JP7452206B2 - Active energy ray curable adhesive composition - Google Patents

Description

The present invention provides an active energy ray-curable adhesive that can bond various base materials with gaps between them, preferably plastic sheet-like base materials, by irradiation with active energy rays such as electron beams or ultraviolet rays. Regarding agent compositions, it belongs to the technical field.

2. Description of the Related Art Conventionally, thermosetting adhesive compositions have been used as adhesive compositions for bonding components and members in the manufacture of building materials, electronic parts, mechanical parts, optical parts, and the like. However, thermosetting adhesive compositions have a problem of low productivity due to their long curing time.
To solve this problem, adhesive compositions that are not thermosetting but are cured by irradiation with active energy rays such as ultraviolet rays have been proposed. Since the active energy ray-curable adhesive composition completes adhesion in an extremely short time, it is possible to significantly improve productivity.

For example, Patent Document 1 describes 30 to 70% by weight of urethane (meth)acrylate with a number average molecular weight of 10,000 to 40,000 and 30 to 60% by weight of an ethylenically unsaturated monomer whose homopolymer has a glass transition temperature of 60°C or higher. A liquid curable resin composition is disclosed.
This composition has excellent adhesion to plastic substrates, as well as excellent heat resistance and water resistance, and is suitable for polyvinyl chloride (hereinafter referred to as "PVC") sheets and polyethylene terephthalate (hereinafter referred to as "PET") films. It has been disclosed that it is useful for laminating various parts and for adhering various parts.

Japanese Patent Application Publication No. 2004-115757

By the way, when bonding components or members in the production of building materials, electronic parts, mechanical parts, optical parts, etc., if there is a large gap between the adherends, the liquid may leak after the adhesive composition is injected. There is a problem that it sag and cannot be properly adhered.
The present inventors investigated and found that although the composition disclosed in Patent Document 1 has excellent adhesion to plastic sheets such as PVC sheets and PET films, the gap between adherends is less than 0.1 mm. If the thickness exceeds 0.3 mm, the liquid composition will drip (hereinafter referred to as "drip"), making it impossible to increase the bonding area and ensuring sufficient adhesive strength. It turned out that I couldn't get it.
Furthermore, it was found that if the viscosity of the composition was increased to prevent dripping, although dripping could be suppressed, it became difficult to pour the composition into the gaps between the adherends, significantly reducing workability. .

Furthermore, since the cured product obtained by curing the composition disclosed in Patent Document 1 has a high reflectance, if the part where the composition protrudes is cured and remains, only that part will have an unnatural gloss (shininess). It was also found that the appearance was undesirable.

The purpose of the present invention is to solve the above-mentioned problems of the prior art, to suppress dripping, to have excellent workability, to have excellent adhesion to various adherends, and to be able to maintain sufficient adhesion even when there are large gaps between adherends. An object of the present invention is to provide an active energy ray curable adhesive composition, preferably an active energy ray curable adhesive composition for plastic sheet-like substrates, which exhibits a high adhesive strength and a reduced gloss of the cured product.

As a result of intensive studies to solve the above problems, the present inventors found that urethane (meth)acrylate, (meth)acryloylmorpholine, a compound having one ethylenically unsaturated group, a photoradical polymerization initiator, and a thixotropic An active energy ray-curable adhesive composition containing a specific proportion of an active energy ray-curable adhesive composition having a specific viscosity behavior suppresses dripping after being applied to an adherend and has good workability. The present invention was completed based on the discovery that the material has excellent adhesion to the base material and matte properties.
The present invention will be explained in detail below.

According to the active energy ray-curable adhesive composition of the present invention, dripping is suppressed and workability is good, and the adhesive composition has excellent adhesion to substrates, especially plastic substrates, and is matte. It can also be made to have excellent properties.

The present invention is a composition containing the following components (A) to (C) as curable components, and the following components (D) and (E) as components other than the curable component,
Contains the following components (A) to (C) in the following proportions in 100% by weight of the total amount of curable components,
(A) Component: 5 to 60% by weight
(B) Component: 20 to 70% by weight
(C) Component: 10 to 75% by weight
Contains the following components (D) to (E) in the following proportions based on 100 parts by weight of the total amount of curable components,
The present invention relates to an active energy ray-curable adhesive composition whose viscosity satisfies the following.
(D) component: 0.1 to 15 parts by weight (E) component: 0.1 to 15 parts by weight
・Curing component
(A) Component: Urethane (meth)acrylate (B) Component: Acryloylmorpholine (C) Component: Compound having one ethylenically unsaturated group other than components (A) and (B)
・Components other than curable components
(D) Component: Photoradical polymerization initiator (E) Component: Thixotropic agent
·viscosity
The viscosity measured using a cone-plate rotational viscometer at a temperature of 25°C and a shear rate of 383 s ^-1 according to JIS K 6833 is 50 to 5,000 mPa・s, and JIS K 5101-6-2 2004, the TI value determined at a temperature of 25°C using a cone-plate rotational viscometer is 1.5 to 20.
Components (A) to (E), other components, active energy ray-curable adhesive composition, and method of use will be explained in detail below.
In this specification, acrylate and/or methacrylate is referred to as (meth)acrylate, acryloyl group and/or methacryloyl group is referred to as (meth)acryloyl group, and acrylic acid and/or methacrylic acid is referred to as (meth)acrylic acid, acrylamide. /Methacrylamide is expressed as (meth)acrylamide. Further, ultraviolet light emitted from a light emitting diode as a light source is referred to as UV-LED.
Further, "〇〇~△△" which means a numerical range means 〇〇 or more and △△ or less.

1. Component (A) Component (A) is urethane (meth)acrylate which is a (meth)acrylate compound having a urethane bond.
Component (A) includes a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate [hereinafter referred to as "urethane (meth)acrylate oligomer"], and a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate. (hereinafter referred to as "urethane adduct").
Urethane (meth)acrylate oligomers are preferred as component (A) because the resulting composition has excellent adhesive strength.
The raw material compound and manufacturing method of component (A) will be explained below.

1-1. Raw material compound In the case of urethane (meth)acrylate oligomer, polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate are used as the raw material compound of component (A), and in the case of urethane adduct, organic polyisocyanate and hydroxyl group-containing ( using meth)acrylate.

Specific examples of polyols include polyether polyols, polycarbonate polyols, polyester polyols, and diols having a polyene skeleton.
Examples of polyether polyols include polyalkylene glycols having two or more oxyalkylene units, and specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
Examples of polycarbonate polyols include reaction products of carbonate and diol. Specific examples of carbonates include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. In addition, examples of the diol include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, nonanediol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1, Examples include 5-pentanediol and hydroxypivalic acid neopentyglycol ester (hereinafter referred to as "low molecular weight diol").
Examples of the polyester polyol include a reaction product of at least one selected from the group consisting of the above-mentioned low molecular weight diols, polyether polyols, and polycarbonate polyols and an acid component. Specific examples of acid components include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or their anhydrides, and ring-opening reaction products of polycarbonate diol and caprolactone. etc.
Examples of diols having a polyene skeleton include diols having a polybutadiene skeleton, diols having a polyisoprene skeleton, diols having a hydrogenated polybutadiene skeleton, and diols having a hydrogenated polyisoprene skeleton.
The above polyols may be used alone or in combination of two or more.

