KR102815563B1 - Composition, adhesive containing the same, cured product thereof and method for producing the same - Google Patents

Abstract

Provided are a composition which provides a cured product having excellent curing speed and water resistance, and also excellent adhesive strength, an adhesive containing the composition, a cured product thereof, and a method for producing the same.
A composition containing a radical polymerizable component (A) and a cationic polymerizable component (B), wherein the radical polymerizable component (A) contains 70 to 100 parts by mass of a radical polymerizable compound (A1) having a crosslinked condensed ring, per 100 parts by mass of the radical polymerizable component (A), and the cationic polymerizable component (B) contains 10 to 50 parts by mass of a cationic polymerizable compound (B1) having a crosslinked condensed ring, per 100 parts by mass of the cationic polymerizable component (B).

Description

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

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 which provides a cured product having excellent curing speed and water resistance and also excellent adhesive strength, an adhesive containing the same, a cured product thereof, and a method for producing the same.

Cationic curable compositions are used in the fields of ink, paint, various coating agents, adhesives, optical materials, etc. Various reports have been made on improvements to such curable compositions.

For example, in Patent Document 1, an active energy ray-curable adhesive composition for plastic films and the like is proposed, which has low viscosity, excellent curability, excellent adhesion to various plastic films or sheets, and excellent colorless transparency. In addition, in Patent Document 2, an active energy ray-curable adhesive composition for plastic films and the like is proposed, which has low viscosity, excellent curability, excellent adhesion to various plastic films and the like even when the humidity in the atmosphere at the time of application and curing is high, and excellent colorless transparency. In addition, in Patent Document 3, a low-viscosity photocurable adhesive is proposed, which has excellent curability even when the humidity in the application environment is high, and has good adhesion after a certain period of time, durability, and adhesion after completion of a moisture-heat resistance test. In addition, Patent Document 4 proposes a method for producing a laminate, which includes a step of forming a curable resin composition layer by applying a photo- and thermosetting resin composition having a diacrylate having a dicyclopentadiene skeleton and a diglycidyl ether having a dicyclopentadiene skeleton, and further a step of irradiating the curable resin composition layer with an active energy ray.

Japanese Patent Publication No. 2015-034188 Japanese Patent Publication No. 2015-057467 Japanese Patent Publication No. 2015-143352 Japanese Patent Publication No. 2017-149135

However, the cationic curable compositions proposed in Patent Documents 1 to 4 have a problem in that sufficient curability is not obtained and the water resistance of the cured product obtained is not sufficient. For example, when used as an adhesive, there are cases where the curing speed is insufficient or sufficient adhesive strength and water resistance are not obtained.

Accordingly, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a composition which obtains a cured product having excellent curing speed and water resistance and excellent adhesive strength, an adhesive containing the composition, a cured product thereof, and a method for producing the same.

The inventors of the present invention have diligently studied to solve the above-mentioned problems and have achieved the above-mentioned purpose. Hereinafter, the present invention will be described in detail.

That is, the composition of the present invention is a composition containing a radical polymerizable component (A) and a cationic polymerizable component (B), wherein the radical polymerizable component (A) contains 70 to 100 parts by mass of a radical polymerizable compound (A1) having a crosslinked condensed ring, per 100 parts by mass of the radical polymerizable component (A).

The above cationic polymerizable component (B) is characterized in that it contains 10 to 50 parts by mass of a cationic polymerizable compound (B1) having a crosslinked condensed ring per 100 parts by mass of the cationic polymerizable component (B).

In the composition of the present invention, a radical polymerization initiator (C) and a cationic polymerization initiator (D) are further contained,

Among 100 parts by mass of the total amount of the radical polymerizable component (A), the cationic polymerizable component (B), the radical polymerizable initiator (C), and the cationic polymerizable initiator (D), it is preferable to contain 40 to 60 parts by mass of the radical polymerizable component (A), 30 to 50 parts by mass of the cationic polymerizable component (B), 1 to 10 parts by mass of the radical polymerizable initiator (C), and 1 to 10 parts by mass of the cationic polymerizable initiator (D). The above composition has excellent initial curability.

In addition, in the composition of the present invention, it is preferable that the crosslinked condensed ring included in the radical polymerizable compound (A1) and the cationic polymerizable compound (B1) is a crosslinked condensed ring having a structure represented by the following formula (I). The cured product obtained from the above composition has excellent water resistance.

In addition, in the composition of the present invention, it is preferable to contain, as the cationic polymerizable component (B), a cationic polymerizable compound (B2) having a weight average molecular weight of 1,000 or more and less than 30,000 and not having a crosslinked condensed ring. From the composition described above, a cured product having excellent water resistance is obtained.

In addition, in the composition of the present invention, it is preferable to contain, as the cationic polymerizable component (B), a cationic polymerizable compound (B3) having a weight average molecular weight of 200 or more and less than 1,000 and not having a crosslinked condensed ring. From the composition described above, a cured product having excellent coatability and water resistance is obtained.

In addition, in the composition of the present invention, it is preferable that the cationic polymerizable compound (B3) contains a compound having an oxetanyl group. From the composition described above, a cured product having excellent water resistance is obtained.

In addition, in the composition of the present invention, it is preferable to contain, as the radical polymerizable component (A), a radical polymerizable compound (A2) having a cationic polymerizable group and not having an isocyanurate ring and a crosslinked condensed ring. The above composition has excellent coatability and initial adhesiveness.

In addition, in the composition of the present invention, it is preferable to contain, as the radical polymerizable component (A), a radical polymerizable compound (A3) containing an isocyanurate ring and not having a crosslinked condensed ring. From the composition described above, a cured product having excellent water resistance is obtained.

The adhesive of the present invention is characterized by containing the composition of the present invention. By containing the composition of the present invention, an adhesive is obtained which has an excellent curing speed and a cured product having excellent adhesive strength 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 adhesive strength and water resistance is obtained.

The method for producing a cured product of the present invention is characterized by including a step of irradiating or heating the composition of the present invention with an active energy ray. Since the composition of the present invention includes the above-described components, a cured product having excellent adhesive strength and water resistance can be easily obtained.

According to the present invention, it is possible to provide a composition which provides a cured product having excellent curing speed and water resistance and also excellent adhesive strength, an adhesive containing the composition, a cured product thereof, and a method for producing the same.

Hereinafter, the composition of the present invention, the adhesive containing the same, the cured product thereof, and the manufacturing method thereof will be described in detail.

<Composition>

First, the composition of the present invention will be described.

The composition of the present invention is a composition containing a radically polymerizable component (A) (hereinafter also referred to as “component (A)”) and a cationic polymerizable component (B) (hereinafter also referred to as “component (B)”). In the composition of the present invention, 70 to 100 parts by mass of a radically polymerizable compound (A1) having a crosslinked condensed ring (hereinafter also referred to as “compound (A1)”) is contained per 100 parts by mass of component (A), and 10 to 50 parts by mass of a cationic polymerizable compound (B1) having a crosslinked condensed ring (hereinafter also referred to as “compound (B1)”) is contained per 100 parts by mass of component (B). That is, by containing the compound (A1) and the compound (B1) in an appropriate ratio as described above, a cured product having an excellent curing speed and excellent adhesiveness and water resistance is obtained.

