TWI632215B - Active energy ray-curing adhesive composition - Google Patents

Abstract

The present invention relates to an active energy ray-curable resin composition characterized by comprising a vinyl monomer (A) having no acid group, a macromonomer (B) having a (meth) acrylonitrile group at one end, and light. The active energy ray-curable adhesive composition of the polymerization initiator (C), the glass transition temperature of the above (B) is 30 ° C or more, and the adhesive having the acid group is not used in the production, and the adhesive after curing The glass transition temperature is below -20 °C.

Description

Active energy ray-curing adhesive composition [Reciprocal reference of related applications]

The present application is related to the Japanese Patent Application No. 2013-193597, filed on Sep. 19, 2013, which is hereby incorporated by reference. In this manual.

The present invention relates to an active energy ray-curable adhesive composition, and more particularly relates to a macromonomer having a (meth) acrylonitrile group at the terminal, which has good hardenability and excellent adhesion properties, and does not cause corrosion to metals. Active energy ray-curing adhesive composition.

Adhesives (also known as pressure-sensitive adhesives) have been widely used in adhesive tapes, labels, stickers, and seals. Plastics, paper, metal, glass, and pottery can also be used as the adhesive. Further, the shape of the adherend may be a flat shape or a curved shape.

On the other hand, the adhesive is classified into a natural rubber type, a synthetic rubber type, an acrylic type, etc. based on its main component, wherein the adhesive of the acrylic adhesive is viscous. It is excellent in properties and weather resistance, and can be used in a variety of adhesive products by changing its monomer composition to impart a wide range of adhesive properties. In general, in order to exhibit properties such as adhesion and cohesive force, the adhesive is desirably a polymer having a weight average molecular weight of about 300,000 or more.

The form of the acrylic adhesive is exemplified by a solvent-based adhesive, a water-dispersible (emulsion type) adhesive, and a solventless adhesive. Among them, solvent-based adhesives are criticized for their environmental hygiene and safety problems caused by solvents. On the other hand, the water-dispersible pressure-sensitive adhesive requires a considerable amount of drying energy to evaporate the water of the medium, and there is a problem that the obtained coating film is deteriorated in water resistance due to the incorporation of an emulsifier or the like.

In contrast, the solvent-free adhesive, particularly the active energy ray-curable adhesive, has no problem due to the solvent described above, and is excellent in adhesion performance. Therefore, various proposals have been made regarding an active energy ray-curable adhesive and an adhesive product using the same.

Patent Document 1 discloses a method of obtaining an adhesive product by irradiating ultraviolet rays having a wavelength of 300 nm to 400 nm at a strength of not more than 7 mW/cm ² with a photopolymerizable composition containing an alkyl acrylate or the like as a main component and containing no organic solvent. Further, Patent Document 2 describes an ultraviolet curable adhesive composition comprising an alkyl acrylate, a monofunctional monomer, a specific polyfunctional oligoacrylate, and a photopolymerization initiator, and is adhered to ultraviolet rays in two stages. The method of manufacturing the tape. Further, Patent Document 3 discloses a photopolymerizable composition containing an acrylate monomer, a vinyl compound monomer, a macromonomer, and a photopolymerization initiator.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] U.S. Patent No. 4,181,752

[Patent Document 2] Japanese Patent Laid-Open No. Hei 7-331198

[Patent Document 3] Japanese Patent Laid-Open No. Hei 4-366103

However, the invention described in Patent Document 1 is one in which a polymer having a high molecular weight is obtained by irradiating ultraviolet rays having a weak light intensity to exhibit good adhesion properties. Therefore, it is difficult to put it into practical use in terms of a slow polymerization reaction rate and low productivity. Further, since the ultraviolet curable adhesive composition described in Patent Document 2 has a polyfunctional acrylate as an essential component, the adhesive strength tends to be greatly reduced when the blending amount is increased, and there is a problem in that it is difficult to obtain an adhesive property balance. Moreover, the productivity aspect is not sufficient.

On the other hand, the photopolymerizable composition described in Patent Document 3 can obtain an adhesive article by a short-time light ray, and the microphase separation structure of the macromonomer portion can exhibit good adhesion even if the molecular weight is not high enough. However, problems such as haze, time-dependent coloring, and metal corrosion of the cured product cannot be used in the vicinity of electronic materials and optical materials.