Examples of the organic polyisocyanate include diisocyanate and triisocyanate.
Specific examples of diisocyanates include aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate and naphthalene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; isophorone diisocyanate; Examples include alicyclic diisocyanates such as '-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylene diisocyanate.
Specific examples of triisocyanates include 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate.
The above organic polyisocyanates may be used alone or in combination of two or more.

Specific examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1, 4-Cyclohexanedimethylol mono(meth)acrylate, pentanediol mono(meth)acrylate, hexanediol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono (meth)acrylate, mono(meth)acrylate of polyethylene glycol, mono(meth)acrylate of dipropylene glycol, mono(meth)acrylate of tripropylene glycol, mono(meth)acrylate of polypropylene glycol, 2-hydroxy-3-phenoxy Hydroxyl group-containing monofunctional (meth)acrylates such as propyl (meth)acrylate and 2-hydroxy-3-butoxypropyl (meth)acrylate; and
Mono- or di-(meth)acrylate of trimethylolpropane, mono-, di- or tri(meth)acrylate of pentaerythritol, mono-, di- or tri(meth)acrylate of ditrimethylolpropane and mono-, di-, tri-, tetra-acrylate of dipentaerythritol. Alternatively, hydroxyl group-containing polyfunctional (meth)acrylates such as penta(meth)acrylate and epoxy(meth)acrylate may be mentioned.
The above hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.

As component (A), (meth)acryloyl is a reaction product using a diol as a polyol, a diisocyanate as an organic polyisocyanate, and a hydroxyl group-containing monofunctional (meth)acrylate as a hydroxyl group-containing (meth)acrylate. Urethane (meth)acrylate containing two groups is preferred because the resulting composition has excellent adhesive strength.
In addition, polyether-based urethane (meth)acrylate, polyester-based urethane (meth)acrylate, and polycarbonate-based polyol using polyether polyol, polyester polyol, and polycarbonate polyol as raw material polyols can further improve adhesive strength. Urethane (meth)acrylate is preferred, and polyether urethane (meth)acrylate and polyester urethane (meth)acrylate are more preferred.

1-2. Production method Among components (A), in the case of urethane (meth)acrylate oligomer, polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate are heated in the presence of a urethanization catalyst and, if necessary, a reaction solvent. - Can be manufactured by stirring and converting into urethane.
In this case, the polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate can be charged all at once and reacted (hereinafter referred to as "one-stage reaction"), and the polyol and organic polyisocyanate are reacted to form an isocyanate group-containing prepolymer. After producing , a hydroxyl group-containing (meth)acrylate can also be added (hereinafter referred to as "two-stage reaction").
In the case of a urethane adduct, it can be produced by urethanization by heating and stirring in the presence of an organic polyisocyanate, a hydroxyl group-containing (meth)acrylate, and a urethanization catalyst, and if necessary in the presence of a reaction solvent.

Examples of urethanization catalysts include amine compounds and metal catalysts.
Specific examples of amine compounds include triethylamine and the like.
Specific examples of the metal catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin diacetylacetonate, bismuth dioctate, iron (III) acetylacetonate, zinc acetylacetonate, and aluminum acetylacetonate.
The above urethanization catalysts may be used alone or in combination of two or more.

In the case of urethane (meth)acrylate oligomers, the ratio of polyol and organic polyisocyanate may be set appropriately depending on the structure of the urethane (meth)acrylate to be finally obtained. The total amount of isocyanate groups in the organic polyisocyanate is preferably 1.05 to 2 mol per 1 mol of the total amount.
The proportion of the hydroxyl group-containing (meth)acrylate is preferably such that no isocyanate group remains in the resulting urethane (meth)acrylate.
When producing by the above two-stage reaction, the amount of hydroxyl group-containing (meth)acrylate is preferably 1.0 to 1.5 mol per 1 mol of the total amount of isocyanate groups in the isocyanate group-containing prepolymer.
In the case of manufacturing by the one-stage reaction described above, per mole of the total amount of isocyanate groups remaining in the isocyanate group-containing prepolymer calculated based on the structure of the urethane (meth)acrylate to be finally obtained, The proportion of the hydroxyl group-containing (meth)acrylate is preferably 1.0 to 1.5 moles.
In this case, the ratio of the total amount of hydroxyl groups in the polyol and acid group-containing (meth)acrylate to 1 mol of isocyanate groups in the organic polyisocyanate is preferably 1.0 to 1.5 mol.

In the case of urethane adducts, the ratio of hydroxyl group-containing (meth)acrylate is preferably such that no isocyanate groups remain in the resulting urethane (meth)acrylate, and the ratio of hydroxyl group-containing (meth)acrylates to 1 mole of the total amount of isocyanate groups in the organic polyisocyanate is preferable. The content of (meth)acrylate is preferably 1.0 to 1.5 moles.

Incidentally, if the molecular weight of component (A) produced by this reaction becomes high, the reaction mixture becomes highly viscous and stirring may become difficult, so a reaction solvent may be blended into the reaction components.
The reaction solvent is preferably one that does not participate in the urethanization reaction, and includes organic solvents such as aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
When using an organic solvent, the amount may be appropriately determined depending on the viscosity of component (A) to be produced, but it is preferably set so that it is 0 to 70% by weight in the reaction solution.
Here, the reaction solution means the total amount of the raw material compounds when only the raw material compounds are used, and the total amount including these when using the reaction solvent in addition to the raw material compounds. Specifically, it is used to mean a solution containing a polyol, an organic polyisocyanate, a hydroxyl group-containing (meth)acrylate, a reaction solvent used as necessary, and the like.

Component (A) and (meth)acrylate compounds other than component (A) (hereinafter referred to as "other (meth)acrylates") used as a component of the composition together with or in place of the organic solvent as a reaction solvent. ) can also be blended. As other (meth)acrylates, those described below as other components can be used. When blending other (meth)acrylates and performing a urethanization reaction, and blending the obtained urethane (meth)acrylate into an active energy ray-curable adhesive composition, unlike the case where the organic solvent is blended, the composition This is preferable because there is no need to dry the product after applying it.
The amount of other (meth)acrylates to be added to the reaction component may be determined as appropriate depending on the proportion of other (meth)acrylates to be finally added to the composition. It is preferably set to 70% by weight, more preferably 10 to 50% by weight.

