TW202019985A - Composition, adhesive including same, cured object obtained therefrom, and production method therefor - Google Patents

Abstract

Provided is a composition excellent in terms of curing rate and water resistance and capable of giving cured objects having excellent adhesive strength. Also provided are an adhesive including the composition, a cured object obtained therefrom, and a production method therefor. The composition comprises a radical-polymerizable ingredient (A) and a cationically polymerizable ingredient (B). The radical-polymerizable ingredient (A) includes a radical-polymerizable compound (A1) having a bridged fused ring, in an amount of 70-100 parts by mass per 100 parts by mass of the radical-polymerizable ingredient (A). The cationically polymerizable ingredient (B) includes a cationically polymerizable compound (B1) having a bridged fused ring, in an amount of 10-50 parts by mass per 100 parts by mass of the cationically polymerizable ingredient (B).

Description

Composition, adhesive containing it, hardened product thereof, and method of manufacturing the same

The present invention relates to a composition, an adhesive agent containing the same, a cured product thereof, and a method for producing the same. Specifically, it relates to a composition which can obtain a cured product excellent in curing speed, water resistance, and adhesion, and containing the cured product. Adhesive, its hardened product and its manufacturing method.

The cationic hardening composition is used in the fields of inks, paints, various coating agents, adhesives, optical components, and the like. There are various reports on the improvement of such hardenable compositions.

For example, Patent Document 1 proposes an active energy ray-curable adhesive composition such as a plastic film having a low viscosity, excellent curability, adhesion to various plastic films or sheets, and colorless transparency. In addition, Patent Document 2 proposes low viscosity and excellent curability. Even if the environmental humidity during coating/curing is high, the adhesion to various plastic films is excellent, and the colorless transparency is also excellent. Energy ray hardening type adhesive composition. Furthermore, Patent Document 3 proposes light with a low viscosity even when the humidity of the coating environment is high, the curability is excellent, the adhesion after a certain period of time, durability, and the adhesion after the end of the humid heat test are good. Hardening adhesive. Still further, Patent Document 4 proposes to apply a photo- and thermosetting resin composition having a diacrylate having a dicyclopentadiene skeleton and a diglycidyl ether having a dicyclopentadiene skeleton, and having formation hardening The step of producing a layered resin composition layer, and the method of manufacturing a laminate in the step of further irradiating the curable resin composition layer with active energy rays. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-034188 [Patent Document 2] Japanese Patent Laid-Open No. 2015-057467 [Patent Document 3] Japanese Patent Laid-Open No. 2015-143352 [Patent Document 4] Japanese Patent Application Publication No. 2017-149135

[Problems to be solved by the invention]

However, the cationic curable compositions proposed in Patent Documents 1 to 4 have a problem that sufficient curability cannot be obtained and the resulting cured product has insufficient water resistance. For example, when used as an adhesive, the curing rate may be insufficient, or sufficient adhesion and water resistance may not be obtained.

Therefore, the present invention is made in view of the above-mentioned problems, and an object of the present invention is to provide a composition, an adhesive containing the cured product, a cured product thereof, and a cured product having excellent curing speed, water resistance, and excellent adhesion. Its manufacturing method. [Means to solve the problem]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have achieved the above-mentioned object. The present invention will be described in detail below.

That is, the composition of the present invention contains a radically polymerizable component (A) and a cationically polymerizable component (B), characterized in that the radically polymerizable component (A) is a (A) 100 to 100 parts by mass, containing 70 to 100 parts by mass of a radically polymerizable compound (A1) having a cross-linked condensation ring, The cationic polymerizable component (B) contains 10 to 50 parts by mass of the cationic polymerizable compound (B1) having a cross-linked condensation ring in 100 parts by mass of the cationic polymerizable component (B).

In the composition of the present invention, it is preferable to further contain a radical polymerizable initiator (C) and a cationic polymerizable initiator (D), and In 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), Contains 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 the cationic polymerization 1 to 10 parts by mass of sexual initiator (D). This composition is excellent in initial hardenability.

Further, in the composition of the present invention, the cross-linked condensation ring contained in the radical polymerizable compound (A1) and the cationic polymerizable compound (B1) preferably has a structure represented by the following formula (I) Cross-linked condensation ring. This composition and the resulting hardened product have excellent water resistance.

Furthermore, the composition of the present invention preferably contains a cationic polymerizable compound (B2) having a weight average molecular weight of 1,000 or more and not more than 30,000 without a cross-linked condensation ring as the aforementioned cationic polymerizable component (B). From this composition, a hardened product excellent in water resistance can be obtained.

Still further, the composition of the present invention preferably contains a cationic polymerizable compound (B3) having a weight average molecular weight of 200 or more and not more than 1,000 that does not have a cross-linked condensation ring as the aforementioned cationic polymerizable component (B). From this composition, a cured product excellent in coatability and water resistance can be obtained.

In the composition of the present invention, the cationic polymerizable compound (B3) preferably contains a compound having an oxetanyl group. From this composition, a hardened product excellent in water resistance can be obtained.

Further, the composition of the present invention preferably contains a radically polymerizable compound (A2) having a cationic polymerizable group and not having an isocyanurate ring and a cross-linked condensation ring, as the aforementioned radical polymerizable Ingredient (A). This composition is excellent in coatability and initial adhesion.

Still further, the composition of the present invention preferably contains a radically polymerizable compound (A3) containing an isocyanurate ring and not having a cross-linked condensation ring as the aforementioned radically polymerizable component (A). From this composition, a hardened product excellent in water resistance can be 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, it becomes an adhesive agent that is excellent in hardening speed and can obtain a hardened product excellent in adhesive strength and water resistance.

The hardened product of the present invention is characterized by the hardened product of the composition of the present invention. By using the composition of the present invention, it becomes a cured product excellent in adhesion and water resistance.

The method for producing a hardened product of the present invention is characterized by including the step of irradiating active energy rays or heating the composition of the present invention. Since the composition of the present invention contains the above-mentioned components, a cured product excellent in adhesion and water resistance can be easily obtained. [Effect of invention]

According to the present invention, it is possible to provide a composition capable of obtaining a cured product excellent in curing speed and water resistance, and excellent in adhesion, an adhesive agent containing the cured product, a cured product thereof, and a method for manufacturing the same.

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

<Composition> First, the composition of the present invention will be explained. The composition of the present invention is a composition containing a radical polymerizable component (A) (hereinafter also referred to as "component (A)") and a cationic polymerizable component (B) (hereinafter also referred to as "component (B)") Thing. In the composition of the present invention, in 100 parts by mass of the component (A), it contains 70 to 100 parts by mass of a radically polymerizable compound (A1) having a crosslinked condensation ring (hereinafter also referred to as "compound (A1)"). And 100 parts by mass of the component (B) contains 10 to 50 parts of the cationic polymerizable compound (B1) having a cross-linked condensation ring (hereinafter also referred to as "compound (B1)". That is, by the above By containing the compound (A1) and the compound (B1) in a proper ratio, a hardened product with excellent hardening speed and excellent adhesion and water resistance can be obtained.

In the composition of the present invention, in addition to the compound (A1) and the compound (B1), a radical polymerizable initiator (C) (hereinafter also referred to as "component (C)") and a cationic polymerizable initiator are included (D) (hereinafter also referred to as "component (D)") is preferable because a composition with high curability can be obtained. The preferred ratios of component (A), component (B), component (C) and component (D) in the composition of the present invention are those of component (A), component (B), component (C) and component (D) ) Of 100 parts by mass, 40-60 parts by mass of component (A), 30-50 parts by mass of component (B), 1-10 parts by mass of component (C) and 1-10 parts by mass of component (D) . With this ratio, a hardened composition having excellent hardening speed and excellent adhesion and water resistance can be obtained.