In the composition of the present invention, in addition to the compound (A1) and the compound (B1), it is preferable to contain 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)"), since a highly curable composition can be obtained. The preferable ratios of the components (A), (B), (C), and (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, per 100 parts by mass of the total amount of the components (A), (B), (C), and (D). By using the above ratio, it is possible to obtain a composition in which a cured product having an excellent curing speed and excellent adhesion and water resistance is obtained.

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

<Radical polymerization component (A)>

Component (A) is a compound having a radical polymerizable group. This radical polymerizable group means a group capable of polymerizing in the presence of a radical, and examples thereof include an acrylic group, a methacrylic group, a vinyl group, and a thiol group. Component (A) is composed of a compound (A1), a radical polymerizable compound (A2) having a cationically polymerizable group and not having an isocyanurate ring and a crosslinked condensed ring (hereinafter also referred to as “compound (A2)”), a radical polymerizable compound (A3) having an isocyanurate ring and not having a crosslinked condensed ring (hereinafter also referred to as “compound (A3)”), and other radical polymerizable compounds that do not belong to compounds (A1) to (A3). In addition, these compounds can be used alone or in mixtures of two or more.

From the viewpoints of the ease of application, curing speed, etc. of the composition of the present invention, component (A) preferably contains a low molecular weight compound. Furthermore, since the low molecular weight compound is excellent in dispersibility or solubility in the composition, etc., a cured product having excellent transparency can be obtained. On the other hand, from the viewpoints of the adhesive strength of the composition of the present invention, etc., the radical polymerizable compound preferably contains a high molecular weight compound. From the viewpoints of the balance of the ease of application, curing speed, and adhesive strength of the composition, the radical polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound. Furthermore, since the high molecular weight compound can be used together with the low molecular weight compound, the dispersibility 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 any one that can obtain the desired coating properties, etc., and may be, for example, 1,000 or less, preferably 50 or more and 500 or less, and more preferably 50 or more and 300 or less. The molecular weight of the high-molecular-weight compound may be any one that can obtain the desired ease of adhesion, etc., and may be, for example, larger than 1,000, and preferably 1,000 or more and 50,000 or less, and more preferably 5,000 or more and 20,000 or less. In the following, the molecular weight represents the weight average molecular weight (Mw) when the compound is a polymer.

Here, the weight average molecular weight can be obtained as a standard polystyrene conversion value by gel permeation chromatography (GPC). The weight average molecular weight Mw can be obtained by measuring, for example, using GPC (LC-2000plus series) manufactured by Nippon Asakusa Co., Ltd., using tetrahydrofuran as an eluting solvent, using polystyrene standards for calibration curves with Mw 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and using KF-804, KF-803, KF-802 (manufactured by Showa Denko Co., Ltd.) as the measuring column. Additionally, the measurement temperature can be 40℃ and the flow rate can be 1.0mL/min.

The content of component (A) contained in the composition of the present invention is preferably 40 to 60 parts by mass, and particularly preferably 45 to 55 parts by mass, based on 100 parts by mass of the composition, since the composition has excellent water resistance.

<Compound (A1)>

Compound (A1) is a radically polymerizable compound having a bridged condensed ring. The bridged condensed ring of compound (A1) means a condensed ring sharing three or more carbon atoms, and it is preferable that the compound (A1) includes a bridged condensed ring having a structure represented by general formula (I).

Examples of cross-linked condensed rings with this type of structure include the following cross-linked condensed rings.

Among the crosslinked condensed rings exemplified, an adhesive containing a compound (A1) having crosslinked condensed rings No. 6, No. 7, and No. 8 is preferable because it has high adhesive strength and water resistance. Crosslinked condensed ring No. 6 is particularly preferable because it has a stable structure and high productivity.

Compounds (A1) having 1 to 4 radical polymerizable groups are preferable because they have a good balance of adhesiveness and coatability, and compounds (A1) having 1 to 3 radical polymerizable groups are particularly preferable.

Examples of the compound (A1) include tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl oxyethyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, norbornyl(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, adamantane(meth)acrylate, 2-isopropyl-2-adamantyl(meth)acrylate, etc.

As the compound (A1), commercially available products may be used. Commercially available products include, for example, Kayarad R-684 (manufactured by Nippon Chemical Industry); A-DCP and DCP (manufactured by Shin-Nakamura Chemical Industry); FA-511AS, FA-512AS, FA-513AS, FA-512M, FA-512MT, FA-513M (manufactured by Hitachi Chemical Industry).

<Compound (A2)>

As the compound (A2), any radical polymerizable compound having a cationic polymerizable group and not having an isocyanurate ring or a crosslinked condensed ring is acceptable, and is not particularly limited.

The cationically polymerizable group refers to a group capable of polymerization in the presence of an acid, and examples thereof include a hydroxyl group, an epoxy group, an alicyclic epoxy group, an oxetanyl group, and a vinyl ether group. As the cationically polymerizable group possessed by the compound (A2), from the viewpoint of adhesion to a substrate, a hydroxyl group is preferable. From the viewpoints of initial curability and adhesive strength, an epoxy group is preferable.

Examples of the compound (A2) include hydroxyl group-containing acrylic acid esters such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-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 epoxy (meth)acrylates of ethylene glycol diglycidyl ether, mono (meth)acrylate of diethylene glycol diglycidyl ether, mono (meth)acrylate of triethylene glycol diglycidyl ether, mono (meth)acrylate of polyethylene glycol diglycidyl ether, mono (meth)acrylate of propylene glycol diglycidyl ether, mono (meth)acrylate of tripropylene glycol diglycidyl ether, mono (meth)acrylate of polypropylene glycol diglycidyl ether, mono (meth)acrylate of neopentyl glycol diglycidyl ether; (meth)acrylic acid glycidyl, and the following compounds (A2) No. 1 to No. 4, (3-ethyloxetan-3-yl)methyl acrylate, etc.

As the radical polymerizable group of the compound (A2), from the viewpoint of excellent curing properties, an acrylic group is preferable as the radical polymerizable group. Furthermore, from the viewpoint of low viscosity and excellent coating properties, it is preferable to have one or two radical polymerizable groups.

When a radical polymerizable compound (A2) is contained in the radical polymerizable component (A), the preferable content of the radical 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 radical polymerizable component (A), since it has excellent adhesiveness, water resistance, and fluidity.

<Compound (A3)>

As the compound (A3), any radical polymerizable compound containing an isocyanurate ring and not having a crosslinked condensed ring is acceptable, and is not particularly limited.

Examples of the compound (A3) include tris[(meth)acryloxyalkyl]isocyanurates such as ε-caprolactone-modified tris[2-(meth)acryloxyethyl]isocyanurate, tri[(meth)acryloylethyl]isocyanurate, and tris[3-(meth)acryloxypropyl]isocyanurate, and di[(meth)acryloylethyl]-2-hydroxyethyl isocyanurate, monoallyl isocyanurate, diaryl isocyanurate, triallyl isocyanurate, and the following compound (A3) No. 1.

As the compound (A3), a commercial product may be used. Commercial products include, for example, Aronix M-215, M-315 (all manufactured by Toa Synthetic); NK Ester A-9300, A-9300-1CL, A-9300-3CL (all manufactured by Shin-Nakamura Chemical); and Daiku (manufactured by Mitsubishi Chemical).