The amount of the urethanization catalyst may be a catalytic amount, for example, preferably 0.01 to 1,000 wtppm, more preferably 0.1 to 1,000 wtppm, based on the reaction solution. When the amount of the metal compound is 0.01 wtppm or more, the urethanization reaction can proceed preferably, and when it is 1,000 wtppm or less, coloring of the resulting component (A) can be suppressed. .

In the case of urethane (meth)acrylate oligomers, the urethanization catalyst is added at the time of preparing the polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate for a one-stage reaction, and added at the time of preparing the polyol and organic polyisocyanate for a two-stage reaction. It can be added at the time of isocyanate preparation.
In the case of urethane adduct, it can be added at the time of preparing the organic polyisocyanate and the hydroxyl group-containing (meth)acrylate.

In the urethanization reaction, a small amount of a chain extender may be added for the purpose of molecular weight adjustment.
As the chain extender, those commonly used in urethanization reactions can be used, including those similar to the above-mentioned low molecular weight polyols.

In the urethanization reaction, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization of the (meth)acryloyl group of the raw material or product, and furthermore, an oxygen-containing gas may be introduced into the reaction solution.
Specific examples of polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, and phenothiazine. organic polymerization inhibitors such as copper chloride and copper sulfate, organic salt polymerization inhibitors such as copper dibutyl dithiocarbamate, 4-hydroxy-2,2,6,6-tetra Examples include stable radicals such as methylpiperidine-1-oxyl free radical and galbinoxyl.
The polymerization inhibitors may be used alone or in any combination of two or more. The proportion of the polymerization inhibitor in the reaction solution is preferably 5 to 20,000 wtppm, more preferably 25 to 3,000 wtppm.
Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

The reaction temperature may be appropriately set depending on the raw materials used and the structure and molecular weight of the desired component (A), but is usually preferably 25 to 150°C, more preferably 30 to 120°C. The reaction time may be appropriately set depending on the raw materials used and the structure and molecular weight of the target urethane (meth)acrylate, but it is usually preferably 1 to 70 hours, more preferably 2 to 30 hours.

1-3. Preferred component (A)/content ratio The weight average molecular weight (hereinafter referred to as "Mw") of component (A) in the present invention is preferably 1,000 to 50,000 from the viewpoint of improving the adhesive strength of the composition. .
In the present invention, Mw is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") into polystyrene, and means a value measured under the following conditions.
・Detector: Differential refraction system (RI detector)
・Column type: Cross-linked polystyrene column ・Column temperature: 40℃
・Eluent: Tetrahydrofuran ・Molecular weight standard: Polystyrene

As component (A), only one type can be used or two or more types can be used in combination.

The content of component (A) is 5 to 60% by weight, preferably 10 to 50% by weight, and more preferably 20 to 40% by weight, based on 100% by weight of the total amount of curable components.
If the proportion of component (A) is less than 5% by weight, the durability after adhesion will decrease, and if it exceeds 60% by weight, the composition will have a high viscosity and the coating workability of the composition will decrease. will decrease.

Furthermore, as component (A), it is more preferable to use two types of urethane (meth)acrylates having different Mws in combination, since the matting properties of the cured composition are improved.
Specific examples include urethane (meth)acrylate with an Mw of 1,000 to 15,000 (hereinafter referred to as "(AL) component"), and urethane (meth)acrylate with an Mw of over 15,000 to 50,000. ) acrylate [hereinafter referred to as "component (AH)"] is preferred.
The term "improved matteness" here means that when the reflectance of the cured product obtained by curing the composition is high, if the part where the composition protrudes is cured and remains, only that part will have an unnatural shine. This means that shine is suppressed by making the cured composition matte because it is easily recognized and is unfavorable in terms of appearance.
Furthermore, the Mw of the (AL) component is preferably 2,000 to 10,000, and the Mw of the (AH) component is preferably 20,000 to 40,000.
The proportions of the (A-L) and (A-H) components are 60 to 95% by weight and 5 to 95% by weight of the (A-H) components in the total 100% by weight of these components. It is preferable to contain 40% by weight, more preferably 70 to 90% by weight of component (AL) and 10 to 30% by weight of component (AH).

2. Component (B) Component (B) is (meth)acryloylmorpholine, and is a component for improving the curability of the composition and improving the adhesiveness to a substrate, preferably the adhesiveness to a plastic substrate.

The content of component (B) is 20 to 70% by weight, preferably 25 to 60% by weight, based on 100% by weight of the total amount of curable components.
If the proportion of component (B) is less than 20% by weight, the curability will decrease, and if it exceeds 70% by weight, the adhesiveness to the substrate, preferably the adhesive force to the plastic substrate will decrease.

3. Component (C) Component (C) is a compound having one ethylenically unsaturated group other than components (A) and (B).

As component (C), various compounds can be mentioned as long as they have one ethylenically unsaturated group other than components (A) and (B), and (meth) having one (meth)acryloyl group can be mentioned. Acrylate [hereinafter referred to as "monofunctional (meth)acrylate"], (meth)acrylamide having one (meth)acryloyl group, vinyl compound having one vinyl group, allyl compound having one allyl group, etc. can be mentioned.

Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2- Ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1,4-cyclohexanedimethylol mono(meth)acrylate, dicyclopentanyl ( meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate of phenol alkylene oxide adduct, (meth)acrylate of p-cumylphenol alkylene oxide adduct meth)acrylate, (meth)acrylate of o-phenylphenol alkylene oxide adduct, (meth)acrylate of nonylphenol alkylene oxide adduct, 2-methoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-ethylhexyl alcohol (meth)acrylate of alkylene oxide adducts, pentanediol mono(meth)acrylate, hexanediol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate (meth)acrylate, mono(meth)acrylate of polyethylene glycol, mono(meth)acrylate of dipropylene glycol, mono(meth)acrylate of tripropylene glycol, mono(meth)acrylate of polypropylene glycol, 2-hydroxy-3-phenoxy Propyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, (2-ethyl-2-methyl-1,3- dioxolan-4-yl) methyl (meth)acrylate, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth)acrylate, (1,4-dioxaspiro[4,5]decane- 2-yl)methyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, 2-(meth)acryloyl Oxyethyl isocyanate, allyl (meth)acrylate, N-(meth)acryloyloxyethylhexahydrophthalimide, N-(meth)acryloyloxyethyltetrahydrophthalimide, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalimide, ) Acryloyloxyethylsuccinic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxy Examples include propyldimethoxymethylsilane, 3-(meth)acryloyloxypropyltriethoxysilane, and 2-(meth)acryloyloxyethyl acid phosphate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Examples of (meth)acrylamide include N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and hydroxyethyl (meth)acrylamide.
Examples of the vinyl compound include N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylformamide.
Examples of allyl compounds include allyl alcohol and the like.

