition containing the compound (B3) having 1 to 3 cationically polymerizable groups can achieve both adhesion and coatability, and therefore the compound (B3) having 1 to 2 cationically polymerizable groups is particularly preferable.

The alicyclic epoxy compound as the compound (B3) is a cationically polymerizable compound having an alicyclic epoxy group (3, 4-epoxycyclohexyl group) and a weight average molecular weight of 200 or more and less than 1000 without a bridged fused ring. The use of an alicyclic epoxy compound as the compound (B3) is preferable because the initial curability is improved.

Examples of the alicyclic epoxy compound include 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexanecarboxylate, 6-methyl-3, 4-epoxycyclohexylmethyl-6-methyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexanecarboxylate, 3, 4-epoxy-5-methylcyclohexylmethyl-3, 4-epoxy-5-methylcyclohexanecarboxylate, epoxy-3, 4-epoxycyclohexylmethyl-3, 4-epoxymethylcyclohexanecarboxylate, and epoxy-5-methylcyclohexanecarboxylate, Bis (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), propane-2, 2-diyl-bis (3, 4-epoxycyclohexane), 2-bis (3, 4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3, 4-epoxycyclohexanecarboxylate), dioctylphthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3, 4-epoxycyclohexane, 1, 2-epoxy-2-epoxyethylcyclohexane, 7-oxabicyclo [4.1.0] heptane, poly [ oxy- (1-oxo-1, 6-hexanediyl) ] derivatives, hexanedioic acid bis [ (7-oxabicyclo [4.1.0] heptan-3-yl) methyl ] ester, alpha-pinene oxide, limonene dioxide.

As the alicyclic epoxy compound, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate or 3, 4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylhexanecarboxylate and 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate are preferable from the viewpoint of improving the adhesive force.

As the alicyclic epoxy compound, commercially available products can be used, and examples thereof include CELLOXIDE2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE 3000, CYCLOMER M100 (manufactured by DAICEL Co., Ltd.); CYRACURE UVR-6128(Dow Chemical Co., Ltd.).

The content of the alicyclic epoxy compound is not limited as long as a desired curing rate and adhesive strength can be obtained, and may be, for example, 0 to 50 parts by mass, and preferably 1 to 20 parts by mass, among 100 parts by mass of the compound (B). When the content is in this range, the curing rate and the adhesive strength of the composition of the present invention become excellent.

The aliphatic epoxy compound as the compound (B3) is a cationically polymerizable compound having a weight average molecular weight of 200 or more and less than 1000 without a bridged fused ring, which is not classified into an alicyclic epoxy compound and an aromatic epoxy compound described later, and is a compound not containing an aliphatic ring and an aromatic ring.

Specific examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl etherate of aliphatic alcohol and glycidyl ester of alkyl carboxylic acid; and polyfunctional epoxy compounds such as polyglycidyl ether compounds of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyl esters of aliphatic long-chain polybasic acids.

Representative examples of the aliphatic epoxy compound include glycidyl ethers of polyhydric alcohols such as 1, 4-butanediol diglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ethers, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; and polyglycidyl etherates of polyether polyols and diglycidyl esters of aliphatic long-chain dibasic acids obtained by adding 1 or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerol. Further, there may be mentioned monoglycidyl ether of aliphatic higher alcohol, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, epoxidized polybutadiene and the like.

As the aliphatic epoxy compound, a glycidyl ether of an aliphatic alcohol or a polyglycidyl ether of an aliphatic polyol or an alkylene oxide adduct thereof is preferable because viscosity, coatability and reactivity are improved, and further, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1, 6-hexanediol diglycidyl ether is preferable.

As the aliphatic epoxy compound, commercially available products can be used, examples thereof include 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, DEOL EX-861, DEOL EX-911, DENACOL EX-941, DENACOL EX-920, and DENACOL EX-Chemtex (Nagaex, the above company; EPOLIGHT M-1230, EPOLIGHT40E, EPOLIGHT 100E, EPOLIGHT 200E, EPOLIGHT 400E, EPOLIGHT 70P, EPOLIGHT 200P, EPOLIGHT 400P, EPOLIGHT 1500NP, EPOLIGHT 1600, EPOLIGHT 80MF and EPOLIGHT 100MF (manufactured by Kyoeisha chemical Co., Ltd.); adeka Glycylol ED-503, Adeka Glycylol ED-503G, Adeka Glycylol ED-506, Adeka Glycylol ED-523T, Adeka Resin EP-4088S, KRM-523P, KRM-408, KRM-140 (manufactured by ADEKA corporation); 2EH (manufactured by Nissan synthetic Co., Ltd.).

The content of the aliphatic epoxy compound is not limited as long as a desired curing rate and adhesive strength can be obtained, and may be, for example, 0 to 90 parts by mass, and preferably 30 to 80 parts by mass, based on 100 parts by mass of the compound (B). When the content is in this range, the curing rate and the adhesive strength of the composition of the present invention become excellent.

The aromatic epoxy compound as the compound (B3) is an aromatic ring-containing epoxy compound having no bridged fused ring and a weight average molecular weight of 200 or more and less than 1000, which is not classified as an alicyclic epoxy compound.