As the radical polymerizable group of the compound (A3), from the viewpoint of excellent curability, an acrylic group is preferable. Furthermore, from the viewpoint of excellent curability, it is preferable to have a plurality of radical polymerizable groups, and in particular, 2 to 3 are preferable.

When a radical polymerizable compound (A3) is contained in the radical polymerizable component (A), the preferable content of the radical 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 radical polymerizable component (A), since it has excellent water resistance and fluidity.

<Other radical polymerizable compounds>

Examples of other radical polymerizable compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, himicic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], and ω-carboxypolycaprolactone mono(meth)acrylate; Unsaturated polybasic acids such as polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups; (Meth)acrylate methyl, (meth)acrylate butyl, (meth)acrylate isobutyl, (meth)acrylate-tert-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 tetrahydrofuryl, (meth)acrylate vinyl, (meth)acrylate allyl, (meth)acrylate benzyl, 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, Esters of unsaturated monobasic acids such as pentaerythritol tetra(meth)acrylate, polyester(meth)acrylate oligomers, and polyhydric alcohols or polyhydric phenols; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; acid anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydro phthalic anhydride, tetrahydro phthalic anhydride, trialkyltetrahydro phthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro phthalic anhydride-maleic anhydride adducts, dodecenyl succinic anhydride, and methylhimic anhydride; Amides of unsaturated monobasic acids and polyhydric amines, such as (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(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; There are vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinylthioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone and vinylpyridine, and vinylurethane compounds of polyisocyanate compounds.

As other radical polymerizable compounds, commercially available products can also be used. Commercially available products include, for example, Karaya DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (all manufactured by Nippon Gunyaku); NK Ester A-DOD-N, A-DPH, A-TMPT, A-HD-N, TMPT, NPG, and HD-N (all manufactured by Shin-Nakamura Chemical Industry); SPC-1000, SPC-3000 (all manufactured by Showa Denko); NK Oligo U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U-122A, U-340A, U-324A, UA-53H, UA-100, AH-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.), Artresin UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH-500, SH-9832, UN-901T, These include UN-904, UN-905, UN-906, UN-906S, UN-907, UN-952, UN-953, UN-954, H-91, H-135 (manufactured by Negami Industries, Ltd.), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (manufactured by Sartomer), and EBECRYL 8810 (manufactured by Daicel).

<Cation polymerizable component (B)>

The cationically polymerizable component (B) included in the composition of the present invention is a compound having a cationically polymerizable group and not having a radically polymerizable group. The component (B) is composed of a compound (B1), a cationically polymerizable compound (B2) having a cationically polymerizable group and not having a crosslinked condensed ring and having a weight average molecular weight of 1,000 or more and less than 30,000 (hereinafter also referred to as “compound (B2)”), a cationically polymerizable compound (B3) not having a crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000 (hereinafter also referred to as “compound (B3)”), and other cationically polymerizable compounds that do not belong to compounds (B1) to (B3). In the composition of the present invention, components (B) can be used singly or in mixtures of two or more. In addition, when the compound is a polymer, the molecular weight represents the weight average molecular weight (Mw).

The content of component (B) contained in the composition of the present invention is preferably 30 to 50 parts by mass, and particularly preferably 40 to 50 parts by mass, based on 100 parts by mass of the composition, since the composition has excellent water resistance.

From the viewpoints of the ease of application, curing speed, etc. of the composition of the present invention, component (B) preferably contains a low molecular weight compound. Furthermore, since the low molecular weight compound has excellent dispersibility or solubility in the composition, etc., a cured product with excellent transparency can be obtained. On the other hand, from the viewpoints of the adhesive strength of the composition of the present invention, etc., the cationically polymerizable compound preferably contains a high molecular weight compound. Furthermore, from the viewpoints of the balance of the ease of application, curing speed, and adhesive strength of the composition, the cationically polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound. Furthermore, since the high molecular weight compound can be used together with the low molecular weight compound, the dispersion or solubility in the composition of the present invention can be improved, and a cured product with excellent transparency can be obtained.

The content of the high molecular weight compound is not particularly limited as long as the desired curing speed and adhesive strength are obtained, and is appropriately adjusted from the viewpoint of the balance of, for example, adhesive strength and transparency, etc. The content of the high molecular weight compound can be specifically set to 0 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the solid content of the composition of the present invention, 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. When the content is within the above range, the composition of the present invention becomes excellent in curing speed and adhesive strength, and in particular, it becomes possible to form a cured product having excellent adhesive strength and excellent transparency.

<Compound (B1)>

Compound (B1) is a cationic polymerizable compound having a crosslinked condensed ring. Among crosslinked condensed rings, a crosslinked condensed ring having a structure represented by the general formula (I) is preferable because it has excellent water resistance, and in particular, an adhesive containing compound (B1) having crosslinked condensed rings No. 6, No. 7, and No. 8 has high adhesive strength and water resistance, and is therefore preferable. Crosslinked condensed ring No. 6 is particularly preferable because it has a stable structure and high productivity.

As compounds (B1), there are, for example, compounds (B1) No. 1 to No. 22 below.

As a compound (B1), a commercial product may be used. Commercial products include, for example, Adeka Resin EP-4088L, 4088S (all manufactured by ADEKA); XD-1000 (manufactured by Nippon Gunpowder Chemical), HP-7200 (manufactured by DIC), etc.

As the cationically polymerizable group of the compound (B1), from the viewpoints of high curability and excellent adhesiveness, an epoxy group is preferable, and a glycidyl ether group is particularly preferable. Furthermore, from the viewpoint of excellent curability, it is preferable to have a plurality of cationically polymerizable groups, and 2 to 3 are particularly preferable.

<Compound (B2)>

The compound (B2) is not particularly limited and may be a cationic polymerizable compound having a weight average molecular weight of 1,000 or more and less than 30,000 and not having a crosslinked condensed ring. The weight average molecular weight can be measured by the above-described measuring method. A composition containing the compound (B2) is preferable because it has improved water resistance.

Examples of the compound (B2) include copolymers of glycidyl methacrylate, such as polymers of glycidyl methacrylate and copolymers of glycidyl methacrylate and methyl methacrylate, and some modified ones of these, and examples of the glycidyl methacrylate include glycidyl methacrylate, 2-methyl glycidyl methacrylate, 4-hydroxybutyl methacrylate, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and the like. Furthermore, in addition to these, examples include polymers such as novolak-type epoxy resins, 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylol propane trivinyl ether, and copolymers thereof.

As a compound (B2), a commercial product may be used. Commercial products include, for example, G-0130M (manufactured by Nichiyu) and EOCN-104S (manufactured by Nippon Gunpowder).

As for the compound (B2), an epoxy equivalent of 1,000 or less is preferable because the curing property is excellent, and an epoxy equivalent of 200 to 600 is particularly preferable.

In addition, as the cationic polymerizable group possessed by the compound (B2), an epoxy group is preferable, and in particular, a glycidyl ether group is preferable, since a composition having high curability and high adhesive strength is obtained.

The preferred content of the cationic polymerizable compound (B2) that may be contained in the cationic polymerizable component (B) is 0 to 30 parts by mass per 100 parts by mass of the cationic polymerizable component (B), and particularly preferably 5 to 20 parts by mass, because it has excellent water resistance and fluidity.