As component (C), 4-hydroxybutyl acrylate, (meth)acrylate of phenol alkylene oxide adduct, ethoxyethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. ) acrylate and N-(meth)acryloyloxyethyltetrahydrophthalimide are preferred, and 4-hydroxybutyl acrylate and ethoxyethoxyethyl (meth)acrylate are even more preferred in terms of their low odor.

The content of component (C) is 10 to 75% by weight, preferably 15 to 70% by weight, based on 100% by weight of the total amount of curable components.
If the proportion of component (C) is less than 10% by weight, the adhesive strength of the composition will decrease, and if it exceeds 75% by weight, the dripping properties and water resistance of the cured composition will decrease.

5. Component (D) Component (D) is a photoradical polymerization initiator. Component (D) is a compound that generates radicals upon irradiation with active energy rays and initiates polymerization of the curable components [components (A) to (C)], which are compounds having ethylenically unsaturated groups.

Specific examples of component (D) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane. 1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1- on, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)] -benzyl]-phenyl]-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one , Adeka Optomer N-1414 (manufactured by Asahi Denka), aromatic ketone compounds such as phenylglyoxylic acid methyl ester, ethyl anthraquinone, and phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1- [4-(4-Benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis Benzophenones such as (diethylamino)benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone Compound;
Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine and bis(2, Acyl phosphine oxide compounds such as 6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthon-2-yl]oxy]- Thioxanthone compounds such as 2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone and 10-butyl-2-chloroacridone;
1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -1-(O-acetyloxime) and other oxime esters, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxy) phenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p- methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethoxyphenyl)-4,5-diphenyl Examples include 2,4,5-triarylimidazole dimers such as imidazole dimers; and acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane.

As component (D), the above-mentioned compounds may be used alone or in combination of two or more.

As component (D), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane is used, since the composition has excellent curability. -1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4 -1-(methylvinyl)phenyl]propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred, and 1-hydroxycyclohexyl phenyl ketone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are more preferred.

Further, as component (D), when a UV-LED is used as a light source, it is preferable to use an acylphosphine oxide compound, specific examples of which are as listed above.
Furthermore, when curing under air, it is preferable to use an acylphosphine oxide compound and an aromatic ketone compound in combination, since curability can be further increased. Specific examples of the aromatic ketone compound are as listed above.

The content of component (D) is 0.1 to 15 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total amount of curable components.
If the proportion of component (D) is less than 0.1 parts by weight, the active energy ray curability of the composition will decrease, resulting in a decrease in adhesive properties, while if it exceeds 15 parts by weight, , the internal curability of the adhesive layer decreases, resulting in a decrease in adhesiveness.

6. Component (E) Component (E) is a thixotropic agent.
By blending component (E), structural viscosity can be imparted to the composition, and the viscosity is low under the high shear force when the composition is injected into the adherend, resulting in good workability. Under low shear force, the viscosity becomes high and dripping can be effectively prevented.

As component (E), any compound can be used as long as it can impart structural viscosity to the Newtonian liquid, including organic thixotropic agents and inorganic thixotropic agents, and these can also be used in combination.
Examples of organic thixotropic agents include polymers other than component (A), hydrogenated castor oil, amide, oxidized polyethylene, vegetable oil polymers, surfactants, and composites using these in combination. Can be mentioned.
Specific examples of polymers other than component (A) include polymers such as polyhydroxycarboxylic acid amide, polyhydroxycarboxylic acid ester, polyurethane, poly(meth)acrylate, polyamide, polyurea, nylon, polystyrene, polyethylene, and polypropylene, and carbon nanotubes. , cellulose nanofibers, and the like.
Organic thixotropic agents are commercially available, and specifically include RHEOBYK-405, 430, 431, 7410ET, 7411ES, R605, R606 and R607, BYK-410, 420, 425, 428, 430, and 431 (all , BIC Chemie Japan Co., Ltd. (trade name), and DISPARLON 6900-20X (Kusumoto Kasei Co., Ltd. trade name).

Examples of the inorganic thixotropic agent include inorganic fillers.
Specific examples of inorganic fillers include silica, hollow silica, alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and antimony tin oxide (ATO). , cerium oxide, potassium oxide, composite oxides made of two or more of these compounds, and bentonite.
Among these, silica and bentonite are preferred, and silica is more preferred.

In order to improve the dischargeability of the liquid, it is preferable that component (E) is free of aggregates as much as possible.
Therefore, in order to disperse the component (E), as a mechanical method, kneading and stirring using a bead mill, three-roll kneader, planetary mixer, or the like is preferable. Among these, kneading and stirring using a planetary kneader is particularly preferred since it has good dispersibility and good workability.

Furthermore, from the viewpoint of handling and transparency, the average primary particle diameter of component (E) is preferably 1 nm or more and 200 nm or less, particularly preferably 5 nm or more and 100 nm or less. When the average primary particle diameter is 1 nm or more, the particle surface has low activity, so it is easy to maintain a dispersed state, and aggregation and gelation are less likely to occur. On the other hand, if the average primary particle diameter is 200 nm or less, haze due to Rayleigh scattering is difficult to observe. Since Rayleigh scattering is proportional to the square of the particle volume, that is, the sixth power of the particle diameter, scattering is small for particles with an average primary particle diameter of 1/4 or less of the wavelength of visible light, which reduces active energy ray curability. It can be made into a good one.
The average primary particle diameter can be determined by, for example, observing inorganic oxide fine particles with a high-resolution transmission electron microscope, arbitrarily selecting 100 inorganic oxide particle images from the observed fine particle images, and using a known image data statistical processing method. It can be determined as a number average particle diameter.

The content of component (E) is 0.1 to 15 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total amount of curable components.
If the proportion of component (E) is less than 0.1 parts by weight, dripping properties will be reduced, while if it exceeds 15 parts by weight, workability will be reduced.

As described above, silica is more preferable as component (E).
Examples of the silica include hydrophobic silica and hydrophilic silica depending on the surface condition, and tampered silica can also be used. Silica is commercially available, and examples of hydrophilic silica include Aerosil 50, 130, and 200, and examples of hydrophobic silica include R972, R974, RX50, RX200, RX300, and RY200S [all of which are Nippon Aerosil ( Co., Ltd. product name], etc.

Among the above-mentioned compounds, as component (E), silica and a polymer other than component (A) are preferred from the viewpoint of excellent storage stability of the composition, and silica is preferred from the viewpoint of excellent matting properties of the cured composition. More preferred.

There are no particular limitations on the powder properties of silica, such as specific surface area and surface condition, but considering ease of dispersion into the composition and structural viscosity, the specific surface area is preferably 50 to 300 m ² /g, and the surface Hydrophobicity is preferred as the state.
In the present invention, the specific surface area means a value measured by the BET method (low-temperature, low-humidity physical adsorption of an inert gas).