Specific examples of the aromatic epoxy compound include mono/polyglycidyl etherates of monohydric phenols having at least 1 aromatic ring such as phenol, cresol, and butylphenol, or alkylene oxide adducts thereof, for example, glycidyl etherates of bisphenol a and bisphenol F, or compounds obtained by further adding alkylene oxide thereto, and phenol novolac-type epoxy compounds; glycidyl ethers of aromatic compounds having 2 or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; polyglycidyl ether compounds of aromatic compounds having 2 or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol; polyglycidyl esters of polybasic acid aromatic compounds having 2 or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimellitic acid; polyglycidyl esters of benzoic acids such as benzoic acid, toluic acid, and naphthoic acid, glycidyl esters of benzoic acid, and epoxides of styrene oxide and divinylbenzene. Among them, from the viewpoint of reducing the viscosity of the composition of the present invention, at least one selected from the group consisting of polyglycidyl ethers of phenols, polyglycidyl etherates of aromatic compounds having 2 or more alcoholic hydroxyl groups, polyglycidyl etherates of polyphenols, polyglycidyl esters of benzoic acids, and polyglycidyl esters of polybasic acids is preferably contained. As the aromatic epoxy compound, a bisphenol a type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound, and a phenol novolac type epoxy compound are preferable because of excellent adhesive force.

As the aromatic epoxy compound, commercially available products can be used, and examples thereof include DENACOL EX-145, DENACOL EX-146, DENACOL EX-147, DENACOL EX-201, DENACOL EX-203, DENACOL EX-711, DENACOL EX-721, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051, ONCOAT EX-1010, ONCOAT EX-1011, and ONCOAT 1012 (manufactured by Nagase Chemtex); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (manufactured by Osaka gas chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC corporation); ESN-475V (New Nippon iron King chemical Co., Ltd.); EPICOAT YX8800 (available from Mitsubishi chemical Co., Ltd.); marproof G-0105SA and Marproof G-0130SP (manufactured by Nichigan oil Co., Ltd.); EPICLON N-665, EPICLON HP-7200 (available from DIC corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kagaku Co., Ltd.); adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901, Adeka Resin EP-3300E, Adeka Resin EP-3950S, KRM-430, KRM-501 (manufactured by ADEKA corporation); TECHMORE VG-3101L (manufactured by PRINTEC, Inc.), and the like.

The content of the aromatic epoxy compound may be set to 0 part by mass or more and 90 parts by mass or less, and preferably 10 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the compound (B), as long as the desired curing rate and adhesive strength can be obtained. When the content is in this range, the curing rate and the adhesive strength of the composition of the present invention become excellent.

The oxetane compound as the compound (B3) is an oxetane compound having an oxetanyl group and no bridged fused ring and having a weight average molecular weight of 200 or more and less than 1000.

From the viewpoint of excellent balance between curability and coatability, an oxetane compound containing 1 to 3 oxetanyl groups is preferable, and an oxetane compound containing 2 oxetanyl groups is particularly preferable.

Examples of the oxetane compound include 3, 3' - [ oxybis (methylene) ] bis (3-ethyloxetane), (3, 7-bis (3-oxetanyl) -5-oxanonane, 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, Difunctional oxetane compounds such as 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 dioxetane and the like; monofunctional oxetane compounds such as 3-ethyl-3- [ (phenoxy) methyl ] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, and 3-ethyl-3- (chloromethyl) oxetane are preferred from the viewpoint of viscosity and reactivity to be monofunctional aliphatic oxetane compounds. These may be used alone in 1 kind or in combination of two or more kinds.

As the OXETANE compound, commercially available products containing a cationically polymerizable monomer as a main component can be used, and examples thereof include ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 and OXT-221 (manufactured by Toyo chemical Co., Ltd.); ENACOL OXBP, OXTP (product of Utsu corporation), etc.

The content of the oxetane compound is not limited as long as a desired curing rate and adhesive strength can be obtained, and for example, may be 0 to 50 parts by mass, and preferably 5 to 30 parts by mass, among 100 parts by mass of the compound (B). When the content is in this range, the coating property and curing speed of the composition of the present invention become excellent.

< radical polymerization initiator (C) >

As the component (C) used in the composition of the present invention, a conventionally known radical polymerizable initiator can be used.

The component (C) is a photo radical polymerization initiator or a thermal radical polymerization initiator. From the viewpoint of high reactivity, a photo radical polymerizable initiator is more preferable.

The component (C) is not particularly limited as long as it generates radicals by irradiation with light, and conventionally known compounds can be used, and preferable compounds include, for example, acetophenone compounds, benzil compounds, benzophenone compounds, thioxanthone compounds, oxime ester compounds, and the like.

Examples of the acetophenone-based compound include α -hydroxyacetophenone-based compounds such as benzoin, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4' -isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxymethyl-2-methylpropiophenone, and 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one; α -alkoxyacetophenone compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, diethoxyacetophenone, and 2, 2-dimethoxy-1, 2-diphenylethane-1-one; α -aminoacetophenone-based compounds such as p-dimethylaminoacetophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanone-1 and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; p-tert-butyl dichloroacetophenone, p-tert-butyl trichloroacetophenone and p-azidobenzylidene acetophenone.

In the composition of the present invention, an acetophenone-based compound is preferable, and particularly, an α -hydroxyacetophenone-based compound is particularly preferable, from the viewpoint of excellent transparency of the obtained cured product.

Examples of the benzil-based compound include benzil and the like.

Examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, michler's ketone, 4' -bisdiethylaminobenzophenone, 4 '-dichlorobenzophenone, and 4-benzoyl-4' -methylbenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2, 4-diethylthioxanthone.

The oxime ester compound is a compound having an oxime ester group, and is preferable because of its good sensitivity among photo radical polymerizable initiators.

Examples of the preferable oxime ester compounds include compounds nos. c1 to c14 shown below.