<Compound (B3)>

The compound (B3) is not particularly limited as long as it is a cationic polymerizable compound having a weight average molecular weight of 200 or more and less than 1,000 and not having a crosslinked condensed ring. A composition containing the compound (B3) is preferable because it can achieve both adhesiveness and coatability. Examples of the compound (B3) include aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and oxetane compounds. However, 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 has excellent curability, and a composition containing a compound (B3) having an epoxy equivalent of 200 or less is particularly preferable.

As the cationic polymerizable group possessed by the compound (B3), an epoxy group is preferable, and a glycidyl ether group is particularly preferable, since a composition having high curability and high adhesive strength is obtained. In addition, as the compound (B3), a compound having an oxetanyl group is also preferable, since a composition having excellent water resistance is obtained.

When the cationic polymerizable compound (B3) is contained in the cationic polymerizable component (B), the preferred content is 0 to 90 parts by mass, and particularly preferably 35 to 80 parts by mass, per 100 parts by mass of the cationic polymerizable component (B), since it has excellent water resistance and fluidity.

A composition containing a compound (B3) containing 1 to 3 cationically polymerizable groups is preferable because it can achieve both adhesiveness and applicability, and a compound (B3) containing 1 to 2 cationically polymerizable groups is particularly preferable.

The alicyclic epoxy compound as a compound (B3) means a cationic polymerizable compound having an alicyclic epoxy group (3,4-epoxycyclohexyl group) and no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000. By using an alicyclic epoxy compound as a compound (B3), the initial curing property is improved, which is preferable.

As the alicyclic epoxy compound, for example, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylethyl-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, bis(3,4-epoxycyclohexylethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 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)] derivative, hexanoic acid There are bis[(7-oxabicyclo[4.1.0]heptan-3-yl)methyl], α-pinene oxide, and limonene dioxide.

As the alicyclic epoxy compound, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate and 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexylcarboxylate are preferable from the viewpoint of improving adhesion.

As the alicyclic epoxy compound, commercially available products can be used, and examples thereof include Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000, Cyclomer M100 (manufactured by Daicel); and CYRACURE UVR-6128 (manufactured by Dow Chemical Company).

The content of the alicyclic epoxy compound may be set so as to obtain the desired curing speed and adhesive strength, and for example, it may be 0 to 50 parts by mass per 100 parts by mass of compound (B), and among these, it is preferably 1 to 20 parts by mass. When the content is within the above range, the composition of the present invention has excellent curing speed and adhesive strength.

An aliphatic epoxy compound as a compound (B3) means a cationic polymerizable compound having a weight average molecular weight of 200 or more and less than 1,000, which does not have a crosslinked condensed ring and is not classified as an alicyclic epoxy compound or an aromatic epoxy compound described later, and does not contain an aliphatic ring or an aromatic ring.

Specific examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyfunctional epoxy compounds such as polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyl esters of aliphatic long-chain polybasic acids.

Representative compounds of aliphatic epoxy compounds 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 ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether, and also polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin. Examples include polyglycidyl ethers, diglycidyl esters of aliphatic long-chain dibasic acids. In addition, examples include monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, and epoxidized polybutadiene.

As the aliphatic epoxy compound, a glycidyl ether of an aliphatic alcohol or a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because the 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, a commercially available product can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (all manufactured by Nagase Chemtex); Eporite M-1230, Eporite 40E, Eporite 100E, Eporite 200E, Eporite 400E, Eporite 70P, Eporite 200P, Eporite 400P, Eporite 1500NP, Eporite 1600, Eporite 80MF, Eporite 100MF (all manufactured by Kyoeisha Chemical), Adecaglycirol ED-503, Adecaglycirol ED-503G, Adecaglycirol ED-506, Adecaglycirol ED-523T, Adecaresin EP-4088S, KRM-523P, KRM-408, KRM-140 (all manufactured by ADEKA); There are 2EH (Yokkaichi Synthetic Manufacturing), etc.

The content of the aliphatic epoxy compound may be any amount that can obtain the desired curing speed and adhesive strength, and for example, it may be 0 to 90 parts by mass per 100 parts by mass of the compound (B), and among these, it is preferably 30 to 80 parts by mass. When the content is within the above range, the composition of the present invention has excellent curing speed and adhesive strength.

An aromatic epoxy compound as a compound (B3) means an epoxy compound that is not classified as an alicyclic epoxy compound and contains an aromatic ring having a weight average molecular weight of 200 or more and less than 1,000 and does not have a crosslinked condensed ring.

Specific examples of the aromatic epoxy compound include monohydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or mono/polyglycidyl ethers of alkylene oxide adducts thereof, for example, glycidyl ethers of bisphenol A, bisphenol F, or compounds to which alkylene oxide is further added, or phenol novolak-type epoxy compounds; glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethanol, and benzenedibutanol; Examples thereof include polyglycidyl esters of polybasic aromatic compounds having two 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; epoxides of styrene oxide or divinylbenzene, and the like. Among these, from the viewpoint of lowering the viscosity of the composition of the present invention, it is preferable to contain at least one selected from the group consisting of polyglycidyl ethers of phenols, polyglycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups, polyglycidyl ether compounds of polyhydric phenols, polyglycidyl esters of benzoic acids, and polyglycidyl esters of polybasic acids. As aromatic epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds, and phenol novolac type epoxy compounds are preferable because they have excellent adhesive strength.

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, 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 Co., Ltd.); ESN-475V (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Corporation); Maproof G-0105SA, Maproof G-0130SP (manufactured by Nichiyu Corporation); Epiclone N-665, Epiclone HP-7200 (manufactured by 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 Gunkyaku Co., Ltd.); These include 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); TECHMORE VG-3101L (manufactured by PRINTEC), etc.

The content of the aromatic epoxy compound may be any amount that can obtain the desired curing speed and adhesive strength, and for example, it may be 0 to 90 parts by mass per 100 parts by mass of the compound (B), and among these, it is preferably 10 to 50 parts by mass. When the content is within the above range, the composition of the present invention has excellent curing speed and adhesive strength.

An oxetane compound as a compound (B3) means an oxetane compound having an oxetanyl group and no bridged condensed ring and having a weight average molecular weight of 200 or more and less than 1,000.

Since the balance between curability and coating properties is excellent, an oxetane compound containing 1 to 3 oxetanyl groups is preferable, and an oxetane compound containing 2 oxetanyl groups is particularly preferable.

As oxetane compounds, 3,3'-[oxybis(methylene)]bis(3-ethyloxetane), (3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, Examples thereof include bifunctional oxetane compounds such as 3-ethyl-3-(3-ethyl-3-oxetanylmethyloxymethyl)oxetane and xylylenebisoxetane; 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; and monofunctional aliphatic oxetane compounds are preferable in terms of viscosity and reactivity. These can be used singly or in combination of two or more.

As the oxetane compound, a commercially available product containing a cationic polymerizable monomer as a main component can be used, and examples thereof include alonoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, OXT-221 (manufactured by Doa Synthetic Co., Ltd.), etanacol OXBP, OXTP (manufactured by Ube Kosan Co., Ltd.), etc.