Only one type of thixotropic agent may be used, or a plurality of types may be used in combination.
For example, when using hydrophilic silica, the structural viscosity can be further changed by adding polyhydroxycarboxylic acid amide (BYK-R605) or polyhydroxycarboxylic acid ester (BYK-R606).

7. Other Components The composition of the present invention has components (A) to (E) as essential components, but various other components can be added depending on the purpose.

Other components include radical curable components other than component (A) having two or more unsaturated double bonds in the molecule (hereinafter referred to as component (F)), sensitizers, ultraviolet absorbers, and polymerization inhibitors. agents, silane coupling agents, antioxidants, surface modifiers, and the like.
Other components to be described later may be used alone or in combination of two or more.

7-1. (F) Component

As radically curable components other than component (A) having two or more unsaturated double bonds in the molecule, compounds having two or more (meth)acryloyl groups in the molecule [hereinafter referred to as "polyfunctional (meth) ) acrylate], and compounds having two or more vinyl groups in the molecule (hereinafter referred to as "polyfunctional vinyl compounds"). Furthermore, various molecular weights can be selected, and they may be monomers, oligomers, or polymers.

Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 , 6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate and 1,9 - di(meth)acrylates of aliphatic diols, such as nonanediol di(meth)acrylates;
Di(meth)acrylates of alicyclic diols such as cyclohexane dimethylol di(meth)acrylate and tricyclodecane dimethyloldi(meth)acrylate;
Alkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate;
The esterification reaction product of neopentyl glycol, hydroxypivalic acid, and (meth)acrylic acid (hereinafter referred to as "neopentyl hydroxypivalate glycol di(meth)acrylate"), caprolactone-modified neopentyl glycol di(meth)acrylate hydroxypivalate, ) acrylate;
Di(meth)acrylate of alkylene oxide adduct of bisphenol compound such as di(meth)acrylate of bisphenol A alkylene oxide adduct;
Di(meth)acrylates of hydrogenated bisphenol compounds such as di(meth)acrylates of hydrogenated bisphenol A;
Di(meth)acrylate of isocyanuric acid alkylene oxide adduct, tri(meth)acrylate of isocyanuric acid alkylene oxide adduct, di(meth)acrylate of caprolactone-modified isocyanuric acid alkylene oxide adduct, caprolactone-modified isocyanuric acid alkylene oxide adduct Poly(meth)acrylates of isocyanuric acid alkylene oxide adducts such as tri(meth)acrylates;
Polyol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, dipentaerythritol penta- or hexa(meth)acrylate;
Tri(meth)acrylate of trimethylolpropane alkylene oxide adduct, tetra(meth)acrylate of ditrimethylolpropane alkylene oxide adduct, tri- or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, dipentaerythritol alkylene oxide adduct Poly(meth)acrylates of polyol alkylene oxide adducts such as penta- or hexa(meth)acrylates:
Examples include epoxy (meth)acrylate; and polyester (meth)acrylate.
The polyester (meth)acrylate may be a dendrimer type (meth)acrylate.
In the alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Specific examples of hydroxyl group-containing polyfunctional (meth)acrylates include trimethylolpropane mono- or di-(meth)acrylate, pentaerythritol mono-, di- or tri-(meth)acrylate, and di-trimethylolpropane mono-, di- or tri(meth)acrylate. Mention may be made of acrylates and dipentaerythritol mono-, di-, tri-, tetra- or penta(meth)acrylates, epoxy(meth)acrylates.

Epoxy (meth)acrylate is a compound obtained by adding (meth)acrylic acid to an epoxy resin, and examples include the compounds described on pages 74 to 75 of the above-mentioned document "UV/EB Curing Materials". It will be done.

Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adduct; phenol novolak type epoxy resin and cresol novolak type epoxy resin. Examples include novolac type epoxy resins such as epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester;
In addition to these, there are also two chapters of the literature "Epoxy Resins - Recent Advances" (Shokodo, published in 1990), and the literature "Kobunshi Processing" Special Volume 9, Volume 22 Extra Issue Epoxy Resins [Kobunshi Publishing Co., Ltd., Compounds such as those described on pages 4 to 6 and pages 9 to 16 of ``Published in 1972'' can be mentioned.

Specific examples of aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. diglycidyl ether of polyalkylene glycol; diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct; di- or triglycidyl ether of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adduct; and polyglycidyl ethers of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts; di- or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; diglycidyl tetrahydrophthalate Ethers include hydroquinone diglycidyl ether and the like.
In addition to these, compounds described on pages 3 to 6 of the above-mentioned document "Polymer Processing" special edition of epoxy resins can be mentioned.

In addition to these aromatic epoxy resins and aliphatic epoxy resins, there are epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC [Nissan Chemical Co., Ltd.], Denacol EX-310 [Nagase Kasei Co., Ltd.], etc. Compounds such as those described on pages 289 to 296 of the above-mentioned literature "Polymer Processing" special edition of epoxy resins may be mentioned.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide, propylene oxide, or the like.

Examples of the allyl compound include monofunctional allyl compounds such as allyl alcohol, and polyfunctional allyl compounds such as diallyl phthalate, triallyl isocyanurate, and triallyl cyanurate.

In addition to these, compounds such as those described on pages 53 to 56 of the document "Latest UV Curing Technology" [Printing Information Association Co., Ltd., published in 1991] may be mentioned.

7-2． Sensitizer The sensitizer is blended for the purpose of further increasing the photoreactivity of the composition by sensitizing component (D).
As the sensitizer, when a hydrogen abstraction type photoradical polymerization initiator such as a benzophenone compound and a thioxanthone compound is used as the component (D), an amine compound and a thiol compound are preferable.
Specific examples of amine compounds include aliphatic amines such as triethanolamine, methyldiethanolamine, and triisopropanolamine, and aromatic amines such as diethylaminophenone, ethyl dimethylaminobenzoate, and isoacyl dimethylaminobenzoate.
Specific examples of thiol compounds include primary thiols such as trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and 1 , 4-bis(3-mercaptobutyryloxy)butane and the like.
Among these compounds, aliphatic amines are preferred as sensitizers because they have excellent storage stability, little odor, excellent curability, and little coloration of the cured product.
Furthermore, the amine compound is a preferred compound that can reduce the viscosity of the dispersed composition when an inorganic thixotropic agent such as silica is blended and dispersed as component (E).
The content of the sensitizer is preferably 0 to 5 parts by weight, more preferably 0 to 3 parts by weight, based on 100 parts by weight of the solid content of the composition.

7-3． Ultraviolet absorber The composition of the present invention can improve adhesive strength by containing an ultraviolet absorber, and for reasons unknown, the curing speed can be suppressed by cutting ultraviolet rays in the low wavelength range. This is presumed to be because the residual stress at the adhesive interface decreases.

Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.

The content ratio of the ultraviolet absorber may be appropriately set depending on the purpose, and is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of curable components. It is. When the content is 0.1 parts by weight or more, the adhesive strength can be increased, and when the content is 5 parts by weight or less, deterioration in curability can be suppressed.