Examples of the other radical polymerizable initiator include phosphine oxide compounds such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis (cyclopentadienyl) bis [2, 6-difluoro-3- (pyrrol-1-yl) ] titanium.

As commercially available radical initiators, there may be mentioned ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831 and NCI-930 (manufactured by ADEKA Co., Ltd.); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, and IRGACURE784 (available from BASF corporation); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (made by Tronly Co., Ltd.).

The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used, and preferable compounds include azo compounds, peroxides, persulfates, and the like.

Examples of the azo compound include 2,2 '-azobisisobutyronitrile, 2' -azobis (methyl isobutyrate), 2 '-azobis-2, 4-dimethylvaleronitrile, and 1, 1' -azobis (1-acetoxy-1-phenylethane).

Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and the like.

Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

In the composition of the present invention, one or a mixture of two or more of the components (C) described in the examples so far may be used.

The content of the component (C) in the composition of the present invention is not particularly limited, and is preferably 1 to 10 parts by mass in 100 parts by mass of the total amount of the components (a) to (D), and is preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass with respect to 100 parts by mass of the component (a) in view of good curability. When the content of the component (C) is within the above range, a polymerizable composition having good curability and excellent storage stability without precipitation of a polymerizable initiator can be obtained, and therefore, the content is preferable.

< cationic polymerizable initiator (D) >

The component (D) used in the composition of the present invention is a compound capable of generating an acid by irradiation with an active energy ray such as a visible ray, an ultraviolet ray, an X-ray, an electron ray or a high frequency ray (hereinafter, also referred to as "active energy ray") (hereinafter, also referred to as "photocationic polymerization initiator") or a compound capable of generating an acid by heating (hereinafter, also referred to as "thermal cationic polymerization initiator").

In the composition of the present invention, the component (D) has an aromatic ring and the number of aromatic rings is 3 or more. Examples of the aromatic ring include aromatic hydrocarbon rings in which the atoms forming the ring structure, such as a benzene ring, a naphthalene ring, and an anthracene ring, are all carbon atoms; furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, etc. form an aromatic heterocyclic ring containing an atom other than carbon atoms as an atom forming the ring structure.

In the composition of the present invention, both a photocationic polymerizable initiator and a thermal cationic polymerizable initiator can be used as the component (D), and a photocationic polymerizable initiator is preferable from the viewpoint of sensitivity.

As the photo cation polymerizable initiator, onium salt double salts or derivatives thereof, oxime sulfonate compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, diazomethane compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, acetophenone derivative compounds, and the like can be used, and these may be used alone or in combination of two or more.

Among the above, in the composition of the present invention, the photo cation polymerizable initiator is preferably a double salt of an onium salt or a derivative thereof. This is because: by using such a photo cation polymerizable initiator, the curing speed and the adhesive strength of the composition of the present invention become excellent.

Among the onium salt double salts and derivatives thereof, examples of the compound having 3 or more aromatic rings include salts of cations and anions represented by the following general formula (1).

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

Here, the cation [ A ]]^m+Preferably, onium, the structure of which can be represented by the following general formula (2).

[(R¹⁰)^aQ]^m+ (2)

Here, R¹⁰The number of carbon atoms of (1) to (60) is an organic group optionally containing a plurality of atoms other than carbon atoms.

a is an integer of 1 to 5.

a number of R¹⁰Each independently optionally being the same or different.

a number of R¹⁰At least 1 of the above groups is the above organic group having an aromatic ring, a is R¹⁰The number of aromatic rings contained in (1) is 3 or more. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N ═ N. Further, a cation [ A ]]^m+When the valence of Q in (2) is Q, a relationship of "a" to "Q" must be established. Wherein N is lookedThe valence is 0.

Furthermore, an anion [ B ]]^m-The halide complex is preferably represented by the following general formula (3).

[LX_b]^m- (3)

Here, L is a metal or semimetal (Metalloid) which 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. Furthermore, an anion [ B ]]^m-When the valence of L in (b) is p, the relationship of m ═ b-p must be established.

As anions of the general formula (3) [ LX_b]^m-Specific examples of (2) include tetrakis (pentafluorophenyl) borate [ (C)₆F₅)₄B]^-Tetrafluoroborate (BF)₄)^-Hexafluorophosphate radical (PF)₆)^-Hexafluoroantimonate (SbF)₆)^-Hexafluoroarsenate (AsF)₆)^-Hexachloroantimonate (SbCl)₆)^-Tris (pentafluoromethyl) trifluorophosphate ion (FAP anion), and the like.

Furthermore, an anion [ B ]]^m-A structure represented by the following general formula (4) can also be preferably used.

[LX_b-1(OH)]^m- (4)

Here, L, X, b is the same as described above. Examples of the other anions that can be used include perchlorate ion (ClO)₄)^-Trifluoromethyl sulfite ion (CF)₃SO₃)^-Fluorosulfonate ion (FSO)₃)^-Tosylate anion, trinitrobenzene sulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctansulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like.

Among such onium salts, the composition of the present invention is particularly effective to use a sulfonium cation shown in the following group I or group II, and a sulfonium salt such as hexafluoroantimonate ion or tetrakis (pentafluorophenyl) borate ion. Of these, 1 kind of them may be used alone or two or more kinds may be used in combination.

< group I >

< group II >

Among these, from the viewpoint of practical use and photosensitivity, aromatic iodonium salts and aromatic sulfonium salts are preferably used, particularly aromatic sulfonium salts, and from the viewpoint of sensitivity, aromatic sulfonium salts represented by the following general formula (5) are more preferably used. This is because: by using the aromatic sulfonium salt as the photo cation polymerizable initiator, the curing speed and the adhesive strength of the composition of the present invention become excellent.