The content of the oxetane compound may be any amount that can obtain the desired curing speed and adhesive strength, and for example, it may be 0 to 50 parts by mass per 100 parts by mass of the compound (B), and among these, it is preferably 5 to 30 parts by mass. When the content is within the above range, the composition of the present invention has excellent coatability and curing speed.

<Radical polymerization initiator (C)>

As the component (C) used in the composition of the present invention, it is possible to use a conventionally known radical polymerization initiator.

Component (C) is a photo-radical polymerization initiator and a thermal radical polymerization initiator. Since it has high reactivity, a photo-radical polymerization initiator is more preferable.

As for the component (C), there is no particular limitation as long as it generates radicals by light irradiation, and it is possible to use a conventionally known compound. For example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, and oxime ester compounds can be exemplified as preferable ones.

As acetophenone compounds, for example, α-hydroxyacetophenone compounds such as benzoin, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxymethyl-2-methylpropiophenone, and 1-[4-(2-hydroxy ethoxy)-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 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-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, and p-azidobenzalacetophenone.

In the composition of the present invention, an acetophenone-based compound is preferable because the resulting cured product has excellent transparency, and an α-hydroxyacetophenone-based compound is particularly preferable.

Examples of benzyl compounds include benzyl, etc.

Examples of benzophenone compounds include benzophenone, o-benzoyl methyl benzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

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

An oxime ester compound means a compound having an oxime ester group, and is preferable among photoradical polymerization initiators because it has good sensitivity.

As preferred oxime ester compounds, there are, for example, the following compounds No. C1 to No. C14.

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

Examples of commercially available radical initiators include ADEKAOPTOMER N-1414, N-1717, N-1919, ADEKAACLES NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by Tronly).

As a thermal radical polymerization initiator, any compound known in the art can be used without particular limitation as long as it generates radicals by heating, and examples thereof include azo compounds, peroxides, and persulfates.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane.

Examples of peroxides include benzoyl peroxide, di-tert-butylbenzoyl peroxide, tert-butylperoxypivalate, and di(4-tert-butylcyclohexyl)peroxydicarbonate.

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

In the composition of the present invention, component (C) can be used by mixing one or more of the components exemplified so far.

In the composition of the present invention, the content of component (C) is not particularly limited, but is preferably 1 to 10 parts by mass based on 100 parts by mass of the total amount of components (A) to (D), and further, since curability is good, it is preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass based on 100 parts by mass of component (A). When the content of component (C) is within the above range, a polymerizable composition having good curability and excellent storage stability that does not entail precipitation of a polymerization initiator is obtained, which is preferable.

<Cationic polymerization 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 (hereinafter also simply referred to as an “active energy ray”) such as visible light, ultraviolet light, X-ray, electron beam, or high frequency (hereinafter also referred to as a “photocationic polymerization initiator”), or a compound capable of generating an acid by heating (hereinafter also referred to as a “thermal cationic polymerization initiator”).

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

In the composition of the present invention, as the type of component (D), both a photo-cationic polymerization initiator and a thermal-cationic polymerization initiator can be used, but from the standpoint of sensitivity, a photo-cationic polymerization initiator is preferable.

As a photo-cationic polymerization initiator, a compound salt or a derivative thereof, which is an onium salt, or

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, etc. can be used, and these can be used alone or in combination of two or more.

In the composition of the present invention, it is preferable that the photocationic polymerization initiator is an onium salt double salt or a derivative thereof. This is because, by being the above-mentioned photocationic polymerization initiator, the composition of the present invention has excellent curing speed and adhesive strength.

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

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

Here, it is preferable that the positive ion [A] m+ is onium, and its structure can be expressed by, for example, the following general formula (2).

[(R ¹⁰ ) ^a Q] ^m+ (2)

Here, R ¹⁰ is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms.

a is an integer from 1 to 5.

a R ¹⁰ may be the same or different, and each may be independent.

a R ¹⁰ is an organic group having at least one aromatic ring, and the number of aromatic rings included in a R ¹⁰ is 3 or more. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. In addition, when the valence of Q in the cation [A] ^m+ is set to q, the relationship m=aq must be established. However, N=N is treated as having a valence of 0.

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

[LX _b ] ^m- (3)

Here, L is a metal or metalloid that is the central atom of the halide complex, such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc.

X is a halogen atom.

b is an integer from 3 to 7.

In addition, when the valence of L in the anion [B] ^m- is set to p, the relationship m=bp needs to be established.

Specific examples of the anion [LX _b ] ^m- of general formula (3) include tetrakis(pentafluorophenyl)borate [(C ₆ F ₅ ) ₄ B] ^- , tetrafluoroborate (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarcetate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion), etc.

In addition, the anion [B] ^m- can also preferably be used with a structure represented by the following general formula (4).

[LX _b-1 OH)] ^m- (4)

Here, L, X, and b are the same as above. In addition, examples of other anions that can be used include perchlorate ion (ClO ₄ ) ^, trifluoromethylsulfite ^ion (CF ₃ SO ₃ ), fluorosulfonic acid ion (FSO ₃ ) ^, toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, and tetrakis(pentafluorophenyl)borate.

In the composition of the present invention, among such onium salts, it is particularly effective to use a sulfonium salt such as a sulfonium cation represented by Group I or Group II below, a hexafluoroantimony ion, a tetrakis(pentafluorophenyl)borate ion, etc. Among these, one type may be used alone or two or more types may be used in mixture.

<Army I>

<Army II>

Among these, from the viewpoints of practicality and photosensitivity, it is preferable to use an aromatic iodonium salt or an aromatic sulfonium salt, and in particular, an aromatic sulfonium salt is preferable, and an aromatic sulfonium salt represented by the following general formula (5) is more preferable from the viewpoint of sensitivity. In addition, since the photocationic polymerization initiator is an aromatic sulfonium salt, the composition of the present invention has excellent curing speed and adhesive strength.

Here, in general formula (5), R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ and R ¹³⁰ each independently represent 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.

R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms,

R ¹³⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any one of the substituents selected from the following chemical formulas (A) to (C), An ^q- represents an anion having a valence of q, and p represents a coefficient that makes the charge neutral.

Among the chemical formulas (A) to (C) above,

R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ , R ²³⁶ , R ²³⁷ , R ²³⁸ , R 239 , R ²⁴⁵ , R ²⁴⁶ , R ²⁴⁷ , R ²⁴⁸ and ^{R 249 each} independently represent 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,

R ²⁴⁰ , R ²⁴¹ , R ²⁴² , R ²⁴³ and R ²⁴⁴ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and * represents a bonding position with S in general formula (5).

In a compound represented by general formula (5), R ¹²¹ , R ¹²² , R 123 , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁵ , R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ , R ²³⁶ , ^R237 , R ²³⁸ , R ²³⁹ , R Examples of halogen atoms represented by R ²⁴⁰ , R ²⁴¹ , R ²⁴² , R ²⁴³ , R ²⁴⁴ , R ²⁴⁵ , R ²⁴⁶ , R ²⁴⁷ , R ²⁴⁸ and R ²⁴⁹ include fluorine, chlorine, bromine and iodine.