The present invention has been made in view of the above problems, and an object thereof is to provide a fast curing rate, excellent adhesion and cohesive force, and can suppress fogging, coloring, and metal corrosion of a cured product, and thus can be particularly utilized for electronic materials and optical materials. Active energy ray-curing adhesive composition for use Things.

As a result of a positive review of the above problems, the present inventors have found that it is possible to obtain a hardened substance with a high degree by using a vinyl monomer having no acid group and a specific macromonomer having a (meth)acryl fluorenyl group at one end. The present invention is completed by the adhesion and retention, and the reduction of the haze and coloration of the cured product, thereby suppressing the active energy ray-curable resin composition of metal corrosion.

The present invention is as follows.

[1] An active energy ray-curable adhesive composition comprising a vinyl monomer (A) having no acid group, a macromonomer (B) having a (meth) acrylonitrile group at one end, and light The active energy ray-curable adhesive composition of the polymerization initiator (C), the glass transition temperature of the above (B) is 30 ° C or more, and the raw material having an acid group is not used in the production, and the adhesive after curing is used. The glass transition temperature is below -20 °C.

[2] The active energy ray-curable adhesive composition according to the above [1], wherein the total of the above (A) and (B) is 100 parts by mass, and the above-mentioned (A) is contained in an amount of 90 to 98 parts by mass. ), 2 to 10 parts by mass of the above (B).

[3] The active energy ray-curable adhesive composition according to the above [1] or [2] wherein the weight average molecular weight of the above (B) is 5,000 to 20,000.

[4] The active energy ray-curable adhesive composition according to any one of the above [1], wherein the terminal polymerizable functional group (B) is an acrylonitrile group.

[5] A cured product of the active energy ray-curable adhesive composition according to any one of [1] to [4], wherein the product is an adhesive product.

[6] The article according to [5], comprising: a substrate; and the cured product applied to at least a part of the substrate.

[7] The article according to [5] or [6] wherein the adhesive article is an electronic material or an optical material.

[8] A method for producing an adhesive product, which is characterized in that the active energy ray-curable adhesive composition according to any one of [1] to [4] is supplied to one or more of them. a step of at least a part of the substrate, and a step of curing the composition by irradiating the composition with an active energy ray to exhibit adhesiveness.

[9] The production method according to [8], wherein the adhesive article is an electronic material or an optical material.

The active energy ray-curable adhesive composition of the present invention has good hardenability and can have adhesiveness and cohesive force to a high degree. The turbidity of the hardened material and the adhesive product which is less colored and can inhibit metal corrosion.

Hereinafter, specific examples of the present disclosure and non-limiting examples will be described in detail. The detailed description is intended to be illustrative of the preferred embodiments of the invention, and is not intended to limit the scope of the invention. Further, the additional features and inventions disclosed below are intended to provide a further improved active energy ray-curable adhesive composition, and may be used separately or in combination with other features or inventions.

The combination of the features and the steps disclosed in the following detailed description is not necessary in the broadest sense of the invention. In addition, the various features of the above-described and representative specific examples, and the various features described in the independent and dependent items, when providing additional and useful embodiments of the present disclosure, are not necessarily required to be as shown in the specific examples described herein. Or combine them in the order listed.

All the features described in the specification and/or the scope of the claims and the features described in the examples and/or claims are independent of the disclosure of the application and the specific scope of the patent application, which means individual And reveal each other independently. In addition, the description of all numerical ranges and groups or groups is intended to be a limitation of the disclosure of the application and the specifics of the application.

Hereinafter, the present invention will be described in detail. Again, this is said In the specification, acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, acrylate and/or methacrylate is represented by (meth) acrylate, and acrylonitrile and/or methacrylic acid oxime The base system is represented by a (meth) acrylonitrile group.

<Ethylene-based monomer (A) having no acid group>

The vinyl monomer (A) having no acid group in the present invention (hereinafter also referred to as "(A) component") means a monomer other than the vinyl monomer having an acid group such as a carboxyl group or a sulfonic acid group. When a vinyl monomer having an acid group is used, since the obtained adhesive product is corroded when it is in contact with a metal for a long period of time, a monomer having an acid group cannot be used as the component (A). Further, the component (A) is a monomer having no acid group as described above, but the case where the monomer used as the raw material contains an acid group as an impurity is allowed.

The component (A) is preferably an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbons, and is exemplified by, for example, n-butyl (meth)acrylate, from the viewpoint of obtaining a polymer having a low Tg and having an adhesive property. , isobutyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (a) Base) n-decyl acrylate, isodecyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, etc., preferably monomer is n-butyl (meth) acrylate, (A) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, etc. having a carbon number of 4 ~9 alkyl alkyl (meth) acrylate, one of these can be used Kind or more than two.