Here, in the general formula (5), R¹²¹、R¹²²、R¹²³、R¹²⁴、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹And R¹³⁰Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms,

R¹³¹、R¹³²、R¹³³and R¹³⁴Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms,

R¹³⁵represents a hydrogen atom, a halogen atom, An alkyl group having 1 to 10 carbon atoms or An optional substituent group represented by the following chemical formulae (A) to (C), An^q-Represents an anion having a valence of q, and p represents a coefficient for making the charge neutral.

In the chemical formulas (A) to (C), R²²¹、R²²²、R²²³、R²²⁴、R²²⁵、R²²⁶、R²²⁷、R²²⁸、R²²⁹、R²³⁰、R²³¹、R²³²、R²³³、R²³⁴、R²³⁶、R²³⁷、R²³⁸、R²³⁹、R²⁴⁵、R²⁴⁶、R²⁴⁷、R²⁴⁸And R²⁴⁹Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms,

R²⁴⁰、R²⁴¹、R²⁴²、R²⁴³and R²⁴⁴Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and represents a position bonded to S in the general formula (5).

In the compound represented by the general formula (5), R is¹²¹、R¹²²、R¹²³、R¹²⁴、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R¹³¹、R¹³²、R¹³³、R¹³⁴、R¹³⁵、R²²¹、R²²²、R²²³、R²²⁴、R²²⁵、R²²⁶、R²²⁷、R²²⁸、R²²⁹、R²³⁰、R²³¹、R²³²、R²³³、R²³⁴、R²³⁶、R²³⁷、R²³⁸、R²³⁹、R²⁴⁰、R²⁴¹、R²⁴²、R²⁴³、R²⁴⁴、R²⁴⁵、R²⁴⁶、R²⁴⁷、R²⁴⁸And R²⁴⁹Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

As R¹²¹、R¹²²、R¹²³、R¹²⁴、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R¹³¹、R¹³²、R¹³³、R¹³⁴、R¹³⁵、R²²¹、R²²²、R²²³、R²²⁴、R²²⁵、R²²⁶、R²²⁷、R²²⁸、R²²⁹、R²³⁰、R²³¹、R²³²、R²³³、R²³⁴、R²³⁶、R²³⁷、R²³⁸、R²³⁹、R²⁴⁰、R²⁴¹、R²⁴²、R²⁴³、R²⁴⁴、R²⁴⁵、R²⁴⁶、R²⁴⁷、R²⁴⁸And R²⁴⁹Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, tribromomethyl, difluoropentyl, tridecafluorohexyl, heptadecafluorooctyl, methoxymethyl, etc, 1, 2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, n-ethylthiomethyl, n-butylthiomethyl, n-butylthioethyl, n-butylthiomethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxyPropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1, 2-dihydroxyethyl, and the like.

As R¹²¹、R¹²²、R¹²³、R¹²⁴、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R²²¹、R²²²、R²²³、R224、R²²⁵、R²²⁶、R²²⁷、R²²⁸、R²²⁹、R²³⁰、R²³¹、R²³²、R²³³、R²³⁴、R²³⁶、R²³⁷、R²³⁸、R²³⁹、R²⁴⁵、R²⁴⁶、R²⁴⁷、R²⁴⁸And R²⁴⁹Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a sec-butyloxy group, a tert-butyloxy group, an isobutyloxy group, a pentyloxy group, an isopentyloxy group, a tert-pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a cyclohexylmethyloxy group, a tetrahydrofuryloxy group, a tetrahydropyranyloxy group, a 2-methoxyethyloxy group, a 3-methoxypropyloxy group, a 4-methoxybutyloxy group, a 2-butoxyethyloxy group, a methoxyethoxyethyloxy group, a 3-methoxybutyloxy group, a 2-methylthioethyloxy group, and a trifluoromethyloxy group.

As R¹²¹、R¹²²、R¹²³、R¹²⁴、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R²²¹、R²²²、R²²³、R²²⁴、R²²⁵、R²²⁶、R²²⁷、R²²⁸、R²²⁹、R²³⁰、R²³¹、R²³²、R²³³、R²³⁴、R²³⁶、R²³⁷、R²³⁸、R²³⁹、R²⁴⁵、R²⁴⁶、R²⁴⁷、R²⁴⁸And R²⁴⁹Examples of the ester group having 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl and acetylOxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.

As pAn in the general formula (5)^q-The q-valent anion is represented by the formula [ B ] as the above-mentioned anion]^m-Among the anions listed above, an anion having a predetermined valence may be used.

In the compositions of the invention, R¹³⁵Preferably selected from the formulae (A) to (C), and among them, preferably selected from the formulae (A) or (C). This is because: by reacting R¹³⁵With the above structure, the dispersion stability of the component (D) is excellent in balance with the curing speed and the adhesive force. In the composition of the present invention, R is R from the viewpoint of dispersion stability of the component (D)¹³⁵Preferred is formula (C). On the other hand, from the viewpoint of further improving the curing rate and the adhesive strength, R is¹³⁵Preferred is formula (A). In the composition of the present invention, it is preferable that the component (D) contains R from the viewpoint of excellent balance between dispersion stability of the component (D) and curing rate and adhesive force¹³⁵Is a component of the formula (A) and R¹³⁵Both of which are components of formula (C).