In the composition of the present invention, the ratio of component (A) to component (B) is preferably 50 to 130 parts by mass relative to 100 parts by mass of component (A). When the ratio of the component (A) to the component (B) is within the above range, a cured product excellent in adhesion and water resistance can be obtained, which is preferable. Each component is explained in detail below.

<Free radical polymerizable component (A)> The component (A) is a compound having a radical polymerizable group. The radical polymerizable group means a group that can be polymerized in the presence of free radicals, and examples thereof include acryloyl, methacryloyl, vinyl, and thiol groups. The component (A) consists of a compound (A1), a radically polymerizable compound (A2) having a cationic polymerizable group and having no isocyanurate ring and cross-linked condensation ring (hereinafter also referred to as "compound (A2) )), a radically polymerizable compound (A3) having an isocyanurate ring and no crosslinking condensation ring (hereinafter also referred to as "compound (A3)") and not belonging to compound (A1) to compound (A3) ) Of other radical polymerizable compounds. Furthermore, these compounds can be used individually or in mixture of 2 or more types.

From the viewpoint of ease of coating, curing speed, and the like of the composition of the present invention, component (A) preferably contains a low molecular weight compound. In addition, since the low molecular weight compound has excellent dispersibility and solubility in the composition, it is possible to obtain a cured product having excellent transparency. On the other hand, from the viewpoint of adhesion of the composition of the present invention, the radically polymerizable compound preferably contains a high molecular weight compound. From the viewpoint of the balance of ease of application of the composition, hardening speed, and adhesion, the radically polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound. Furthermore, the use of a high molecular weight compound together with a low molecular weight compound can improve the dispersion or solubility in the composition of the present invention, and a cured product excellent in transparency can be obtained.

The molecular weight of the low-molecular-weight compound may be as long as the desired coatability and the like can be obtained. For example, it may be 1,000 or less, preferably 50 or more and 500 or less, and particularly preferably 50 or more and 300 or less. The molecular weight of the high-molecular-weight compound may be as long as the desired ease of adhesion can be obtained. For example, it may be greater than 1,000, preferably 1,000 or more and 50,000 or less, and particularly preferably 5,000 or more and 20,000 or less. Furthermore, in the following, when the compound is a polymer, the molecular weight system represents the weight average molecular weight (Mw).

Here, the weight average molecular weight can be obtained by gel permeation chromatography (GPC) as a standard polystyrene conversion value. For weight-average molecular weight Mw, for example, GPC (LC-2000plus series) manufactured by Japan Spectroscopy Co., Ltd. can be used, the dissolution solvent is tetrahydrofuran, and the calibration curve polystyrene standards are Mw1,110,000, 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 the measurement columns are KF-804, KF-803, KF-802 (Showa Denko (shares) ) Made) to be measured. In addition, the measurement temperature may be 40°C, and the flow rate may be 1.0 mL/minute.

The content of the 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 relative to 100 parts by mass of the composition due to its excellent water resistance. .

<Compound (A1)> The compound (A1) is a radical polymerizable compound having a cross-linked condensation ring. The cross-linked condensed ring possessed by the compound (A1) means a condensed ring having 3 or more carbon atoms, and preferably includes a cross-linked condensed ring having the structure represented by the general formula (I).

Examples of the cross-linked condensation ring having such a structure include the following cross-linked condensation rings.

Among the exemplified cross-linked condensed rings, the adhesive containing the compound (A1) having cross-linked condensed rings No. 6, No. 7 and No. 8 is particularly preferable because of its high adhesive strength and water resistance. The cross-linked condensation ring No. 6 is excellent because of its stable structure and high productivity.

Compounds (A1) with 1 to 4 radical polymerizable groups are preferred because of a good balance of adhesion and coating properties; compounds (A1) with 1 to 3 radical polymerizable groups It is especially good.

Examples of the compound (A1) include tricyclodecane dimethanol di(meth)acrylate, dicyclopentoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Dicyclopentyl ester, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dimethylol dicyclopentane di(methyl) Acrylate, dimethylol-tricyclodecane di(meth)acrylate, adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, etc.

The compound (A1) can also use a commercial item. Examples of commercially available products include Kayarad R-684 (above, manufactured by Nippon Kayaku); A-DCP and DCP (above, manufactured by Shin Nakamura Chemical Industry); FA-511AS, FA-512AS, FA-513AS, FA-512M, FA-512MT, FA-513M (above, Hitachi Chemical).

<Compound (A2)> The compound (A2) is not particularly limited as long as it is a radically polymerizable compound having a cationic polymerizable group and not having an isocyanurate ring and a cross-linked condensation ring.

The cationic polymerizable group means a group that can be polymerized 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. The cationic polymerizable group possessed by the compound (A2) is preferably a hydroxyl group from the viewpoint of base material adhesion. From the viewpoint of initial hardenability and adhesion, epoxy groups are preferred.

The compound (A2) includes, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl ) 2-hydroxy-3-acryloxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. Ester; N-2-hydroxyethyl (meth)acrylamide, N-vinylformamide, etc., containing hydroxyl groups of propionamide; vinyl phenol, allyl alcohol, crotyl alcohol, etc. vinyl alcohol; containing hydroxyl groups Vinyl monomer, epoxy (meth)acrylate of ethylene glycol diglycidyl ether obtained by reacting (meth)acrylic acid with an epoxy compound, mono(methyl) of diethylene glycol diglycidyl ether ) Acrylate, mono(meth)acrylate of triethylene glycol diglycidyl ether, mono(meth)acrylate of polyethylene glycol diglycidyl ether, mono(meth)acrylic acid of propylene glycol diglycidyl ether Ester, mono(meth)acrylate of tripropylene glycol diglycidyl ether, mono(meth)acrylate of polypropylene glycol diglycidyl ether, mono(meth)acrylate of neopentyl glycol diglycidyl ether, etc. Epoxy (meth)acrylate; glycidyl (meth)acrylate, and the following compounds (A2) No. 1 to No. 4, acrylic acid (3-ethyloxetan-3-yl) methyl Ester etc.

As the radical polymerizable group of the compound (A2), from the viewpoint of excellent curability, the radical polymerizable group is preferably an acryl group. In addition, from the viewpoint of low viscosity and excellent coatability, it preferably has one or two radical polymerizable groups.

When the radically polymerizable component (A) contains the radically polymerizable compound (A2), since the adhesiveness, water resistance and fluidity are excellent, the preferable content of the radically polymerizable compound (A2) is preferably free Out of 100 parts by mass of the base polymerizable component (A), 0 to 20 parts by mass, particularly preferably 5 to 10 parts by mass.

<Compound (A3)> The compound (A3) is not particularly limited as long as it is a radically polymerizable compound containing an isocyanurate ring and not having a cross-linked condensation ring.

Examples of the compound (A3) include modified ε-caprolactone [2-(meth)acryloyloxyethyl]isocyanurate, tri[(meth)acryloylethyl]isotricyanate Polycyanate, ginseng [3-(meth)acryloxypropyl] isocyanurate, etc. [(meth)acryl oxyalkyl] isocyanurate, and di [(Meth)acryloylethyl]-2-hydroxyethyl isocyanurate, monoallyl isocyanurate, diallyl isocyanurate, triallyl Isocyanurate and the following compound (A3) No. 1 etc.

As the compound (A3), commercially available products can also be used. Examples of commercially available products include Aronix M-215 and M-315 (above, synthesized by East Asia); NK ESTER A-9300, A-9300-1CL, and A-9300-3CL (above, manufactured by Shin Nakamura Chemical Industry); TAIC ( Mitsubishi Chemical) etc.

The radically polymerizable group of the compound (A3) is preferably an acryl group from the viewpoint of excellent curability. In addition, from the viewpoint of excellent curability, it preferably has a plurality of radical polymerizable groups, and particularly preferably 2 to 3.