The amount of the (meth)acrylic acid alkyl ester used is preferably from 30 to 100 parts by mass, more preferably from 50 to 98 parts by mass, per 100 parts by mass of the component (A), based on the viewpoint of obtaining a polymer having good adhesion. The range is preferably in the range of 60 to 95 parts by mass.

In addition to the aforementioned (meth)acrylic acid alkyl ester, the component (A) may be a monomer which can be copolymerized with it insofar as the adhesive properties are not impaired. Examples of the monomer which can be copolymerized include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate having a carbon number of 1 to 3. Alkyl alkyl (meth) acrylate; vinyl aromatic monomer such as styrene, α-methyl styrene, vinyl toluene; cyclohexyl (meth) acrylate, methyl (meth) acrylate An aliphatic ring-based vinyl monomer such as cyclohexyl ester, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate or isobornyl (meth)acrylate; (methyl) 2-hydroxyethyl acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and poly a monomer having a hydroxyl group such as ethylene glycol-polypropylene glycol mono(meth)acrylate; (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylonitrile Amine, N-isopropyl (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) acrylamide, (meth) propylene Mercaptomorpholine, N-methylol acrylamide, N-methoxymethyl propyl Amides N- methoxybutyl acrylamide and other ethylenically unsaturated amines and carboxylic acyl substituted compounds N-; allyl alcohol of the unsaturated alcohol; (meth) One or two or more of these may be used, such as acrylonitrile, vinyl acetate, glycidyl (meth)acrylate, and acrylamide.

As the component (A), a polyfunctional monomer having two or more vinyl groups in the molecule may be additionally used.

The polyfunctional monomer is exemplified by, for example, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 , 9-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, 3-methyl-1 , 5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-decanediol diacrylate, 2-methyl-1,8-octanediol di(a) Acrylate, 2-hydroxy-1,3-bis(methyl)propenyloxypropane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth) acrylate, glycerol Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, two a polyol poly(meth)acrylate such as pentaerythritol hexa(meth) acrylate or di-trimethylolpropane tetra(meth) acrylate; an alkylene oxide of a raw material alcohol of the poly(meth) acrylate Poly(meth)acrylates of [ethylene oxide and propylene oxide, etc.] adducts; such poly(methyl) a poly(meth) acrylate of a caprolactone modification of an acrylate raw material alcohol; a di(meth) acrylate of ethylene oxide modified isocyanuric acid and a modified one of cyclohexane modified isocyanuric acid ( The alkylene oxide such as methyl acrylate is modified with poly(meth) acrylate such as isocyanuric acid, but is not limited thereto.

Oligomers can also be used for polyfunctional (meth) acrylates, specifically One or two or more of these may be used for the urethane (meth) acrylate, the polyester (meth) acrylate, the epoxy (meth) acrylate, and the like.

The amount of the polyfunctional monomer used is preferably less than 5% by mass of the entire component (A). When a polyfunctional monomer of 5% by mass or more is used, the cohesive force of the obtained adhesive becomes high, but the adhesive strength tends to be deteriorated. Further, when the amount of the polyfunctional copolymer used is large, the curing rate at the time of hardening by the active energy ray may be lowered.

The component (A) is preferably selected such that the calculated glass transition temperature (Tg) of the polymer is less than -45 °C. Here, the calculated value of Tg is calculated by the calculation of the following formula (1) based on the Tg of each homopolymer described in "POLYMER HANDBOOK 4th Edition" (issued by John Wiley & Sons, Inc.). Out of value.

[Number 1] 1/Tg={W(a)/Tg(a)}+{W(b)/Tg(b)}+{W(c)/Tg(c)}+‧‧‧ (1)

In the above formula,

Tg: Tg of polymer

W(a): the weight fraction of the structural unit formed by the monomer (a) in the polymer

W(b): the weight fraction of the structural unit formed by the monomer (b) in the polymer

W(c): the weight fraction of the structural unit formed by the monomer (c) in the polymer

Tg(a): glass transition temperature of the homopolymer of monomer (a)

Tg(b): glass transition temperature of the homopolymer of monomer (b)

Tg(c): glass transition temperature of the homopolymer of monomer (c)

<A macromonomer having a (meth)acryl fluorenyl group at one end (B)>

The macromonomer (B) having a (meth)acryl fluorenyl group at one end (hereinafter also referred to as "(B) component") is a polymer having a vinyl monomer as a main structural unit, and has a single terminal (methyl group). ) Acetylene base.