Component (D) contains R¹³⁵Is a component of the formula (A) and R¹³⁵When both are components of the formula (C), R is the same as R¹³⁵Is 100 parts by mass of the component of the formula (C), R¹³⁵The content of the component of the formula (a) may be 10 parts by mass or more and 200 parts by mass or less, and among them, preferably 50 parts by mass or more and 200 parts by mass or less, and preferably 80 parts by mass or more and 120 parts by mass or less. This is because: when the content is in this range, the dispersion stability of the component (D) is excellent in balance with the curing rate and the adhesive force.

R¹²¹、R¹²²、R¹²³、R¹²⁴、R¹²⁵、R¹²⁶、R¹²⁷、R¹²⁸、R¹²⁹、R¹³⁰、R¹³¹、R¹³²、R¹³³And R¹³⁴Is a hydrogen atom, a halogen atom, a carbon atom of 1 to 10An alkyl group, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, wherein a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferred, and a hydrogen atom is particularly preferred. This is because: by the functional group, the composition of the present invention has excellent balance between dispersion stability of the component (D), curing speed and adhesive force. This is because: the above cationic polymerization initiator can be easily synthesized.

R²²¹、R²²²、R²²³、R²²⁴、R²²⁵、R²²⁶、R²²⁷、R²²⁸、R²²⁹、R²³⁰、R²³¹、R²³²、R²³³、R²³⁴、R²³⁶、R²³⁷、R²³⁸、R²³⁹、R²⁴⁰、R²⁴¹、R²⁴²、R²⁴³、R²⁴⁴、R²⁴⁵、R²⁴⁶、R²⁴⁷、R²⁴⁸And R²⁴⁹Preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom. This is because: by the functional group, the composition of the present invention has excellent balance between dispersion stability of the component (D), curing speed and adhesive force. This is because: the above cationic polymerization initiator can be easily synthesized.

The content of the component (D) in the composition of the present invention may be any content as long as the desired curing rate and adhesive strength can be obtained, and for example, is preferably 0.1 part by mass or more and 10 parts by mass or less, of these, preferably 0.5 part by mass or more and 8 parts by mass or less, and particularly preferably 1.0 part by mass or more and 7 parts by mass or less, of these, particularly preferably 1.5 parts by mass or more and 6 parts by mass or less, and of these, particularly preferably 2.0 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the solid content of the composition of the present invention. When the content is within this range, the composition of the present invention has excellent balance between dispersion stability of the component (D), curing rate and adhesive force. The solid component of the composition of the present invention includes all components except the solvent.

Examples of commercially available products of the cationic polymerization initiator (D) include "CPI-100P" and "CPI-101A" (manufactured by SAN-APRO. LTD.); "IRGACURE 250" (manufactured by BASF SE), "ADEKA OPTOMERSP-172", "ADEKA OPTOMERSP-170", "ADEKA OPTOMERSP-152" and "ADEKA OPTOMERSP-150" (manufactured by ADEKA CORPORATION); "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L", and "SAN-AID SI-150L" (manufactured by Sanxin chemical industries, Ltd.).

In the composition of the present invention, the content of the component (D) is preferably 1 to 10 parts by mass in 100 parts by mass of the total amount of the components (a) to (D), and is preferably 1 part by mass or more and 8 parts by mass or less, particularly preferably 1.5 parts by mass or more and 7 parts by mass or less, particularly preferably 2.0 parts by mass or more and 6 parts by mass or less, particularly preferably 3.0 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the component (B), from the viewpoint of excellent curing speed and adhesive strength.

< solvent >

The composition of the present invention may use a solvent, which is a compound that can disperse or dissolve each component in the composition and is liquid at normal temperature and pressure. As the solvent, a solvent containing no compound having an acryloyl group, a methacryloyl group, a vinyl group, an epoxy group, or an oxetanyl group can be used.

As such a solvent, water or an organic solvent can be used, but an organic solvent can be preferably used. The content of the organic solvent is preferably 80 parts by mass or more, preferably 90 parts by mass or more, and preferably 95 parts by mass or more, particularly preferably 100 parts by mass, based on 100 parts by mass of the solvent, that is, the solvent preferably contains only the organic solvent, as long as the desired curing rate and adhesive strength can be obtained. This is because: when the content is in this range, the composition of the present invention has excellent balance between dispersion stability of the component (C) and the component (D), curing rate, and adhesive force.

Examples of the organic solvent include carbonates such as propylene carbonate, ethylene carbonate, 1, 2-butylene carbonate, dimethyl carbonate, and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, and derivatives thereof; cyclic ethers such as dioxane; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl glutarate, methyl acetoacetate, ethyl glutarate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; lactones such as γ -caprolactone, δ -caprolactone, e-caprolactone, dimethyl-e-caprolactone, δ -valerolactone, γ -valerolactone and γ -butyrolactone, and these solvents may be used in 1 kind or as a mixed solvent of two or more kinds. Among the organic solvents, derivatives, lactones, and carbonates of polyhydric alcohols are preferable, carbonates are particularly preferable, and propylene carbonate is particularly preferable among them. This is because: by using these organic solvents, the composition of the present invention has excellent balance between dispersion stability of the component (C) and the component (D), and curing speed and adhesive force.

The molecular weight of the organic solvent is preferably 50 or more and 300 or less, of these, preferably 80 or more and 200 or less, and preferably 90 or more and 150 or less, from the viewpoint of excellent balance between solubility or dispersion stability of the components (a) to (D) and curing rate and adhesive force.

The boiling point of the organic solvent is preferably 100 ℃ to 350 ℃, more preferably 130 ℃ to 300 ℃, particularly preferably 200 ℃ to 300 ℃, and most preferably 200 ℃ to 250 ℃, from the viewpoint of reducing volatilization of the organic solvent from the cured product. The boiling point indicates a value under atmospheric pressure.