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

<Other radical polymerizable compounds> Other radically polymerizable compounds include, for example, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, himic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid Acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxy polycaprolactone Mono(meth)acrylates of polymers with carboxyl and hydroxyl groups at both ends, such as ester mono(meth)acrylates; polyfunctional (methyl) with one carboxyl group and two or more (meth)acryloyl groups ) Unsaturated polybasic acids such as acrylates; methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, (methyl) Cyclohexyl 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, (methyl ) Dimethylaminopropyl acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ( Ethylhexyl methacrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic acid Benzyl methyl ester, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate ) Acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) Group) acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate , Unsaturated monobasic acids such as polyester (meth)acrylate oligomers and esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-side Oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl Anhydrides of unsaturated polybasic acids such as norbornenic diacid anhydride; (meth)acrylamide, methylene bis-(meth)acrylamide, diethylenetriamine ginseng (meth)acrylamide, shendi Tolyl bis (meth) acrylamide, α-chloropropene amide Unsaturated monobasic acids such as amines and amides of polyamines; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene chloride, allyl cyanide, etc. ; Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzene Unsaturated aromatic compounds such as formic acid, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone ; Unsaturated amine compounds such as vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl piperidine; vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, iso Vinyl ethers such as butyl vinyl ether, allyl glycidyl ether, etc.; unsaturated amide imines such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. Indens such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, poly(methyl) Macromolecular monomers with mono(meth)acryloyl groups at the end of polymer molecular chains such as methyl acrylate, poly-(meth)acrylate n-butyl acrylate, polysiloxane, etc.; vinyl chloride, vinylidene chloride Ethylene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl Carbazole, vinyl pyrrolidone, vinyl pyridine and vinyl carbamate compounds of polyisocyanate compounds.

Other radically polymerizable compounds can also be used on the market. Commercial products include, for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (above, manufactured by Nippon Kayaku); NK ESTER A-DOD-N, A-DPH, A-TMPT , A-HD-N, TMPT, NPG and HD-N (above, manufactured by Shin Nakamura Chemical Industry); SPC-1000, SPC-3000 (above, 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 (above, Shin Nakamura Chemical Industry ( Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (above, Kyoeisha Chemical Co., Ltd.), Artrejin UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH-500, SH-9832, UN-901T, UN-904, UN-905, UN-906, UN-906S, UN-907, UN- 952, UN-953, UN-954, H-91, H-135 (above, Root Industry Co., Ltd.), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (above, Sartomer Company), EBECRYL 8810 (made by Daicel), etc.

<Cationic polymerizable component (B)> The cationic polymerizable component (B) contained in the composition of the present invention is a compound having a cationic polymerizable group and not having a radical polymerizable group. Component (B) is composed of compound (B1), a cationic polymerizable compound (B2) having a weight average molecular weight of 1,000 or more and less than 30,000 having a cationic polymerizable group and no cross-linked condensation ring (hereinafter also referred to as "compound ( B2)"), a cationic polymerizable compound (B3) (hereinafter also referred to as "compound (B3)") that does not have a cross-linked condensation ring weight average molecular weight of 200 or more and less than 1,000, and does not belong to compound (B1) to compound (B3) Other cationic polymerizable compounds. Furthermore, in the composition of the present invention, two or more components (B) may be used alone or in combination. In addition, when the compound is a polymer, the molecular weight refers to the weight average molecular weight (Mw).

The content of the component (B) contained in the composition of the present invention is preferably 30-50 parts by mass and particularly preferably 40-50 parts by mass due to excellent water resistance relative to 100 parts by mass of the composition.

From the viewpoint of ease of coating, curing speed, and the like of the composition of the present invention, component (B) preferably contains a low molecular weight compound. In addition, since the low molecular weight compound has excellent dispersibility and solubility in the composition, it is possible to obtain a cured product with excellent transparency. On the other hand, from the viewpoint of adhesion of the composition of the present invention, the cationic polymerizable compound preferably contains a high molecular weight compound. In addition, from the viewpoint of the balance of ease of application of the composition, curing speed, and adhesion, the cationic polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound. In addition, it is because a high molecular weight compound, when used together with a low molecular weight compound, can increase the dispersion or solubility in the composition of the present invention, and a hardened 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 rate and adhesive strength can be obtained. For example, it is appropriately adjusted from the viewpoint of the balance between adhesive strength and transparency. The content of the high molecular weight compound may specifically be 0 parts by mass or more and 20 parts by mass or less, out of 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, in particular It is preferably 3 parts by mass or more and 10 parts by mass or less. The reason is that by setting the content within this range, the composition of the present invention has excellent curing speed and excellent adhesion, and particularly because a cured product having excellent adhesion and excellent transparency can be formed.

<Compound (B1)> The compound (B1) is a cationic polymerizable compound having a cross-linked condensation ring. Among the cross-linked condensed rings, particularly because of their excellent water resistance, it is preferably a cross-linked condensed ring having the structure represented by the above general formula (I), especially containing No. 6, No. 7 and No. The adhesive of Compound 8 (B1) of 8 is preferable because of its high adhesive strength and water resistance. The cross-linked condensation ring No. 6 is excellent because of its stable structure and high productivity.

Examples of the compound (B1) include the following compounds (B1) No. 1 to No. 22 and the like.

As the compound (B1), commercially available products can also be used. Examples of commercially available products include Adeka Resin EP-4088L and 4088S (above, manufactured by ADEKA); XD-1000 (manufactured by Nippon Kayaku) and HP-7200 (manufactured by DIC).

The cationically polymerizable group of the compound (B1) is preferably epoxy-based and particularly preferably a glycidyl ether group from the viewpoint of high curability and excellent adhesion. In addition, from the viewpoint of excellent curability, it preferably has a plurality of cationic polymerizable groups, and particularly preferably 2 to 3.

<Compound (B2)> The compound (B2) is not particularly limited as long as it is a cationic polymerizable compound that does not have a weight average molecular weight of 1,000 or more and less than 30,000 without a cross-linked condensation ring. The weight average molecular weight can be measured by the above-mentioned measurement method. The composition containing the compound (B2) is preferable because the water resistance is improved.

Examples of the compound (B2) include copolymers of glycidyl methacrylate, copolymers of glycidyl methacrylate and copolymers of glycidyl methacrylate and methyl methacrylate, and some of these Modified by glycidyl methacrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 4-hydroxybutyl methacrylate, diglycidyl ether of bisphenol A, bis Phenol F bis glycidyl ether and so on. In addition, novolac type epoxy resin, 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, trimethylol propane trivinyl ether Such as polymers and copolymers.

As the compound (B2), commercially available products can also be used. Examples of commercially available products include G-0130M (above, manufactured by NOF Corporation), EOCN-104S (manufactured by Nippon Kayaku), and the like.

As for the compound (B2), when the epoxy equivalent is 1,000 or less, it is preferable because of its excellent hardenability, and the epoxy equivalent is preferably 200 to 600.

In addition, the cationic polymerizable group included in the compound (B2) can obtain a composition having high curability and high adhesion, and therefore is preferably an epoxy group and particularly preferably a glycidyl ether group.

The preferred content of the cationic polymerizable compound (B2) that can be contained in the cationic polymerizable component (B) is 0 to 30 parts by mass out of 100 parts by mass of the cationic polymerizable component (B) due to its excellent water resistance and fluidity. , Especially good is 5~20 parts by mass.

<Compound (B3)> The compound (B3) is not particularly limited as long as it is a cationic polymerizable compound that does not have a weight average molecular weight of 200 or more and less than 1,000 and has no cross-linked condensed ring. The composition containing the compound (B3) is preferable because it can balance adhesion and coating properties. Examples of the compound (B3) include aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and oxetane compounds. However, compounds with epoxy groups and oxetane groups in the same molecule are classified as oxetane compounds.