7-4. Polymerization inhibitor Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors.
Specific examples of organic polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4- Phenol compounds such as tert-butylcatechol, quinone compounds such as benzoquinone, galvinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 Examples include stable radicals such as -oxyl, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, and the like.
Specific examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate.
Specific examples of organic salt-based polymerization inhibitors include nitroso compounds such as N-nitroso-N-phenylhydroxylamine aluminum salt, ammonium N-nitrosophenylhydroxylamine, and copper dibutyldithiocarbamate.

Among these, stable radicals and nitroso compounds are preferred because they cause little coloring of the composition, prevent thickening and gelation of the composition, and improve storage stability.
The content ratio of the polymerization inhibitor may be appropriately set depending on the purpose, and is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 parts by weight, based on 100 parts by weight of the total amount of curable components. Parts by weight. When the content is 0.0001 part by weight or more, the thermal stability and photostability of the composition can be improved, and when the content is 1 part by weight or less, the photocurability of the composition is excellent. Can be done.

7-5. Silane coupling agent Specific examples of the silane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acrylic Roxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3 -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-amino Examples include propyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These may be used alone or in combination of two or more.

7-6． Antioxidants Examples of antioxidants include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.
Specific examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.
Specific examples of phosphorus-based antioxidants include phosphines such as trialkylphosphines and triarylphosphines, trialkyl phosphites, and triaryl phosphites. Commercially available derivatives of these include, for example, Adekastab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010 manufactured by Adeka Co., Ltd. etc.
Specific examples of sulfur-based antioxidants include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include combinations of phenolic antioxidants and phosphorus antioxidants, and combinations of phenolic antioxidants and sulfur antioxidants.

7-7． Surface modifiers Surface modifiers include surface conditioning agents, surfactants, leveling agents, antifoaming agents, slippery agents, antifouling agents, etc. These known surface modifiers are used. can do.
Among these, silicone-based surface modifiers and fluorine-based surface modifiers are preferably mentioned.
Specific examples include silicone polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone polymers and oligomers having silicone chains and polyester chains, and fluorine polymers having perfluoroalkyl groups and polyalkylene oxide chains. and oligomers, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains.
Furthermore, in order to improve durability, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may be used.

8. Active energy ray curable adhesive composition The present invention is an active energy ray curable adhesive composition containing the components (A) to (E) as essential components in a specific proportion.
The composition can be produced by stirring and mixing the components (A) to (E) and, if necessary, other components according to a conventional method.
In this case, heating can be performed if necessary. The heating temperature may be appropriately set depending on the composition, substrate, purpose, etc. used, but is preferably 30 to 80°C.

The viscosity of the composition should be 50 to 5,000 mPa·s, preferably 100 to 3,000 mPa·s, in order to have excellent workability when injecting into an adherend. It is s. If the viscosity is less than 50 mPa・s, dripping of the composition will occur, and if the viscosity exceeds 5,000 mPa・s, the force required to inject the composition into the gap between the adherends will be reduced. It cannot be reduced, and work efficiency is reduced.
・Viscosity measured according to JIS K 6833 using a cone-plate rotational viscometer at a temperature of 25°C and a shear rate of 383 s ^-1

Furthermore, in order to satisfy the above-mentioned viscosity and prevent dripping, the composition of the present invention must have a TI value of 1.5 to 20 obtained under the following conditions, which is an index of the structural viscosity of the composition. Yes, preferably 1.8 to 10. If the TI value is less than 1.5, the composition will drip, and if the TI value exceeds 20, the force required to inject the composition into the gap between the adherends will be reduced. cannot be done, and work efficiency decreases.
・TI value determined at a temperature of 25°C using a cone-plate rotational viscometer according to JIS K 5101-6-2:2004

9. Method of use The composition of the present invention can be used for adhesion between substrates of the same type or between different types of substrates, preferably for adhesion between sheet-like substrates of the same type or sheets of different types. It can be used for adhesion between shaped substrates.
Specific examples of usage include applying it to one base material and then bonding it to another base material and irradiating it with active energy rays. Examples include a method of injecting a composition and irradiating it with active energy rays.

9-1. Substrate The composition of the present invention can be applied to various types of substrates as adherends, including plastics, wood, metals, inorganic materials, and paper.
Plastics include hydrophilic plastics and hydrophobic plastics.
Specific examples of hydrophilic plastics include polyvinyl alcohol and cellulose ester plastics.
Specific examples of hydrophobic plastics include polycarbonate, polyethylene terephthalate, polyethylene naphthalate, acrylic polymer, acrylic/styrene copolymer, aliphatic polyamide (nylon), aromatic polyamide, polyurethane, polyimide, and ethylene-vinyl acetate copolymer. Examples include polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polycycloolefin, polystyrene, ABS resin, chlorinated polypropylene, and polyacetal.
Examples of the wood include natural wood and synthetic wood.
Examples of metals include aluminum, stainless steel, copper, silver, iron, tin, and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
Examples of inorganic materials include glass, mortar, concrete, and stone.
Examples of the paper include imitation paper, high-quality paper, kraft paper, art coated paper, caster coated paper, pure white roll paper, parchment paper, waterproof paper, glassine paper, and corrugated paper.
Among these, plastic is preferred.

The shape of the base material can be various depending on the purpose, and as described above, the composition of the present invention is preferably used as a sheet-like base material, and is preferably used for adhesion of plastic sheet-like base materials. can do.
The type of base material in this case may be selected depending on the purpose. Specifically, it can be applied to adhesion between base materials of the same type and adhesion of different types.
The composition of the invention can be preferably applied to bonding plastics, in which case at least one plastic is used.
Specifically, examples include adhesion between plastics, and materials other than plastics. When used to bond plastics together, it can be used to bond the same type of plastic or different types of plastic, and it is preferable to use it to bond the same type of plastic.

9-2. Coating and Injecting Methods Conventionally known methods may be used as coating and injecting methods for the base material, depending on the type of base material and composition to be used, and the intended use.
Examples of the coating method include screen printing, stencil printing, roll printing, a dispenser, a jet dispenser, a brush, and the like.
Examples of the injection method include a method in which a container with a nozzle at the tip of a syringe or syringe is filled with the composition, and the composition is discharged from the tip.
Further, the thickness of the cured product (adhesive layer thickness) of the composition of the present invention may be selected depending on the substrate used and the application, but is preferably 0.001 to 10 mm, more preferably 0.001 to 10 mm. 05 to 5 mm.
As mentioned above, the composition of the present invention does not have the problem of dripping and has excellent adhesive properties even when the gap between the base materials is 0.1 mm or more, and even when it is 0.3 mm or more. . The upper limit of the gap between the base materials is preferably 3 mm or less.