< other ingredients >

The composition of the present invention may contain other components as required, in addition to the above components. The other components may include, as necessary, various resin additives such as inorganic fillers, organic fillers, pigments, colorants such as silane coupling agents and dyes, photosensitizers, antifoaming agents, thickeners, thixotropic agents, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow control agents, and adhesion promoters. The total content of other components is preferably 30% by mass or less in the solid content of the composition of the present invention.

The method for producing the composition of the present invention is not particularly limited as long as the components can be uniformly mixed, and examples thereof include the following methods: a method of adding and mixing the component (C), the component (D) and a solvent to the component (A) and the component (B). As the mixing method, a method using a known mixing device can be used, and for example, a method using a three-roll mill, a sand mill, a ball mill, or the like can be mentioned.

The method of curing the composition of the present invention can be appropriately set depending on the kinds of the component (C) and the component (D). As the curing method, in the case where the component (C) and the component (D) are a radical photopolymerization initiator and a cationic photopolymerization initiator, a method of performing an active energy ray irradiation treatment of irradiating the composition of the present invention with an active energy ray can be used.

The active energy ray includes visible light, ultraviolet rays, electron beams, X-rays, radiation rays, high frequency rays, and the like, and ultraviolet rays are most preferable because they are economical. Examples of the light source of ultraviolet rays include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp. In addition, the compositions of the present invention can be cured by illuminating an LED light source. The active energy ray from the LED light source may be ultraviolet ray. The wavelength of the active energy ray from the LED light source is 350nm to 405 nm. When the cationic polymerizable initiator is a photo cationic polymerizable initiator, the composition of the present invention can be cured to a dry-to-the-touch state or a solvent-insoluble state by irradiation with active energy rays, usually after 0.1 second to several minutes. The active energy ray and the time of exposure to the active energy ray may be the same as those described in international publication No. 2013/172145 and the like.

As the method for curing the composition of the present invention, a method of heat-treating the composition of the present invention may be used in the case where the component (C) is a thermal radical-polymerizable initiator or the component (D) is a thermal cationic-polymerizable initiator. The conditions for curing the composition of the present invention by heating may be 70 to 250 ℃ for 1 to 100 minutes. The baking may be performed after Pre-baking (PAB) and Post-baking (PEB) under pressure, or may be performed at different temperatures in a plurality of stages. The heating conditions vary depending on the kinds and the blending ratio of the components, and can be set as follows: at 70-180 ℃, the temperature is set to 5-15 minutes for an oven and 1-5 minutes for a heating plate. Thereafter, the coating film is cured at 180 to 250 ℃, preferably 200 to 250 ℃, for example, by heat treatment for 30 to 90 minutes in the case of an oven or 5 to 30 minutes in the case of a hot plate, thereby obtaining a cured film.

The use of the composition of the present invention is not particularly limited as long as it is a use in which a cured product is formed, and examples thereof include optical materials such as optical films, adhesives, spectacles, and photographic lenses; coating material, coating agent, backing agent, ink, high refractive material, water-soluble material, resist for semiconductor/display/MEMS/medical equipment, liquid resist, printing plate, insulating varnish, insulating sheet, laminated plate, printed substrate, sealant for semiconductor device/LED package/liquid crystal injection port/organic EL/optical element/electric insulation/electronic member/separation film, molding material, putty, glass fiber impregnant, caulking agent, passivation film for semiconductor/solar cell, interlayer insulation film, protective film for color filter, separator, DNA separation chip, microreactor, nanobiotechnical device, recording material for hard disk, solid photographic element, light-emitting diode, organic light-emitting device, light-emitting film, fluorescent film, light-emitting film, light, A lens portion of a lens sheet such as a prism lens sheet used for a backlight of a liquid crystal display device, a fresnel prism lens sheet used for a screen of a projection television or the like, a lenticular lens sheet or the like, or a backlight of a sheet using the same, an optical lens such as a microlens, an optical element, an optical connector, an optical waveguide, an injection molding agent for optical modeling, and the like.

The composition of the present invention is preferably used for an adhesive agent, from the viewpoint that the effects of excellent curing speed and adhesive strength can be more effectively exerted. Specific applications of the adhesive include optical materials such as glasses and imaging lenses; electronic material applications represented by laminates and printed boards; head-up displays, in-vehicle devices typified by car navigation, and display panels typified by organic EL and liquid crystal displays. Among them, the transparent resin composition is preferably used for applications requiring transparency, and particularly preferably used for applications such as optical materials, in-vehicle devices, and display panels.

When the composition of the present invention is used as an adhesive, any of inorganic materials and organic materials can be used for adherends to be bonded with the adhesive of the present invention.

Examples of the organic material include cellulose esters such as cellulose diacetate, cellulose Triacetate (TAC), cellulose propionate, cellulose butyrate, cellulose acetate propionate, and nitrocellulose; a polyamide; a polyimide; a polyurethane; an epoxy compound; a polycarbonate; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1, 4-cyclohexanedimethanol terephthalate), polyethylene-1, 2-diphenoxyethane-4, 4' -dicarboxylate, and polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene, polytetrafluoroethylene, cycloolefin polymer, and the like; vinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; a polycarbonate; polysulfones; polyether sulfone; a polyether ketone; a polyetherimide; high polymer materials such as polyoxyethylene and norbornene resins. Further, as the inorganic material, for example, glass such as soda glass and quartz glass; metals, metal oxides, and the like.

< adhesive agent >

Next, the adhesive of the present invention will be described.