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

Since a composition with high curability and high adhesion can be obtained, the cationic polymerizable group possessed by the compound (B3) is preferably an epoxy group and particularly preferably a glycidyl ether group. In addition, since a composition excellent in water resistance can be obtained, the compound (B3) is also preferably a compound having an oxetanyl group.

When the cationic polymerizable component (B) contains the cationic polymerizable compound (B3), the preferred content is preferably 0 to 90 parts by mass out of 100 parts by mass of the cationic polymerizable component (B) due to its excellent water resistance and fluidity. Servings are 35~80 parts by mass.

A composition containing a compound (B3) containing 1 to 3 cationic polymerizable groups is preferable because it can take into account both adhesion and coatability, especially a compound (B3) containing 1 to 2 cationic polymerizable groups is particularly preferred .

As the alicyclic epoxy compound of the compound (B3), it means that it has an alicyclic epoxy group (3,4-epoxycyclohexyl group) and does not have a cross-linked condensed ring. 1,000 cationic polymerizable compounds. By using an alicyclic epoxy compound as the compound (B3), the initial hardenability is improved, which is preferable.

Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 3,4-epoxycyclohexylmethyl-3,4. -Epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate, 6-methyl-3 ,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4 -Epoxy-3-methylcyclohexanecarboxylic acid ester, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylic acid Ester, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexane carboxylate, methylene bis(3,4-cyclo Oxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, bicyclo Pentadiene diepoxide, ethylidene bis(3,4-epoxycyclohexane carboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalic acid Di-2-ethylhexyl ester, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 7-oxygen Heterobicyclo[4.1.0]heptane, poly[oxy-(1-oxo-1,6-hexanediyl)] derivative, adipic acid bis[(7-oxabicyclo[4.1.0] Heptane-3-yl) methyl ester], α-pinene oxide, limonene dioxide.

An alicyclic epoxy compound, from the viewpoint of improvement of adhesion, is preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate or 3,4-epoxy -1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate .

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); Cyracure UVR-6128 (manufactured by Dow Chemical Company), and the like.

The content of the alicyclic epoxy compound may be as long as the desired curing rate and adhesive force can be obtained. For example, it may be 0 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the compound (B), especially 1 part by mass It is preferably not less than 20 parts by mass. By setting the content to this range, the composition of the present invention becomes excellent in hardening speed and adhesion.

The aliphatic epoxy compound as the compound (B3) refers to cationic polymerization which is not classified as an alicyclic epoxy compound or an aromatic epoxy compound described later and has a weight average molecular weight of not less than 200 and not more than 1,000 and which does not have a cross-linked condensed ring. Sexual compounds, which means those that do not contain aliphatic rings and aromatic rings.

Specific examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl etherate of aliphatic alcohol and glycidyl ester of alkyl carboxylic acid, or aliphatic polyhydric alcohol or alkylene oxide adduct thereof Multifunctional epoxy compounds such as polyglycidyl ethers, polyglycidyl esters of aliphatic long-chain polyacids, etc.

Representative compounds of aliphatic epoxy compounds include 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, glycerol triglycidyl ether, trimethylol Propane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and other glycidyl ethers of polyhydric alcohols, etc. Polyglycidyl etherate of polyether polyol obtained by adding 1 type or 2 or more types of alkylene oxide to aliphatic polyol such as propylene glycol, trimethylolpropane, glycerin, aliphatic long chain dibasic acid II Glycidyl ester. Further, examples include monoglycidyl ethers of aliphatic higher alcohols or glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, cyclic Oxidized polybutadiene, etc.

Aliphatic epoxy compounds are glycidyl ethers of aliphatic alcohols or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts. The viscosity, coating properties and reactivity are improved, so Good; more preferably ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether ether.

As the aliphatic epoxy compound, commercially available products can be used, and examples thereof include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (above, manufactured by Nagase ChemteX); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (above, manufactured by Kyoeisha Chemical), Adeka Glycirol ED-503, Adeka Glycirol ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523T, Adeka Resin EP-4088S, KRM-523P, KRM- 408, KRM-140 (above, manufactured by ADEKA); 2EH (manufactured by Yokkaichi), etc.

The content of the aliphatic epoxy compound may be as long as the desired hardening speed and adhesive force can be obtained. For example, it may be 0 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the compound (B), particularly 30 parts by mass. It is preferably at least 80 parts by mass. By setting the content to this range, the composition of the present invention becomes excellent in hardening speed and adhesion.

The aromatic epoxy compound as the compound (B3) means an aromatic ring-containing epoxy compound that is not classified as an alicyclic epoxy compound and does not have a weight-average molecular weight of 200 or more and a cross-linked condensation ring of not more than 1,000.

Specific examples of aromatic epoxy compounds include phenol, cresol, butylphenol, etc., mono/polyglycidyl ethers of monohydric phenols having at least one aromatic ring or their alkylene oxide adducts, for example Bisphenol A, Bisphenol F, or glycidyl etherate or phenol novolac epoxy compound of compounds obtained by further adding alkylene oxide to these; resorcinol, hydroquinone, catechol, etc. have Glycidyl ethers of aromatic compounds with 2 or more phenolic hydroxyl groups; polyglycidyl ethers of aromatic compounds with 2 or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, or benzenedibutanol; o Polyglycidyl esters of polyacid aromatic compounds with more than two carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, etc.; benzoic acids such as benzoic acid, toluic acid, naphthoic acid, etc. Polyglycidyl ester; glycidyl benzoate, styrene oxide or divinylbenzene epoxide, etc. Among them, from the viewpoint of lowering the viscosity of the composition of the present invention, especially polyglycidyl ethers containing polyglycidyl ethers selected from phenols, aromatic compounds having two or more alcoholic hydroxyl groups, and polyphenols At least one type of polyglycidyl etherate, polyglycidyl ester of benzoic acid, and polyglycidyl ester of polybasic acid is preferable. Because of its excellent adhesion, the aromatic epoxy compound is preferably a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol E epoxy compound, or a phenol novolac epoxy compound.

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.); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); Epikote YX8800 (Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epiclon N-665, Epiclon HP-7200 (manufactured by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S , XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku); 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 (made by ADEKA); TECHMORE VG-3101L (made by Printec), etc.

The content of the aromatic epoxy compound may be as long as the desired hardening speed and adhesive force can be obtained. For example, it may be 0 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the compound (B), especially 10 parts by mass It is preferably not less than 50 parts by mass. By setting the content to this range, the composition of the present invention becomes excellent in hardening speed and adhesion.

The oxetane compound as the compound (B3) means an oxetane compound having an oxetane group and having a weight average molecular weight of 200 or more and not more than 1,000 without a cross-linked condensed ring.

Due to the excellent balance of hardenability and coatability, oxetane compounds containing 1 to 3 oxetane groups are preferred, and oxetane groups containing 2 oxetane groups are particularly preferred Butane compounds.

Oxetane compounds include 3,3'-[oxybis(methylene)]bis(3-ethyloxetane), (3,7-bis(3-oxetane Alkyl)-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-oxetanyl methyl) ether, triethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, tetraethylene di Alcohol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6 -Bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-(3-ethyl-3-oxetanylmethoxymethyl) Difunctional oxetane compounds such as oxetane and xylylene dioxetane; 3-ethyl-3-[(phenoxy)methyl]oxetane, 3- Ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-( One functional oxetane compound such as hydroxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, etc., from the viewpoint of viscosity and reactivity, is preferably A monofunctional aliphatic oxetane compound. These can be used alone or in combination of two or more.

As an oxetane compound, a commercially available product mainly containing a cationic polymerizable monomer can be used, and examples include Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, OXT-221 (manufactured by East Asia Synthetic Corporation), Eternacoll OXBP, OXTP (manufactured by Ube Kosei Corporation), etc.