R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁵ , R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ , R ²³⁶ , R ²³⁷ , R ²³⁸ , R ²³⁹ , R ²⁴⁰ , R ²⁴¹ , R ²⁴² , R ²⁴³ , R ²⁴⁴ , R ²⁴⁵ , R ²⁴⁶ , R ²⁴⁷ , R ²⁴⁸ and R ²⁴⁹ , the alkyl group having 1 to 10 carbon atoms is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyl octyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, Tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, tert-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, tert-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, tert-butoxycarbonylmethyl, Examples include ethyloxycarbonylmethyl, ethylcarbonylmethyl, tert-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1,2-dihydroxyethyl, and the like.

The number of carbon atoms represented by R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ , R ²³⁶ , R ²³⁷ , R ²³⁸ , R ²³⁹ , R ²⁴⁵ , R ²⁴⁶ , R 247 , R ²⁴⁸ , R ²⁴⁸ and R ²⁴⁹ Examples of the alkoxy group having a carbon number of 1 to 10 include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, and trifluoromethyloxy.

As ^the ester group having 2 to 10 carbon atoms represented ^by R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , ^R130 , R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ , R ²³⁶ , R ²³⁷ , R ²³⁸ , R 239 , R ²⁴⁵ , R ²⁴⁶ , R 247 , R ²⁴⁸ and R 249, Examples include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, tert-butylcarbonyloxy, methoxyacetyloxy, and benzoyloxy.

As the anion having a q valence represented by pAn ^q- in general formula (5), an anion having a predetermined valence can be used among those exemplified as the anion [B] ^m- mentioned above.

In the composition of the present invention, R ¹³⁵ is preferably selected from chemical formulas (A) to (C), and among them, it is preferably selected from chemical formula (A) or chemical formula (C). This is because, when R ¹³⁵ has the above-described structure, the balance between the dispersion stability of the component (D) and the curing speed and the adhesive strength is excellent. In the composition of the present invention, from the viewpoint of the dispersion stability of the component (D), it is preferable that R ¹³⁵ is chemical formula (C). On the other hand, from the viewpoint of further improving the curing speed and the adhesive strength, it is preferable that R ¹³⁵ is chemical formula (A). In the composition of the present invention, from the viewpoint of improving the dispersion stability of the component (D) and the balance between the curing speed and the adhesive strength, it is preferable that the component (D) contains both R ¹³⁵ of chemical formula (A) and R 135 of chemical formula (C).

When component (D) contains both R ¹³⁵ of chemical formula (A) and R 135 of chemical formula (C), the content of R ¹³⁵ of chemical formula (A) can be 10 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the component of chemical formula (C), and among these, it is 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 the content within the above-mentioned range provides an excellent balance between the dispersion stability of component (D) and the curing speed and adhesive strength.

R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R 129 , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ are each 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, but among these, 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 preferable, and a hydrogen atom is particularly preferable. This is because, by virtue of the functional group described above, the composition of the present invention has an excellent balance between the dispersion stability of component (D) and the curing speed and adhesive strength. In addition, the cationic polymerization initiator facilitates synthesis.

R ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ , R ²³⁶ , R ²³⁷ , R ²³⁸ , R 239 , R ²⁴⁰ , R ²⁴¹ , R ²⁴² , R ²⁴³ , R ²⁴⁴ , R ²⁴⁵ , R ²⁴⁶ , R ²⁴⁷ , R ²⁴⁸ and R ²⁴⁹ are preferably 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 virtue of the aforementioned functional group, the composition of the present invention has an excellent balance between the dispersion stability of component (D) and the curing speed and adhesive strength. In addition, the cationic polymerization initiator is easy to synthesize.

In the composition of the present invention, the content of component (D) may be any amount that can obtain the desired curing speed and adhesive strength, and for example, based on 100 parts by mass of the solid content of the composition of the present invention, it is preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 8 parts by mass or less, and particularly preferably 1.0 parts by mass or more and 7 parts by mass or less, and particularly preferably 1.5 parts by mass or more and 6 parts by mass or less, and particularly preferably 2.0 parts by mass or more and 5 parts by mass or less. By having the content within the above range, the composition of the present invention has an excellent balance between the dispersion stability of component (D) and the curing speed and adhesive strength. In addition, the solid content of the composition of the present invention includes all components other than a solvent.

Examples of commercially available cationic polymerization initiators (D) include “CPI-100P”, “CPI-101A” (all manufactured by San-Apro Co., Ltd.); “IRGACURE 250” (manufactured by BASF SE); “ADEKA OPTOMER SP-172”, “ADEKA OPTOMER SP-170”, “ADEKA OPTOMER SP-152”, “ADEKA OPTOMER SP-150” (all manufactured by ADEKA Corporation); “San-Aid SI-60L”, “San-Aid SI-80L”, “San-Aid SI-100L”, “San-Aid SI-150L” (all manufactured by Sanshin Chemical Industry Co., Ltd.).

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

<Solvent>

The composition of the present invention may use a solvent, and the solvent is a compound capable of dispersing or dissolving each component in the composition and being liquid under normal temperature and pressure. In addition, as the solvent, one that does not contain a compound having an acrylic group, a methacrylic group, a vinyl group, an epoxy group, or an oxetane group can be used.

As such a solvent, both water and organic solvents can be used, but organic solvents are preferably used. The content of the organic solvent may be such that the desired curing speed and adhesive strength are obtained, and is preferably 80 parts by mass or more per 100 parts by mass of the solvent, preferably 90 parts by mass or more, and among these, 95 parts by mass or more is preferable, and in particular, 100 parts by mass, that is, it is preferable that only the organic solvent is contained as the solvent. When the content is within the above range, the composition of the present invention has an excellent balance between the dispersion stability of the component (C) and the component (D), and the curing speed and adhesive strength.

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 and derivatives thereof such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate; cyclic ethers such as dioxane; Esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; Examples thereof include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone, and these solvents can be used as one kind or a mixed solvent of two or more kinds. Among the organic solvents, derivatives of polyhydric alcohols, lactones, and carbonates are preferable, particularly carbonates are preferable, and among these, propylene carbonate is particularly preferable. By using these organic solvents, the composition of the present invention has an excellent balance of dispersion stability of component (C) and component (D), curing speed, and adhesive strength.

As for the molecular weight of the organic solvent, from the viewpoint of achieving an excellent balance between the solubility or dispersion stability of components (A) to (D) and the curing speed and adhesive strength, it is preferably 50 or more and 300 or less, and among these, it is preferably 80 or more and 200 or less, and preferably 90 or more and 150 or less.

As for the boiling point of the organic solvent, from the viewpoint of reducing volatilization into the cured product, it is preferably 100°C or more and 350°C or less, and among these, it is preferably 130°C or more and 300°C or less, and particularly preferably 200°C or more and 300°C or less, and among these, it is especially preferably 200°C or more and 250°C or less. In addition, the boiling point represents the value under atmospheric pressure.

<Other ingredients>

The composition of the present invention may contain other components in addition to the above-described components, if necessary. The other components may contain various resin additives, such as inorganic fillers, organic fillers, pigments, silane coupling agents, colorants such as dyes, photosensitizers, antifoamers, thickeners, thixotropic agents, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, and adhesion promoters, if necessary. The total content of the other components is preferably 30 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 it is a method capable of uniformly mixing the above-mentioned components, and for example, there is a method of adding component (C), component (D) and solvent to component (A) and component (B) and mixing them. In addition, as the mixing method, a method using a known mixing device can be adopted, and for example, there is a method using a 3-roll, sand mill, ball mill, etc.