The adhesive of the present invention comprises the composition of the present invention. The adhesive of the present invention is excellent in curing speed, adhesion and water resistance by containing the composition of the present invention.

The adhesive of the present invention can be produced using the composition of the present invention. The adhesive of the present invention may be composed of only the composition of the present invention, or may be produced by mixing the composition of the present invention with various known additives used in the production of adhesives by a known mixing apparatus. The composition and the adhesive of the present invention may be used in the same manner as described in the composition item, and therefore, the description thereof is omitted here.

When the adhesive of the present invention is used as an adhesive for bonding two members, the thickness of the adhesive of the present invention after curing can be appropriately set according to the use of the adhesive of the present invention, and may be, for example, 0.5 μm or more and 10 μm or less.

< cured product >

Next, the cured product of the present invention will be described.

The cured product of the present invention is a cured product of the composition of the present invention. The cured product of the present invention can be used as an adhesive layer having excellent curing speed and adhesive strength. The composition of the present invention may be the same as that described in the section "composition", and therefore, the description thereof is omitted here.

The cured product of the present invention is a cured product of the composition of the present invention, and includes a polymer of the composition of the present invention. That is, the cured product of the present invention has a bridged condensed ring.

The shape, thickness, and the like of the cured product of the present invention in a plan view can be appropriately set according to the use of the cured product and the like.

The cured product of the present invention is obtained by forming the composition of the present invention into a desired shape and curing the composition, and the production method is not particularly limited. The production method can be the same as that described in the section of the method for producing a cured product to be described later, and therefore, the description thereof is omitted here.

The use of the cured product of the present invention and the like can be the same as those described in the composition item.

< method for producing cured product >

Next, a method for producing a cured product of the present invention will be described.

The method for producing a cured product of the present invention includes a curing step of curing the composition of the present invention. According to the method for producing a cured product of the present invention, since the composition of the present invention is used in the curing step, a cured product having a curing rate and an adhesive force can be obtained. The respective steps of the method for producing a cured product of the present invention will be described in detail below.

1. Curing step

The curing step is a step of curing the composition of the present invention, and includes a step of irradiating an active energy ray or heating. The curing method can be the same as that described in the section "composition a".

2. Other procedures

The method for producing a cured product of the present invention may have other steps as necessary. Examples of such a step include a step of applying the composition of the present invention before a step of curing the composition of the present invention. As a method for applying the composition of the present invention, known methods such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, and dipping can be used. In the coating step, the composition of the present invention may be coated on a substrate.

The base material can be appropriately set according to the use of the cured product, and examples thereof include base materials containing soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like. The cured product may be used by being peeled from a substrate after being formed on the substrate, or may be used by being transferred from the substrate to another adherend.

The cured product produced by the production method of the present invention, the use thereof, and the like can be the same as those described in the section of the cured product.

The composition, the adhesive containing the same, the cured product thereof, and the method for producing the same of the present invention are not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same operational effects are included in the technical scope of the present invention.

Examples

The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples.

Examples 1 to 28 and comparative examples 1 to 7

The compositions were obtained by blending the respective components according to the formulations described in tables 1 to 5 below. The following materials were used for each component. The blending amounts in the tables represent parts by mass of the respective components.

Component (A)

A1-1: dicyclodecane dimethanol diacrylate

A1-2: acrylic acid dicyclopentyl ester

A2-1: acrylic acid 4-n-hydroxybutyl ester

A2-2: compound (A2) No.1

A3-1: tris (acryloylethyl) isocyanurate

A3-2: epsilon-caprolactone modified tris (2-acryloyloxyethyl) isocyanurate

A4-1: 1, 6-hexanediol diacrylate

A4-2: 1, 10-decanediol diacrylate

Ingredient (B)

B1-1: compound (B1) No.1

B1-2: compound (B1) No.2

B2-1: copolymers of glycidyl methacrylate and methyl methacrylate

(weight-average molecular weight is 8000, and epoxy equivalent is 500-600 g/eq.)

B2-2: copolymers of glycidyl methacrylate and methyl methacrylate

(weight-average molecular weight of 15000 and epoxy equivalent of 500-600 g/eq.)

B3-1: 1, 4-butanediol diglycidyl ether

B3-2: 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylic acid ester

B3-3: trimethylolpropane triglycidyl ether

B3-4: 3, 3' - [ oxybis (methylene) ] bis (3-ethyloxetane)

B3-5: diglycidyl ether of bisphenol A

Ingredient (C)

C-1: 1-hydroxycyclohexyl phenyl ketones

Ingredient (D)

D-1: CPI-100P (SAN-APRO. LTD. system)

Additive agent

E-1: flatting agent (Dow Toray Co., SH-29PA manufactured by Ltd.)

[ evaluation ]

The viscosity, initial curability, adhesion and water resistance of each of the obtained compositions were evaluated by the following procedures.

(viscosity)

For each of the obtained compositions, the viscosity was measured at 25 ℃ with an E-type viscometer. The composition having a viscosity of 30 to 80 mPas is excellent in coating property, and the composition having a viscosity of 40 to 70 mPas is particularly preferable.

(method of preparing sample for evaluation)

Each of the obtained compositions was applied to a PMMA FILM (Technilloy 125S001 manufactured by Sumitomo chemical Co., Ltd.) so that the thickness after curing became 3 μm, and then another COP (cycloolefin Polymer, model ZEONOR FILM 14-060 manufactured by ZEON Co., Ltd., Japan) FILM was laminated using a laminator, and irradiated with 1000mJ/cm of an electrodeless ultraviolet lamp through the COP FILM²The sample for evaluation was obtained.