The content of the oxetane compound may be as long as the desired hardening speed and adhesive force can be obtained. For example, it may be 0 parts by mass or more and 50 parts by mass or less out of 100 parts by mass of the compound (B), especially 5 It is preferably at least 30 parts by mass. By setting the content to this range, the composition of the present invention becomes excellent in coatability and hardening speed.

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

Component (C) refers to an optical radical polymerizable initiator and a thermal radical polymerizable initiator. Due to its high reactivity, it is more preferably a photo-radical polymerizable initiator.

The component (C) is not particularly limited as long as it generates free radicals by light irradiation, and conventionally known compounds can be used, for example, acetophenone-based compounds, benzophenone-based compounds, and benzophenone-based compounds can be exemplified. Compounds, thioxanthone-based compounds, oxime ester-based compounds, etc. are preferred.

Examples of the acetophenone-based compound include benzoin, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4'-isopropyl-2-hydroxy-2-methylphenylacetone, 1 -Hydroxycyclohexyl phenyl ketone, 2-hydroxymethyl-2-methylbenzeneacetone and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1- Alpha-hydroxyacetophenone compounds such as propane-1-one; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin Α-alkoxyacetophenone-based compounds such as inoisobutyl ether diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenylethane-1-one; p- Dimethylaminoacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, and 2-benzyl-2-dimethylamine Alpha-1-(4-morpholinylphenyl)-butanone-1 and other α-aminoacetophenone-based compounds; p-third butyl dichloroacetophenone, p-third butyl trichloro Acetophenone, p-azidobenzylidene acetophenone.

In the composition of the present invention, since the obtained cured product is excellent in transparency, it is preferably an acetophenone-based compound, and particularly preferably an α-hydroxyacetophenone-based compound.

Examples of the benzophenone-based compounds include benzophenone.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoyl benzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4' -Dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide, etc.

The thioxanthone compound includes thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethyl Thioxanthone etc.

The oxime ester-based compound means a compound having an oxime ester group, and it is particularly good among photoradical polymerizable initiators, so it is preferred.

Preferred oxime ester-based compounds include, for example, compounds No. C1 to No. C14 shown below.

Other radical polymerizable initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzyl diphenylphosphine oxide and bis(cyclopentadienyl)-bis[2 , 6-difluoro-3-(pyrrol-1-yl)] titanium and other titanocene-based compounds.

Commercially available free radical initiators include Adeka Optomer N-1414, N-1717, N-1919, Adeka Arkls NCI-831, NCI-930 (above, manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, manufactured by Tronly), etc.

The thermal radical polymerizable initiator is not particularly limited as long as it generates free radicals by heating, and conventionally known compounds can be used, for example, azo compounds, peroxides, and persulfates can be exemplified. By.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methyl isobutyrate), and 2,2'-azobis-2,4-dimethyl Valeronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), etc.

Peroxides can be exemplified by benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxytrimethylacetate and bis(4-t-butylcyclohexyl) peroxide Oxydicarbonate, etc.

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

In the composition of the present invention, the component (C) can be used singly or as a mixture of two or more.

In the composition of the present invention, the content of the component (C) is not particularly limited, and it is preferably 1 to 10 parts by mass out of 100 parts by mass of the total amount of the components (A) to (D). Furthermore, since the curability is good Therefore, it is preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass relative to 100 parts by mass of the component (A). When the content of the component (C) is within the above-mentioned range, it is preferable to obtain a polymerizable composition with good curability and excellent storage stability without accompanying precipitation of a polymerizable initiator.

<Cationic polymerizable initiator (D)> The component (D) used in the composition of the present invention is capable of generating acid by irradiating active energy rays (hereinafter also simply referred to as "active energy rays") such as visible rays, ultraviolet rays, X-rays, electron beams, and high-frequency waves. Compound (hereinafter also referred to as "photocationic polymerizable initiator"), or a compound that can generate an acid by heating (hereinafter also referred to as "thermal cationic polymerizable initiator").

In the composition of the present invention, component (D) has an aromatic ring, and the number of aromatic rings is 3 or more. Examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, and other aromatic hydrocarbon rings whose carbon atoms are all carbon atoms; furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, etc. Atoms contain aromatic heterocycles with atoms other than carbon atoms.

In the composition of the present invention, the type of component (D) is both a photocationic polymerizable initiator and a thermal cationic polymerizable initiator. From the viewpoint of sensitivity, a photocationic polymerizable initiator is preferred.

The photo-cationic polymerizable initiator can be a double salt of an onium salt or a derivative thereof, or an oxime sulfonate compound, a halogen-containing compound, a diazo ketone compound, a benzene compound, a sulfonic acid compound, a diazomethane compound, or nitrate The benzophenone compound, benzoin tosylate compound, iron aromatic hydrocarbon complex, acetophenone derivative compound, etc., can be used alone or in combination of two or more.

Among the compositions of the present invention, a particularly preferred photocationic polymerizable initiator is a double salt of an onium salt or a derivative thereof. This is because the photo-cationic polymerizable starter makes the composition of the present invention excellent in curing speed and adhesion.

Among the complex salts of onium salts or derivatives thereof, the compounds having the number of aromatic rings of 3 or more include salts of cations and anions represented by the following general formula (1).

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

Here, R ¹⁰ is an organic group having 1 to 60 carbon atoms and can be used regardless of the number of atoms other than a few carbon atoms. a is an integer from 1 to 5. The a R ¹⁰ series may independently be the same or different. At least one of a R ¹⁰ is the above-mentioned organic group having an 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, and N=N. In addition, when the atomic valence of Q in cation [A] ^m+ is q, the relationship of m=aq must be established. However, N=N is regarded as atomic valence 0.

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

Here, L is the metal or semimetal (Metalloid) of the central atom of the halide complex, which is 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 atomic valence of L in anion [B] ^m- is p, the relationship of m=bp must be established.

Specific examples of the anion [LX _b ] ^m- of the general formula (3) can be exemplified by (pentafluorophenyl) borate [(C ₆ F ₅ ) ₄ B] ^- , tetrafluoroborate (BF ₄ ) ^- , Hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- , ginseng (pentafluoromethyl) trifluorophosphate Ions (FAP anions), etc.

In addition, as the anion [B] ^m- , it is also preferable to use a structure represented by the following general formula (4).

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

Among the onium salts in the composition of the present invention, it is particularly effective to use the cerium salts represented by the following group I or group II, such as cerium cations, hexafluoroantimonate ions, and (pentafluorophenyl) borate ions. . Among these, one type may be used alone, or two or more types may be used in combination.

Among these, from the viewpoints of practical surface and light sensitivity, it is particularly preferable to use aromatic tungsten salts and aromatic monium salts; particularly preferably aromatic monium salts; from the viewpoint of sensitivity, it is more preferably the following general formula (5) Aromatic aromatic salt. In addition, because the photocationic polymerizable initiator is an aromatic osmium salt, the composition of the present invention is excellent in curing speed and adhesion.

Here, in the general formula (5), R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ and R ¹³⁰ independently represent a hydrogen atom and 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, and R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ independently represent hydrogen Atom, halogen atom or 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 selected from the following chemical formulas (A) to (C) The substituent, An ^q- represents a q-valent anion, and p represents a coefficient that makes the charge neutral.

In the chemical formulas (A) to (C), 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 , respectively represent hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, The alkoxy group having 1 to 10 carbon atoms or the ester group having 2 to 10 carbon atoms, R ²⁴⁰ , R ²⁴¹ , R ²⁴² , R ²⁴³ and R ²⁴⁴ independently represent a hydrogen atom, a halogen atom or a carbon atom 1-10 alkyl group, * represents the bonding position with S in the general formula (5).