The curing method of the composition of the present invention is appropriately set depending on the types of component (C) and component (D). As the curing method, when component (C) and component (D) are a photo-radical polymerization initiator and a photo-cationic polymerization initiator, a method of performing an active energy ray irradiation treatment for irradiating the composition of the present invention with an active energy ray can be used.

Examples of the active energy ray include visible light, ultraviolet rays, electron rays, X-rays, radiation, and high frequency, and ultraviolet rays are economically most preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp. In addition, the composition of the present invention can be cured by irradiating it with an LED light source. An example of the active energy ray from the LED light source is ultraviolet rays. An example of the wavelength of the active energy ray from the LED light source is 350 nm to 405 nm. When the cationic polymerization initiator of the composition of the present invention is a photocationic polymerization initiator, it can be cured to a touch-dry state or a solvent-insoluble state usually after 0.1 second to several minutes by irradiation with an active energy ray. The active energy ray and the exposure time to the active energy ray can be the same as those described in International Publication No. 2013/172145, etc.

As a curing method for the composition of the present invention, when component (C) is a thermal radical polymerization initiator, or when component (D) is a thermal cation polymerization initiator, a method of performing a heat treatment on the composition of the present invention can be used. The conditions for curing the composition of the present invention by heating can be 70°C to 250°C for 1 to 100 minutes. After prebaking (PAB; Pre applied bake), pressurization can be performed, and post-baking (PEB; Post exposure bake) can be performed, or baking can be performed at several different temperatures. The heating conditions vary depending on the type and mixing ratio of each component, but can be, for example, 70°C to 180°C for 5 to 15 minutes in an oven, or for 1 to 5 minutes in a hot plate. Thereafter, a cured film can be obtained by heat treatment at 180°C to 250°C, preferably 200°C to 250°C, for 30 to 90 minutes in an oven or for 5 to 30 minutes on a hot plate to harden the film.

The use of the composition of the present invention is not particularly limited as long as it is a use for forming and using a cured product, and includes optical materials represented by optical films, adhesives, glasses, and imaging lenses, paints, coating agents, lining agents, inks, high-refractive-index materials, water-soluble materials, resists for semiconductors, displays, MEMS, and medical devices, liquid resists, printing plates, insulating varnishes, insulating sheets, laminated plates, printed circuit boards, sealants for semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic components, and separators, molding materials, putties, glass fiber impregnating agents, sealants, passivation films for semiconductors, solar cells, and the like, interlayer insulating films, protective films, protective films for color filters, spacers, DNA separation chips, microreactors, nanobiodevices, recording materials for hard disks, solid-state imaging elements, light-emitting diodes, organic light-emitting devices, luminescent films, and fluorescent materials. Examples thereof include films, actuators, holograms, plasmonic devices, polarizing plates, polarizing films, phase difference films, prism lens sheets used for backlights of liquid crystal displays, Fresnel screen sheets used for screens of projection TVs, lens sections of lens sheets such as lenticular lens sheets, or backlights using such sheets, optical lenses such as micro lenses, optical elements, optical connectors, optical waveguides, and optical shaping molding agents.

The composition of the present invention is preferably used in an adhesive from the viewpoint of being able to more effectively exhibit the excellent effects of curing speed and adhesive strength. As specific uses of the adhesive, it can be used in various uses such as optical materials represented by glasses or imaging lenses, electronic materials represented by laminated plates or printed circuit boards, vehicle-mounted devices represented by head-up displays or car navigation systems, and display panels represented by organic EL or liquid crystals. Among them, it is preferably used in uses requiring transparency, and in particular, it is preferably used in uses such as optical materials, vehicle-mounted devices, and display panels.

When the composition of the present invention is used as an adhesive, the adherend to be adhered by the adhesive of the present invention can use both inorganic materials and organic materials.

Examples of the organic materials include cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose; polyamides; polyimides; polyurethanes; epoxy compounds; polycarbonates; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene, polytetrafluoroethylene, and cycloolefin polymers; vinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; There are polymer materials such as acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; polycarbonate; polysulfone; polyethersulfone; polyether ketone; polyether imide; polyoxyethylene, and norbornene resin. In addition, as inorganic materials, there are glasses such as soda glass and quartz glass, metals, and metal oxides, for example.

<Adhesive>

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

The adhesive of the present invention comprises the composition of the present invention. By comprising the composition of the present invention, the adhesive of the present invention has excellent curing speed, adhesive strength, and water resistance.

The adhesive of the present invention can be manufactured using the composition of the present invention. The adhesive of the present invention may be manufactured by only the composition of the present invention, or by mixing the composition of the present invention with various additives known to be used when manufacturing adhesives using a known mixing device. In addition, the use of the composition and adhesive of the present invention can be the same as that described in the composition section, so 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 is appropriately set depending on the intended use of the adhesive of the present invention, but can be, for example, 0.5 µm or more and 10 µm or less.

<Curing Material>

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, for example, as an adhesive layer having excellent curing speed and adhesive strength. In addition, the composition of the present invention can be the same as the contents described in the section of “Composition,” so 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 crosslinked condensation ring.

The shape, thickness, etc. of the cured product of the present invention when viewed from a planar surface can be appropriately set depending on the intended use of the cured product.

The cured product of the present invention is formed by forming the composition of the present invention into a desired shape and curing it, and there is no particular limitation on the manufacturing method. As such a manufacturing method, for example, it can be the same as the content described in the section on the manufacturing method of the cured product described below, and therefore, a description thereof is omitted here.

The uses of the cured product of the present invention, etc. can be the same as those described in the composition section.

<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 process for curing the composition of the present invention. According to the method for producing a cured product of the present invention, since the curing process uses the composition of the present invention, a cured product having a curing speed and adhesive strength can be obtained. Hereinafter, each process of the method for producing a cured product of the present invention will be described in detail.

1. Curing process

The curing process is a process for curing the composition of the present invention, and includes a process for irradiating or heating an active energy ray. The curing method can be the same as that described in the section “A. Composition.”

2. Other processes

The method for producing a cured product of the present invention may include other processes as needed. As such processes, a process of applying the composition of the present invention before the process of curing the composition of the present invention may be exemplified. As a method of applying the composition of the present invention, a known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, or dipping may be used. The applying process may apply the composition of the present invention onto a substrate.

The substrate can be appropriately set depending on the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, etc. In addition, the cured product may be used by being peeled off from the substrate after being formed on the substrate, or may be used by being transferred from the substrate to another adherend.

The cured product and its use, etc. manufactured by the manufacturing method of the present invention can be the same as those described in the section on cured product.

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

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Examples 1 to 28 and Comparative Examples 1 to 7]

According to the mixing ratios described in Tables 1 to 5 below, each component was mixed to obtain a composition. Each component used the following materials. The mixing amount in the table represents the mass part of each component.

Component (A)

A1-1: Tricyclodecane dimethanol diacrylate

A1-2: Dicyclopentanyl acrylate

A2-1: 4-n-hydroxybutylacrylate

A2-2: Compound (A2) No.1

A3-1: Tri(acryloylethyl)isocyanurate

A3-2: ε-caprolactone modified tris(2-acryloxyethyl)isocyanurate

A4-1: 1,6-Hexanediol diacrylate

A4-2: 1,10-decanediol diacrylate

Component (B)

B1-1: Compound (B1) No.1

B1-2: Compound (B1) No.2

B2-1: Copolymer of glycidyl methacrylate and methyl methacrylate

(Weight average molecular weight 8,000, epoxy equivalent 500-600 g/eq.)