9-3. Active energy rays Examples of active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive equipment can be used.
Various light sources can be used for curing with ultraviolet rays, such as pressurized or high-pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, and LEDs. Among these, high-pressure mercury lamps, metal halide lamps, and LEDs are preferred. The amount of ultraviolet ray irradiation is preferably 50 to 5,000 mJ/cm ² , more preferably 100 to 3,000 mJ/cm ² in the UV-A region (near 365 nm). The illuminance of ultraviolet rays is preferably 10 to 5,000 mW/cm ² , more preferably 100 to 2,000 mW/cm ² in the UV-A region (near 365 nm).

In the case of curing with an electron beam, various types of EB irradiation equipment can be used, such as Cockroft-Waldshin type, Vandegraaf type, and resonant transformer type equipment. The absorbed dose of the electron beam is preferably 1 to 200 kGy, more preferably 10 to 100 kGy. The accelerating voltage of the electron beam may be appropriately set in the range of 80 to 300 kV depending on the thickness of the base material, and for example, if the thickness of the base material is 100 μm, 200 kV is preferable. The oxygen concentration in the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.

In the present invention, it is preferable to use a UV-LED because it uses low energy and can be used as a compact irradiation device for on-site construction.
When using a UV-LED, its emission peak wavelength is preferably 350 to 420 nm, and the irradiation energy is preferably 5 to 2,000 mJ/cm 2 , more preferably 10 to 1,000 mJ/cm ² .

9-4. Preferred Usage Examples The composition of the present invention can be used for adhering various substrates, preferably plastic substrates, but is suitable for applications where the gap between the substrates is 0.1 mm or more, preferably 0.3 mm. It can be preferably used for the above purposes.
That is, a method for manufacturing a molded body or a component, in which the above-described active energy ray-curable adhesive composition is injected between two base materials having a gap of 0.1 mm or more, and then irradiated with active energy rays, as well as a base material. It can be preferably used in a method of filling gaps between materials and adhering them.
In this case, it is preferable to use a UV-LED as the active energy ray because it uses low energy and can be used as a compact irradiation device for on-site construction.

Specific examples of preferred usage include manufacturing of optical materials, displays, electronic components, etc., construction and repair in the civil engineering and architectural fields, and manufacturing and repair of daily necessities.
Examples of manufacturing optical materials, displays, electronic components, etc. include adhesion of the base protrusion holding the imaging lens of the CCD holding member and the CCD drive substrate in the manufacturing of solid-state imaging device (CCD) lenses; Examples include adhesion of a type image sensor, CMOS type image sensor, etc. and a lens substrate, adhesion of a liquid crystal display and a touch panel, adhesion of LED lighting and lamps, adhesion of hard disk drive parts, etc.
Examples of construction and repair in the civil engineering and architectural fields include adhesion between acrylic plates used for aquariums, adhesion between tiles, adhesion between wood pieces, and adhesion between polyvinyl chloride and wood flooring materials.
Examples of manufacturing and repair of daily necessities include adhesives for making plastic models, adhesives for repairing plastic daily necessities such as glasses and ballpoint pens, and the like.

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below. In addition, "parts" in each of the following examples means parts by weight.

1. Examples 1 to 10, Comparative Examples 1 to 3
1) Preparation of active energy ray curable adhesive composition Components (A) to (E) shown in Table 1 below and other components are dispersed using a planetary stirring device to produce an active energy ray curable adhesive composition. did.
The obtained compositions shown in Table 1 were used to perform the evaluations described below. The results are shown in Table 1.

Note that the numbers for each component in Table 1 mean parts by weight.
Moreover, the abbreviations in Table 1 mean the following.

◆(A) Component UN1255: Polyester urethane acrylate (Mw8,000), Art Resin UN-1255 (product name) manufactured by Negami Kogyo Co., Ltd.
・UN6305: Polyether urethane acrylate (Mw27,000), Art Resin UN-6305 (product name) manufactured by Negami Kogyo Co., Ltd.
◆(B) Component
・ACMO: Acryloylmorpholine, ACMO (product name) manufactured by KJ Chemicals Co., Ltd.
◆(C) Component
・4HBA: 4-Hydroxybutyl acrylate, 4-HBA (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.
・IBXA: Isobornyl acrylate, light acrylate IB-XA (product name) manufactured by Kyoeisha Chemical Co., Ltd.
◆(D) Component
・O-184: 1-Hydroxycyclohexylphenyl ketone, Omnirad-184D (trade name) manufactured by IGM Resin
・TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, “Omnirad TPO” manufactured by IGM Resin
◆(E) Component
RX200: Trimethylsilyl group surface-modified silica (hydrophobic), specific surface area 200 m ² /g, average primary particle size 12 nm, "AEROSIL RX200" manufactured by Nippon Aerosil Co., Ltd.
RY200S: dimethylsiloxane-treated silica (hydrophobic), specific surface area 130 m ² /g, average primary particle size 16 nm, "AEROSIL RY200S" manufactured by Nippon Aerosil Co., Ltd.
◆Other ingredients
・TEA: Triethanolamine

2) Evaluation of active energy ray curable adhesive composition The obtained composition was evaluated according to the following test method. The results are shown in Table 1.

◆Viscosity (25℃)
Using a cone-plate rotational viscometer "RE-80R" manufactured by Toki Sangyo Co., Ltd., in accordance with JIS K 6833, the temperature was 25℃, the shear rate was 383s ^-1 (cone plate angle 1 degree 34 minutes, rotor radius 2 .4 cm, rotor rotation speed 100 rpm, shear rate coefficient 3.83), and the viscosity value 1 minute after the rotor rotation was defined as the 25° C. viscosity. The unit of viscosity in Table 1 is mPa·s.
Note that the shear rate is obtained by multiplying the shear rate coefficient by the rotational speed.

◆TI value (Thixotropy Index value)
The viscosity was measured at a rotor rotation speed of 10 rpm (shear rate was 38.3 s ^-1 ) according to the same method as for the viscosity described above, and the ratio of the obtained viscosities was calculated to be the TI value.
TI value = Rotor rotation speed 10 rpm viscosity / Rotor rotation speed 100 rpm viscosity

◆Liquid discharge properties The obtained composition was filled into Terumo Corporation's "Terumo Syringe for Medium Mouth Tuberculin (1 mL)" with a nozzle part of 1 mm in diameter x 10 mm in length, and a 500 g weight was placed on the syringe. The liquid ejectability was evaluated by extruding the composition from a nozzle and measuring the time until the entire content of 1 mL could be ejected.
In addition, ◯, △ and × in Table 1 mean the following.
〇: Can be discharged in less than 30 seconds △: Can be discharged in 30 seconds or more and less than 2 minutes ×: Requires 2 minutes or more

◆Dripping property Polycarbonate plates of 5 cm x 2 cm x 2 mm thick were placed facing each other with a gap of 0.5 mm, and the composition filled in Terumo Corporation's "Terumo Syringe Medium Mouth for Tuberculin (1 mL)" was placed in the gap. Pour and fill. Thereafter, it was kept at room temperature for 10 minutes, and it was visually confirmed whether the liquid flowed out from the gap to evaluate the dripping property.
In addition, ◯, △ and × in Table 1 mean the following.
○: The composition does not flow out even after 10 minutes △: Part of the composition flows out, and part remains in the gap. ×: All of the composition flows out, and no composition remains in the gap.