Among the compounds represented by the 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 , The halogen atoms represented by 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 may include fluorine, chlorine and bromine , Iodine, etc.

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 The alkyl group having 1 to 10 carbon atoms represented by ²⁴⁰ , R ²⁴¹ , R ²⁴² , R ²⁴³ , R ²⁴⁴ , R ²⁴⁵ , R ²⁴⁶ , R ²⁴⁷ , R ^248, and R ²⁴⁹ includes methyl, ethyl, and propyl groups , Isopropyl, butyl, s-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyl Octyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxy Ethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, Bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl , Tridecylfluorohexyl, pentafluoroheptyl, heptafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methyl Thiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy ) Methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilyl ethyl Group, t-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, t-butoxycarbonylmethyl, ethoxycarbonylmethyl, ethylcarbonylmethyl Group, t-butoxycarbonylmethyl, acryloxyethyl, methacryloxyethyl, 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, etc.

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 and R ²⁴⁹ The alkoxy group having 1 to 10 carbon atoms includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy, isobutoxy , Pentyloxy, isopentyloxy, t-pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethoxy , 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxyethoxyethoxy, methoxyethoxyethoxyethoxy , 3-methoxybutoxy, 2-methylthioethoxy, trifluoromethoxy, etc.

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 and R ²⁴⁹ Ester groups having 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, phenoxycarbonyl, acetyloxy, propyloxy, butyloxy, chloroethyl Acyloxy, dichloroethoxy, trichloroethoxy, trifluoroethoxy, t-butylcarbonyloxy, methoxyethoxy, benzoyl Oxygen and so on.

The q-valent anion represented by pAn ^q- in the general formula (5) can be used as a specific valence anion among those listed as the above-mentioned anion [B] ^m- .

In the composition of the present invention, R ^{135 is} preferably selected from the chemical formulas (A) to (C), and particularly preferably selected from the chemical formulas (A) or (C). This is because R ¹³⁵ has the above structure, and the balance of the dispersion stability of component (D), the curing speed, and the adhesive force is excellent. In the composition of the present invention, from the viewpoint of the dispersion stability of the component (D), R ^{135 is} preferably a chemical formula (C). On the other hand, from the viewpoint of more excellent curing speed and adhesion, R ^{135 is} preferably the chemical formula (A). In the composition of the present invention, the component (D) preferably contains R ¹³⁵ in the chemical formula (A) and the chemical formula (C) from the viewpoint of excellent balance between the dispersion stability of the component (D), the curing speed and the adhesive force. Of the two.

When component (D) contains both R ¹³⁵ of formula (A) and that of formula (C), R ¹³⁵ is the content of formula (A), relative to 100 parts by mass of formula (C) It may be 10 parts by mass or more and 200 parts by mass or less, among which 50 parts by mass or more and 200 parts by mass or less is particularly preferable, and more preferably 80 parts by mass or more and 120 parts by mass or less. It is because the content in this range is excellent in the balance between the dispersion stability of component (D), the hardening speed, and the adhesive force.

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 hydrogen atoms, halogen atoms, carbon C1-C10 alkyl group, C1-C10 alkoxy group or C2-C10 ester group, especially hydrogen atom, halogen atom, C1-C10 alkyl group, carbon Alkoxy groups with 1 to 10 atoms are preferred; particularly preferred are hydrogen atoms. The reason is that the composition of the present invention has excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive force because of the above functional groups. In addition, it is because the above cationic polymerizable initiator becomes easy to synthesize.

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 , preferably a hydrogen atom, a halogen atom, a carbon number of 1 to 10 Alkyl groups, alkoxy groups having 1 to 10 carbon atoms; particularly preferably hydrogen atoms. The reason is that the composition of the present invention has excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive force because of the above functional groups. In addition, it is because the above cationic polymerizable initiator becomes easy to synthesize.

In the composition of the present invention, the content of the component (D) may be as long as the desired curing rate and adhesive force can be obtained. For example, it is preferably 0.1 part by mass out of 100 parts by mass of the solid content of the composition of the present invention Above and 10 parts by mass or less, particularly preferably 0.5 parts by mass or more and 8 parts by mass or less, 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; Among them, Youzai is preferably 2.0 parts by mass or more and 5 parts by mass or less. With the content in this range, the composition of the present invention is one that has a good balance between the dispersion stability of component (D), the hardening rate, and the adhesive force. In addition, the solid content of the composition of the present invention means all components other than the solvent.

Commercial products of the cationic polymerizable initiator (D) include, for example, "CPI-100P", "CPI-101A" (above, manufactured by San-Apro Co., Ltd.), and "IRGACURE 250" (manufactured by BASF SE) ), "Adeka Optomer SP-172", "Adeka Optomer SP-170", "Adeka Optomer SP-152", "Adeka Optomer SP-150" (above, manufactured by ADEKA Corporation); "San-Aid SI-60L" ", "San-Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-150L" (above, manufactured by Sanshin Chemical Industry Co., Ltd.), etc.

In the composition of the present invention, from the viewpoint of excellent curing speed and adhesion, the content of the component (D) is preferably 1 to 10 parts by mass out of 100 parts by mass of the total of the components (A) to (D), and With respect to 100 parts by mass of component (B), it is preferably 1 part by mass or more and 8 parts by mass or less, particularly preferably 1.5 parts by mass or more and 7 parts by mass or less, and particularly preferably 2.0 parts by mass or more and 6 Less than or equal to parts by mass, of which Yorge is preferably 3.0 parts by mass or more and 5 parts by mass or less.

<Solvent> The composition of the present invention may also use a solvent, which is a compound that can disperse or dissolve the components in the composition, and is a compound that is liquid at normal temperature and pressure. In addition, as the solvent, those containing no acryl, methacryl, vinyl, epoxy, and oxetanyl groups can be used.

Both such solvent-based water and organic solvents can be used, and preferably organic solvents can be used. The content of the organic solvent may be as long as the desired hardening speed and adhesive force can be obtained, preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and particularly preferably 95 parts by mass or more out of 100 parts by mass of the solvent , Tejia is 100 parts by mass, that is, it contains only organic solvents as solvents. The reason is that by setting the content to this range, the composition of the present invention has a good balance between the dispersion stability of component (C) and component (D), the hardening rate, and the adhesive force.

Examples of the organic solvent include carbonates such as propylene carbonate, ethyl carbonate, 1,2-butene carbonate, dimethyl carbonate, and diethyl carbonate; acetone, methyl ethyl ketone, cyclohexanone, methyl alcohol Ketones such as isoamyl ketone and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, di Polyols and derivatives of monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of propylene glycol and dipropylene glycol monoacetate; such as the cyclic form of dioxane Ethers; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl methyl acetate, ethyl ethyl acetate, ethyl pyruvate, ethyl acetate Ethyl oxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate , 2-hydroxy-3-methylbutyric acid methyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and other esters; aromatic hydrocarbons such as toluene and xylene Class; γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone, etc. Lactones and the like can be used as one kind of solvent or as a mixed solvent of two or more kinds. Among organic solvents, derivatives of polyhydric alcohols, lactones, and carbonates are particularly preferred, carbonates are particularly preferred, and propylene carbonate is particularly preferred. This is because by using these organic solvents, the composition of the present invention has a good balance between the dispersion stability of component (C) and component (D), the curing speed, and the adhesive force.

The molecular weight of the organic solvent is preferably 50 or more and 300 or less, and particularly preferably 80 or more in view of the excellent balance of the solubility or dispersion stability of component (A) to component (D) and the curing speed and adhesion. 200 or less, more preferably 90 or more and 150 or less.

The boiling point of the organic solvent is preferably 100°C or higher and 350°C or lower, particularly preferably 130°C or higher and 300°C or lower, particularly preferably 200°C or higher and 300°C or lower, from the viewpoint of less volatility of the self-hardened material. Utega is 200°C or higher and 250°C or lower. Furthermore, the boiling point is a value expressed under atmospheric pressure.