The obtained evaluation samples were subjected to a 90 ° peel test and evaluated according to the following criteria. The results are also shown in tables 1 to 5 below. In the 90 ° peel test, the PMMA film was subjected to tensile peel in the 90 ° direction by a tensile tester FTN1-13A (AIKOH ENGINEERING) at 25 ℃ for the evaluation sample, and the maximum strength of the PMMA film when peeled from the COP film was measured as the adhesive strength.

(initial curing)

The obtained evaluation sample was allowed to stand at 30 ℃ under 50% RH and atmospheric pressure for 3 minutes from the exposure, and then cut out to have a width of 2.0cm to obtain an evaluation sample. The 90 ° peel test was performed using the evaluation sample, and the evaluation was performed according to the following criteria. The results are also shown in tables 1 to 5 below.

A: the adhesive force is more than 0.6N/20mm

B: the adhesive force is more than 0.4N/20mm and less than 0.6N/20mm

C: the adhesive force is less than 0.4N/20mm

An object rated A, B can be preferably used as an adhesive, with an object rated a being particularly preferred. The object evaluated as C is not preferable because the usable use thereof is limited.

(adhesion)

The obtained evaluation sample was exposed to light at 30 ℃ and 50% RH under atmospheric pressure for 12 hours, and then cut out to have a width of 2.0cm to obtain a sample for evaluation of adhesive strength. The obtained sample was subjected to a 90 ° peel test under the above conditions to measure the adhesion, and evaluated according to the following criteria.

A: the adhesive force is more than 2.5N/20mm

B: the adhesive force is more than 1.5N/20mm and less than 2.5N/20mm

C: the adhesive force is more than 1.0N/20mm and less than 1.5N/20mm

D: the adhesive force is less than 1.0N/20mm

An object having an adhesive force of a or B can be used as the adhesive, and an object having an adhesive force of a is particularly preferable. An object having an adhesive force of C, D is not preferable as the adhesive.

(Water resistance)

The water resistance was evaluated by the hot water post-adhesion strength. The obtained evaluation sample was immersed in warm water at 60 ℃ for 48 hours after exposure to light at 30 ℃ and 50% RH under atmospheric pressure for 12 hours, taken out of the warm water and dried, and then cut out to a width of 2.0cm to obtain a warm water post-adhesion evaluation sample. The obtained sample was subjected to a 90 ° peel test by the above method, and the hot water post-adhesion strength was measured and evaluated according to the following criteria.

A: the bonding force after warm water is more than 2.5N/20mm

B: the bonding force after warm water is more than 1.5N/20mm and less than 2.5N/20mm

C: the bonding force after warm water is more than 1.0N/20mm and less than 1.5N/20mm

D: the bonding force after warm water is less than 1.0N/20mm

An object having a hot water post-adhesion of A, B or C can be used as an adhesive having excellent water resistance, and an object having a hot water post-adhesion of A or B is preferable, and an object having a hot water post-adhesion of A is particularly preferable. An object having an adhesive strength D after being warmed with water is not preferable as an adhesive for applications where water resistance is required.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

As can be confirmed from tables 1 to 5: the compositions of the examples were excellent in coatability, initial curability, adhesion and water resistance. Thus, the composition of the present invention is useful as an adhesive.

Claims

1. A composition comprising a radically polymerizable component (A) and a cationically polymerizable component (B),

the radically polymerizable component (A) contains 70 to 100 parts by mass of a radically polymerizable compound (A1) having a bridged condensed ring per 100 parts by mass of the radically polymerizable component (A),

2. The composition according to claim 1, further comprising a radical polymerizable initiator (C) and a cation polymerizable initiator (D),

the composition contains 40 to 60 parts by mass of the radical polymerizable component (A), 30 to 50 parts by mass of the cation polymerizable component (B), 1 to 10 parts by mass of the radical polymerizable initiator (C) and 1 to 10 parts by mass of the cation polymerizable initiator (D) per 100 parts by mass of the total amount of the radical polymerizable component (A), the cation polymerizable component (B), the radical polymerizable initiator (C) and the cation polymerizable initiator (D).

3. The composition according to claim 1 or 2, wherein the bridged condensed ring included in the radically polymerizable compound (A1) and the cationically polymerizable compound (B1) is a bridged condensed ring having a structure represented by the following formula (I),

4. the composition according to any one of claims 1 to 3, wherein the cationically polymerizable component (B) comprises a cationically polymerizable compound (B2) having a weight average molecular weight of 1000 or more and less than 30000 and having no bridged fused ring.

5. The composition according to any one of claims 1 to 4, wherein the cationically polymerizable component (B) comprises a cationically polymerizable compound (B3) having a weight average molecular weight of 200 or more and less than 1000 and no bridged condensed ring.

6. The composition according to claim 5, wherein the cationically polymerizable compound (B3) comprises a compound having an oxetanyl group.

7. The composition according to any one of claims 1 to 6, wherein the radically polymerizable component (A) comprises a radically polymerizable compound (A2) having a cationically polymerizable group and having no isocyanurate ring or bridged condensed ring.

8. The composition according to any one of claims 1 to 7, wherein the radically polymerizable component (A) comprises a radically polymerizable compound (A3) having an isocyanurate ring and no bridged condensed ring.

9. An adhesive comprising the composition according to any one of claims 1 to 8.

10. A cured product comprising the composition according to any one of claims 1 to 8.

11. A method for producing a cured product, comprising: a step of irradiating or heating the composition according to any one of claims 1 to 8 with an active energy ray.