◆Polycarbonate plates with adhesive strength of 5 cm x 2 cm x 2 mm thick were placed facing each other with a gap of 0.5 mm, and the composition filled in "Terumo Syringe Medium Mouth for Tuberculin (1 mL)" manufactured by Terumo Corporation was placed in the gap. Pour and fill. Immediately thereafter, the composition was cured by UV irradiation using a UV-LED device that emits 385 nm light (UV illuminance: 500 mW/cm ² , UV integrated light amount: 2,000 mJ/cm ² ), and the sample was then used for adhesive strength measurement. And so.
Adhesive strength was measured under the following conditions. The unit of adhesive strength in Table 1 is N/10mm.
・Tensile tester: Instron 5564 manufactured by Instron Japan Company Limited
・Test piece: width 2cm (adhesive surface) x length 10cm x 2mm thickness ・Test method: Tensile test ・Peeling speed: 50mm/min

◆Matte A square hole of 5 cm x 5 cm is made in a 2 mm thick silicone rubber and placed on a release film. After that, the composition is poured and filled, and the composition is cured by irradiating it with ultraviolet light (UV illuminance: 500 mW/cm ² , UV cumulative light amount: 2,000 mJ/cm ² ) using a UV-LED device that emits 385 nm light. This was used as a sample for measuring matteness.
The haze of the obtained sample was measured and used as an index of matteness.
In addition, 〇, 〇△, △×, and × in Table 1 mean the following.
〇: Haze 90% or more 〇△: Haze 70-90%
△: Haze 50-70%
△×: Haze 20-50%
×: Haze 0-20%

5) Evaluation Results As is clear from the results of Examples 1 to 10, the composition of the present invention has excellent adhesion between plastic sheet-like substrates, suppresses dripping, and is effective when discharging liquid. It had excellent workability, and the cured product had little gloss and was excellent in design.
On the other hand, the composition of Comparative Example 1, which does not contain the component (E) of the present invention, had poor dripping properties, and the adhesive strength could not be measured because all the liquid flowed out from the gap. . Furthermore, the matting properties after curing were also poor.
Furthermore, although the composition of Comparative Example 2 with a viscosity exceeding 5,000 mPa·s had good dripping properties, adhesive strength, and matte properties, it had poor liquid discharge properties and was lacking in practicality. .
In addition, although the composition of Comparative Example 3, which does not contain the component (B) of the present invention, had good liquid discharge properties, drip properties, and matte properties, it had poor adhesion to the plastic sheet-like base material. It was low and impractical.

The composition of the present invention has excellent adhesion to various adherends, suppresses dripping, exhibits sufficient adhesive strength even with large gaps between adherends, has excellent workability, and has excellent adhesive properties for cured products. The gloss is also small.
Therefore, the composition of the present invention can be used as an active energy ray-curable adhesive composition that requires such physical properties, and preferably as an active energy ray-curable adhesive composition for plastic sheets. It can be used suitably for manufacturing building materials, electronic parts, mechanical parts, optical parts, etc.

Claims (14)

A composition containing the following components (A) to (C) as curable components, and the following components (D) and (E) as components other than the curable component,
(C) component contains 4-hydroxybutyl acrylate,
Contains the following components (A) to (C) in the following proportions in 100% by weight of the total amount of curable components,
(A) Component: 5 to 60% by weight
(B) Component: 20 to 70% by weight
(C) Component: 10 to 75% by weight
Contains the following components (D) to (E) in the following proportions based on 100 parts by weight of the total amount of curable components,
An active energy ray-curable adhesive composition whose viscosity satisfies the following.
(D) component: 0.1 to 15 parts by weight (E) component: 0.1 to 15 parts by weight
・Curing component
(A) Component: Urethane (meth)acrylate (B) Component: (meth)acryloylmorpholine (C) Component: Compound having one ethylenically unsaturated group other than components (A) and (B)
・Components other than curable components
(D) Component: Photoradical polymerization initiator (E) Component: Thixotropic agent
·viscosity
The viscosity measured using a cone-plate rotational viscometer at a temperature of 25°C and a shear rate of 383 s ^-1 according to JIS K 6833 is 50 to 5,000 mPa・s, and JIS K 5101-6-2 2004, the TI value determined at a temperature of 25°C using a cone-plate rotational viscometer is 1.5 to 20. The active energy ray-curable adhesive composition according to claim 1, which contains silica as component (E). The active energy ray-curable adhesive composition according to claim 1 or 2, which contains a polymer other than the component (A) as the component (E). According to any one of claims 1 to 3, the component (A) is a urethane (meth)acrylate having two (meth)acryloyl groups having a weight average molecular weight of 1,000 to 50,000. Active energy ray curable adhesive composition. The component (A) is (AL) a urethane (meth)acrylate having two (meth)acryloyl groups having a weight average molecular weight of 1,000 or more and 15,000 or less, and (A-H) a weight average molecular weight and a urethane (meth)acrylate having two (meth)acryloyl groups having a value of more than 15,000 and less than or equal to 50,000.Active energy ray-curable adhesive according to any one of claims 1 to 4. agent composition. The active energy ray-curable adhesive composition according to any one of claims 1 to 5, wherein component (D) contains an acylphosphine oxide compound. The active energy ray-curable adhesive composition according to any one of claims 1 to 6, wherein the adherend is a plastic sheet-like base material. An ultraviolet ray (hereinafter referred to as "UV-LED") curable adhesive composition using a light emitting diode as a light source, comprising the composition according to any one of claims 1 to 7. After injecting the active energy ray-curable adhesive composition according to any one of claims 1 to 6 between two base materials having a gap of 0.1 mm or more, irradiation with active energy rays. A method for manufacturing parts. 10. The method for manufacturing a member according to claim 9, wherein at least one of the base materials is a plastic sheet-like base material. The method for producing a member according to claim 9 or 10, wherein the active energy ray is a UV-LED. After injecting the active energy ray-curable adhesive composition according to any one of claims 1 to 6 between two base materials having a gap of 0.1 mm or more, irradiation with active energy rays. A method of bonding and filling gaps between base materials. 13. The method for filling gaps between substrates and bonding them together according to claim 12, wherein at least one of the substrates is a plastic sheet-like substrate. 14. The method for filling gaps between substrates and bonding them together according to claim 12 or 13, wherein the active energy ray is a UV-LED.