<Other ingredients> The composition of the present invention may contain other components in addition to the above components as necessary. As for other ingredients, it may contain colorants, light sensitizers, defoamers, tackifiers, shakers, surfactants, surfactants, etc. as needed, including inorganic fillers, organic fillers, pigments, silane coupling agents, dyes, etc. Various resin additives such as leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, and adhesion promoters. The total content of other components is preferably 30% by mass or less of 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 can uniformly mix the above-mentioned components, and examples include component (A) and component (B), added component (C), component (D) and Solvent and mixing method. In addition, as the mixing method, a method using a known mixing device can be used, and for example, a method using a 3-roller, a sand mill, a ball mill, or the like can be used.

The method of curing the composition of the present invention is appropriately set according to the types of the component (C) and the component (D). As the curing method, when the component (C) and the component (D) are a photo-radical polymerization initiator and a photo-cationic polymerizable initiator, an active energy ray irradiation treatment that irradiates the composition of the present invention with an active energy ray can be used Method.

Examples of the active energy rays include visible light, ultraviolet rays, electron beams, X-rays, radiation, and high-frequency waves. Ultraviolet rays are economically the best. Examples of the ultraviolet light source include ultraviolet lasers, mercury lamps, xenon lasers, and metal halide lamps. In addition, the composition of the present invention can be hardened by irradiating an LED light source. The active energy rays from the LED light source may include ultraviolet rays. The wavelength of the active energy line from the LED light source may be 350 nm to 405 nm. The composition of the present invention, when the cationic polymerizable initiator is a photo-cationic polymerizable initiator, can be irradiated by active energy rays, and is usually hardened to a dry state or a solvent insoluble state after 0.1 seconds to several minutes . The active energy ray and the exposure time to the active energy ray may be the same as those described in International Publication No. 2013/172145.

In the method for curing the composition of the present invention, when the component (C) is a thermal radical polymerizable initiator, or the component (D) is a thermal cationic polymerizable initiator, the composition of the present invention can be heat treated Method. The conditions when the composition of the present invention is hardened by heating may be 70°C to 250°C for 1 to 100 minutes. After pre-baking (PAB; Pre applied bake), pressurization and post-baking (PEB; Post exposure bake) can be performed, or baking can be performed at different temperatures in several stages. Although the heating conditions vary depending on the types of ingredients and the blending ratio, for example, it can be 70°C to 180°C, 5 minutes to 15 minutes in the oven, and 1 to 5 minutes in the heating plate. After that, in order to harden the coating film, it can be hardened by 180° C. to 250° C., preferably 200° C. to 250° C., heat treatment in the oven for 30 minutes to 90 minutes, and heat treatment in the hot plate for 5 minutes to 30 minutes. membrane.

The use of the composition of the present invention is not particularly limited as long as it is used to form a cured product. Examples include optical materials such as optical films, adhesives, glasses, and photographic lenses; paints, coating agents, and Lining agents, inks, high-refractive materials, water-soluble materials, semiconductor/display/MEMS/medical equipment resists, liquid resists, printing plates, insulating coatings, insulating sheets, laminates, printed boards, semiconductor devices/LEDs Encapsulant, molding material, putty, glass fiber impregnating agent, hole-filling agent, semiconductor/solar for encapsulation, liquid crystal injection port, organic EL, optical element, electrical insulation, electronic parts, separation film, etc. Passivation films for batteries, interlayer insulating films, protective films, protective films for color filters, spacers, DNA separation wafers, microreactors, nano biological devices, recording materials for hard disks, solid-state imaging elements, light-emitting diodes Polar body, organic light-emitting device, light-emitting film, fluorescent film, actuator, hologram, plasma device, polarizing plate, polarizing film, retardation film, liquid crystal display device used in the backlight lens sheet, Lens parts of lens flakes such as Fresnel lens flakes and lenticular lens flakes used in screens for projection TVs, etc., or optical lenses, optical elements, optical connectors, etc. using backlights such as such flakes, microlenses, etc. Casting agent for optical waveguide and optical forming.

From the viewpoint that the composition of the present invention can more effectively exert the effect of excellent curing speed and excellent adhesion, it is preferably used as an adhesive. The specific application of the adhesive is that it can be used for optical materials such as glasses or photographic lenses, electronic materials such as laminates or printed substrates, automotive equipment such as head-up displays or car navigation, and Various applications such as display panels represented by organic EL or liquid crystal. Among them, the best is used for applications requiring transparency, and the best is used for optical materials, automotive equipment, display panels, etc.

When the composition of the present invention is used as an adhesive, the adherend to be adhered by the adhesive of the present invention may be an inorganic material or an organic material.

Examples of the organic material include cellulose esters such as diethyl cellulose, triethyl cellulose (TAC), propyl cellulose, butyl cellulose, acetyl cellulose, nitrocellulose, etc. Polyamide; Polyimide; Polyurethane; Epoxy compound; Polycarbonate; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate , Poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polyterephthalic acid Polyesters such as butadiene; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene, polytetrafluoroethylene, cycloolefin polymer; polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride , Vinyl compounds such as polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; poly satin; polyether satin; polyether ketone; polyether amide imine; polyoxyethylene , Polymer materials such as norbornene resin. In addition, examples of the inorganic material include glass such as soda glass and quartz glass, metals, and metal oxides.

<Adhesive> Next, the adhesive of the present invention will be described. The adhesive of the present invention contains the composition of the present invention. By containing the composition of the present invention, the adhesive of the present invention is excellent in hardening speed, adhesion and water resistance.

The adhesive of the present invention can be produced using the composition of the present invention. The adhesive of the present invention may contain only the composition of the present invention, or may be produced by mixing the composition of the present invention with various additives known to be used when manufacturing the adhesive using a known mixing device. In addition, the use of the composition and the adhesive of the present invention can be the same as the content described in the item of the composition, so the description is omitted here.

When the adhesive of the present invention is used as an adhesive for joining two members, the thickness of the adhesive of the present invention after hardening is appropriately set according to the use of the adhesive of the present invention, for example, it can be 0.5 μm or more and 10 μm the following.

<hardened product> Next, the cured product of the present invention will be described. The hardened product of the present invention is a hardened product of the composition of the present invention. The cured product of the present invention can be used as an adhesive layer excellent in curing speed and adhesive force, for example. In addition, the composition of the present invention may be the same as the content described in the item of "composition", so the description is omitted here.

The cured product of the present invention is a cured product of the composition of the present invention, which is a polymer containing the composition of the present invention. That is, the hardened product of the present invention has a cross-linked condensation ring.

The apparent shape, thickness, etc. of the cured product of the present invention can be appropriately set according to the application of the cured product.

The hardened product of the present invention is obtained by forming the composition of the present invention into a desired shape and hardened, and the manufacturing method is not particularly limited. Such a manufacturing method may be, for example, the same as described in the item of the manufacturing method of the hardened product described later, and therefore the description is omitted here.

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

<Manufacturing method of hardened product> Next, the method of manufacturing the hardened product of the present invention will be described. The method of manufacturing a hardened product of the present invention has a hardening step of hardening the composition of the present invention. According to the method of manufacturing a hardened product of the present invention, the hardening step is to use the composition of the present invention, and thus a hardened product having a hardening speed and an adhesive force can be obtained. Hereinafter, each step of the method for manufacturing a hardened product of the present invention will be described in detail.

1. Hardening step The hardening step is a step of hardening the composition of the present invention, which includes a step of irradiating active energy rays or heating. This hardening method may be the same as the content described in the item "A. Composition".