B2-2: Copolymer of glycidyl methacrylate and methyl methacrylate

(Weight average molecular weight 15,000, epoxy equivalent 500-600 g/eq.)

B3-1: 1,4-Butanediol diglycidyl ether

B3-2: 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexylcarboxylate

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-Hydroxycyclohexylphenyl ketone

Ingredient (D)

D-1: CPI-100P (manufactured by San-Apro Co., Ltd.)

Additives

E-1: Leveling agent (SH-29PA manufactured by Toray and Dow Corning)

[evaluation]

For each obtained composition, viscosity, initial curing properties, adhesion, and water resistance were evaluated according to the following procedure.

(viscosity)

The viscosity of each obtained composition was measured at 25°C using an E-type viscometer. A composition having a viscosity of 30 to 80 mPa·s is preferable because it has excellent coatability, and a composition having a viscosity of 40 to 70 mPa·s is particularly preferable.

(Method of making samples for evaluation)

Each obtained composition was applied to a PMMA film (Decnoloy 125S001 manufactured by Sumitomo Chemical Co., Ltd.) so that the thickness after curing would be 3 ㎛, and then two more corona-discharge-treated COP (cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd.: serial number Zeonoa Film 14-060) films were bonded together using a laminator, and light equivalent to 1,000 mJ/ ^cm2 was irradiated through the COP film using an electrodeless ultraviolet light lamp to obtain an evaluation sample.

The obtained evaluation sample was subjected to a 90° peel test, and evaluated according to the following criteria. The results are shown in Tables 1 to 5 below. In the 90° peel test, the evaluation sample was peeled by pulling the PMMA film in the 90° direction under conditions of 25°C using a tensile tester FTN1-13A (manufactured by Aiko Engineering Co., Ltd.), and the maximum strength when the PMMA film peels from the COP film was measured as the adhesive strength.

(early hardening)

After the obtained evaluation sample was left stationary for 3 minutes under the conditions of 30°C, 50%RH, and atmospheric pressure, it was cut into 2.0 cm wide pieces to obtain an evaluation sample. Using this evaluation sample, a 90° peel test was performed, and the evaluation was performed according to the following criteria. The results are shown in Tables 1 to 5 below.

A: Adhesion is 0.6N/20mm or more

B: Adhesion is 0.4N/20mm or more and less than 0.6N/20mm

C: Adhesion less than 0.4N/20mm

Those with evaluations of A and B can be preferably used as adhesives, and those with evaluations of A are particularly preferable. Those with evaluations of C are not preferable because their usable uses are limited.

(Adhesion)

For the obtained evaluation sample, 12 hours after exposure under the conditions of 30°C, 50%RH, and atmospheric pressure, the sample was cut into 2.0 cm widths to obtain a sample for adhesion evaluation. For the obtained sample, the adhesion was measured by performing a 90° peel test under the above conditions, and the evaluation was performed according to the following criteria.

A: Adhesive strength is 2.5N/20mm or more

B: Adhesion is 1.5N/20mm or more and less than 2.5N/20mm

C: Adhesion is 1.0N/20mm or more and less than 1.5N/20mm

D: Adhesion less than 1.0N/20mm

Those with adhesive strengths of A or B can be used as adhesives, and those with adhesive strengths of A are particularly preferred. Those with adhesive strengths of C and D are not preferred as adhesives.

(water resistance)

The water resistance was evaluated by the adhesive strength after hot water. For the obtained evaluation sample, 12 hours after exposure under the conditions of 30°C, 50%RH, and atmospheric pressure, it was immersed in hot water at 60°C for 48 hours, taken out from the hot water, dried, and then cut into 2.0 cm wide pieces to obtain a sample for evaluating the adhesive strength after hot water. For the obtained sample, a 90° peel test was performed by the above-mentioned method, the adhesive strength after hot water was measured, and the evaluation was performed according to the following criteria.

A: Adhesion strength after hot water is 2.5N/20mm or more

B: Adhesion after hot water is 1.5N/20mm or more and less than 2.5N/20mm

C: Adhesion after hot water is 1.0N/20mm or more and less than 1.5N/20mm

D: Adhesion after hot water is less than 1.0N/20mm

An adhesive whose adhesive strength after hot water is A, B or C can be used as an adhesive with excellent water resistance, preferably A or B, and particularly preferably A. An adhesive whose adhesive strength after hot water is D is not preferable as an adhesive for applications requiring water resistance.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

From Tables 1 to 5, it was confirmed that the compositions of the examples had excellent applicability, initial curing properties, adhesive strength, and water resistance. Therefore, the compositions of the present invention are useful as adhesives.

Claims (11)

In a composition containing a radical polymerizable component (A) and a cationic polymerizable component (B),
The above radical polymerizable component (A) contains 70 to 100 parts by mass of a radical polymerizable compound (A1) having a crosslinked condensed ring per 100 parts by mass of the radical polymerizable component (A).
The above cationic polymerizable component (B) contains 10 to 33.3 mass parts of a cationic polymerizable compound (B1) having a crosslinked condensed ring per 100 mass parts of the cationic polymerizable component (B).
It further contains a radical polymerization initiator (C) and a cationic polymerization initiator (D),
A composition containing 40 to 60 parts by mass of the radical polymerizable component (A), 30 to 50 parts by mass of the cationic polymerizable component (B), 1 to 10 parts by mass of the radical polymerizable initiator (C), and 1 to 10 parts by mass of the cationic polymerizable initiator (D), among 100 parts by mass of the total amount of the radical polymerizable component (A), the cationic polymerizable component (B), the radical polymerizable initiator (C), and the cationic polymerizable initiator (D). In the first paragraph,
A composition wherein the crosslinked condensed ring included in the radical polymerizable compound (A1) and the cationic polymerizable compound (B1) is a crosslinked condensed ring having a structure represented by the following formula (I):

. In the first paragraph,
A composition containing, as the cationic polymerizable component (B), a cationic polymerizable compound (B2) having a weight average molecular weight of 1,000 or more and less than 30,000 and not having a crosslinked condensed ring. In the first paragraph,
A composition containing, as the cationic polymerizable component (B), a cationic polymerizable compound (B3) having a weight average molecular weight of 200 or more and less than 1,000 and not having a crosslinked condensed ring. In paragraph 4,
A composition wherein the cationic polymerizable compound (B3) comprises a compound having an oxetanyl group. In the first paragraph,
A composition containing, as the radical polymerizable component (A), a radical polymerizable compound (A2) having a cationic polymerizable group and not having an isocyanurate ring or a crosslinked condensed ring. In the first paragraph,
A composition containing, as the radical polymerizable component (A), a radical polymerizable compound (A3) containing an isocyanurate ring and not having a crosslinked condensed ring. An adhesive containing a composition according to any one of claims 1 to 7. A cured product comprising a composition according to any one of claims 1 to 7. A method for producing a cured product, comprising a step of irradiating or heating an active energy ray with the composition described in any one of claims 1 to 7. delete