2. Other steps The manufacturing method of the hardened product of the present invention may have other steps as needed. Such steps may include a step of applying the composition of the present invention before the step of hardening the composition of the present invention. For the method of applying the composition of the present invention, known methods such as a spin coater, a roll coater, a bar coater, a die coater, a shower coater, various printing, and dipping can be used. In the coating step, the composition of the present invention can be coated on a substrate.

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

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

The composition of the present invention, the adhesive containing it, the cured product thereof, and the method for producing the same are not limited to the above-mentioned embodiments. The above embodiments are examples, and those having substantially the same structure as the technical idea described in the patent application scope of the present invention and exerting the same effect are included in the technical scope of the present invention. [Example]

The following examples are given to explain the present invention in more detail, but the present invention is not limited to these examples.

[Examples 1 to 28 and Comparative Examples 1 to 7] The components were blended according to the blending ratios described in Tables 1 to 5 below to obtain compositions. The following materials are used for each component. In addition, the blending amount in the table represents the mass parts of each component.

Ingredients (A) A1-1: Tricyclodecane dimethanol diacrylate A1-2: Dicyclopentyl acrylate A2-1: 4-n-hydroxybutyl acrylate A2-2: Compound (A2) No.1 A3-1: Tris(acryloylethyl) isocyanurate A3-2: Modification of ε-caprolactone ginseng (2-acryloyloxyethyl) isocyanurate A4-1: 1,6-hexanediol diacrylate A4-2: 1,10-decanediol diacrylate

Ingredients (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-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate B3-3: Trimethylolpropane triglycidyl ether B3-4: 3,3’-[oxybis(methylene)]bis(3-ethyloxetane) B3-5: Bisglycol ether of bisphenol A

Ingredients (C) C-1: 1-hydroxycyclohexyl phenyl ketone

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

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

[Evaluation] For each of the obtained compositions, the viscosity, initial hardenability, adhesive strength and water resistance were evaluated in the following order.

(Viscosity) The viscosity of each obtained composition was measured with an E-type viscometer at 25°C. A composition with a viscosity of 30 to 80 mPa･s is preferable because of its excellent coating property, and a composition of 40 to 70 mPa･s is particularly preferable.

(Method for preparing samples for evaluation) Each of the obtained compositions was applied to a PMMA film (Technolloy 125S001 manufactured by Sumitomo Chemical Co., Ltd.) to make the thickness after curing 3 μm. Then, using a bonding machine, Laminated with another COP (cycloolefin polymer, Zeon Corporation, Japan: ZeonorFilm 14-060) film that has undergone corona discharge treatment, uses an electrodeless ultraviolet lamp, and radiates through the COP film equivalent to 1,000 The light of mJ/cm ² was used for evaluation.

The 90˚ peel test of the obtained sample for evaluation was performed and the evaluation was performed according to the following criteria. The results are shown in Tables 1 to 5 below. In addition, in the 90˚ peeling test system, the sample for evaluation was stretched and peeled in the direction of 90˚ with a tensile tester FTN1-13A (manufactured by Aikoh Engineering) at 25°C. The PMMA film was measured by COP The maximum strength when the film is peeled off is used as the adhesion.

(Initial hardening) With respect to the obtained evaluation sample, after standing at 30° C., 50% RH, and atmospheric pressure for 3 minutes from exposure, a 2.0 cm width was cut out to obtain a sample for evaluation. Using this sample for evaluation, 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 force is 0.6N/20mm or more B: The adhesive force is 0.4N/20mm or more and less than 0.6N/20mm C: The adhesion force is less than 0.4N/20mm The materials evaluated as A and B can be preferably used as an adhesive, and the materials evaluated as A are particularly good. The things evaluated as C are limited in usable use, so it is not good.

(Adhesion) With respect to the obtained evaluation sample, under conditions of 30° C., 50% RH, and atmospheric pressure, 12 hours after exposure, a 2.0 cm width was cut out to obtain a sample for evaluation of adhesion. The obtained sample was subjected to a 90˚ peel test under the above conditions, the adhesion was measured, and the evaluation was performed according to the following criteria.

A: Adhesion force is more than 2.5N/20mm B: Adhesion force is more than 1.5N/20mm and less than 2.5N/20mm C: Adhesion force is 1.0N/20mm or more and less than 1.5N/20mm D: The adhesion force is less than 1.0N/20mm Subsequent force of A or B can be used as an adhesive, especially A. Subsequent forces of C and D are poor as adhesives.

(Water resistance) The water resistance is evaluated by the adhesion of warm water. The obtained evaluation sample was immersed in 60°C warm water for 48 hours after exposure for 30 hours at 30°C, 50% RH, and atmospheric pressure. After being immersed in warm water at 60°C for 48 hours, it was taken out from the warm water and dried, and then a 2.0 cm width was cut out. , And then obtain the sample for force evaluation after obtaining warm water. The obtained sample was subjected to a 90˚ peel test by the above-mentioned method, and the adhesive force after warm water was measured, and the evaluation was performed according to the following criteria.

A: The adhesive force after warm water is 2.5N/20mm or more B: The adhesive force after warm water is 1.5N/20mm or more and less than 2.5N/20mm C: The adhesive force after warm water is 1.0N/20mm or more and less than 1.5N/20mm D: The adhesive force after warm water is less than 1.0N/20mm After the warm water, the adhesive force is A, B or C, and it can be used as an adhesive agent with excellent water resistance, preferably A or B, particularly preferably A. The adhesive with a strength of D after warm water is not good as an adhesive for applications requiring water resistance.

From Tables 1 to 5, it can be confirmed that the compositions of the examples are excellent in coatability, initial hardenability, adhesion, and water resistance. Therefore, the composition of the present invention is useful as an adhesive.

Claims (11)

A composition comprising a radical polymerizable component (A) and a cationic polymerizable component (B), characterized by, The radical polymerizable component (A) contains 70 to 100 parts by mass of the radical polymerizable compound (A1) having a cross-linked condensation ring in 100 parts by mass of the radical polymerizable component (A), The cationic polymerizable component (B) contains 10 to 50 parts by mass of the cationic polymerizable compound (B1) having a cross-linked condensation ring in 100 parts by mass of the cationic polymerizable component (B). The composition of claim 1, which further contains a radical polymerizable initiator (C) and a cationic polymerizable initiator (D), and In 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), Contains 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 the cationic polymerization 1 to 10 parts by mass of sexual initiator (D). The composition according to claim 1 or 2, wherein the cross-linked condensation ring contained in the radical polymerizable compound (A1) and the cationic polymerizable compound (B1) has a structure represented by the following formula (I) Cross-linked condensation ring,

The composition according to any one of claims 1 to 3, which contains a cationic polymerizable compound (B2) having a weight average molecular weight of 1,000 or more and not more than 30,000 without a cross-linked condensation ring as the aforementioned cationic polymerizable component (B) . The composition according to any one of claims 1 to 4, which contains a cationic polymerizable compound (B3) having a weight average molecular weight of 200 or more and not more than 1,000 without a cross-linked condensation ring as the aforementioned cationic polymerizable component (B) . The composition according to claim 5, wherein the cationic polymerizable compound (B3) contains a compound having an oxetanyl group. The composition according to any one of claims 1 to 6, which contains a radically polymerizable compound (A2) having a cationic polymerizable group and not having an isocyanurate ring and a cross-linked condensation ring, as the aforementioned freedom Base polymerizable component (A). The composition according to any one of claims 1 to 7, which contains a radical polymerizable compound (A3) containing an isocyanurate ring and not having a cross-linked condensation ring, as the aforementioned radical polymerizable component ( A). An adhesive characterized by containing the composition according to any one of claims 1 to 8. A hardened product characterized by comprising the composition according to any one of claims 1 to 8. A method for manufacturing a hardened product, which comprises the steps of irradiating an active energy ray or heating a composition according to any one of claims 1 to 8.