The method for producing the component (B) is not particularly limited. However, it is preferable to use it in order to make it easy to use in the manufacture of components around the electronic material which does not require heavy metals, and to manufacture it inexpensively. The steps shown are obtained.

First step: a step of polymerizing an ethylene monomer in the presence of a chain transfer agent having a functional group such as a hydroxyl group, an amine group or an alkoxyalkyl group to synthesize a polymer having a functional group at one terminal.

Step 2: a functional group having a single terminal at the terminal of the polymer obtained in the above first step, and a compound having a functional group reactive with the functional group and a (meth)acryl fluorenyl group (hereinafter also referred to as "a compound (D)") a step of obtaining a macromonomer having a (meth)acryl fluorenyl group at one end.

However, when a vinyl monomer having an acid group is used herein, the resulting adhesive article may be corroded when it is in contact with a metal for a long period of time, so that a monomer having an acid group cannot be used as a raw material of the component (B).

(methyl) propyl used to obtain the component (B) The compound (D) of the oxime group corresponds to a reactive functional group which the chain transfer agent has.

For example, when the reactive functional group is a hydroxyl group or an amine group, the compound (D) is one having an isocyanate group. When the reactive functional group is a hydroxyl group, the compound (D) is one having a chlorine group. When the reactive functional group is an alkoxyalkylene group, the compound (D) is one having an alkoxyalkylene group.

In the above, it is preferable that the reactive functional group is a hydroxyl group and the compound (D) has an isocyanate group in terms of a small side reaction, a simple post-reaction treatment, and a raw material availability. Hereinafter, the first step and the second step in the case of using a chain transfer agent having a hydroxyl group and a compound (D) having an isocyanate group will be described in detail.

○Step 1: Synthesis of a polymer having a hydroxyl group at one end

The vinyl monomer is polymerized in the presence of a chain transfer agent having a hydroxyl group using a polymerization initiator to obtain a polymer having a hydroxyl group at one terminal.

Examples of the vinyl monomer are (meth) acrylate, (meth) acrylamide, styrene, α-methyl styrene, acrylonitrile, vinyl acetate, etc., but in order to make copolymerization, The cured product is excellent in adhesive properties, weather resistance, water resistance, and the like, and is preferably a (meth) acrylate.

As the (meth) acrylate, a compound similar to the vinyl monomer which can be used as the component (A) can be used.

Specific examples of the chain transfer agent having a hydroxyl group include 2-mercaptoethanol, 3-mercapto-1-propanol, 6-mercapto-1-hexanol, 3-mercapto-1-hexyl One type or two or more kinds of these may be used for the alcohol, thioglycerol, thiophene or the like. Among these, 2-mercaptoethanol is preferably used from the viewpoint of introducing a small amount of a hydroxyl group efficiently.

The polymerization initiator may be any one as long as it is an initiator capable of generating a radical at a specific reaction temperature. Specific examples are organic peroxides such as di-tert-butyl peroxide and di-trihexyl peroxide, azobisisobutyronitrile, azobiscyclohexanenitrile, azobis(2-methylbutyronitrile), Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-mercaptopropyl) dihydrochloride, 4,4'-azobis(4-cyanopentane) An azo compound such as an acid). From the viewpoint of not easily causing side reactions with various monomers, an azo compound is preferably used.

The polymer having a hydroxyl group at one end is preferably obtained by solution polymerization using a suitable organic solvent. The organic solvent to be used is not particularly limited, and an aromatic hydrocarbon compound, a cyclic ether such as tetrahydrofuran or dioxane, an aromatic hydrocarbon compound such as benzene, toluene or xylene; an ester such as ethyl acetate or butyl acetate; Ketones such as acetone, methyl ethyl ketone and cyclohexanone.

Further, a dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate may be added to remove water in the organic solvent.

The polymerization temperature is appropriately adjusted depending on the conditions of the monomer to be used, the type of the solvent, and the monomer concentration, but it is usually in the range of 50 to 150 ° C, preferably in the range of 60 to 120 ° C.

○Step 2: introduction of (meth)acryloyl group at a single terminal

For the polymer having a hydroxyl group at the single terminal obtained in the first step, A compound (compound (D)) having both a (meth)acryl fluorenyl group and an isocyanate group is reacted to obtain a macromonomer (B) having a (meth) acrylonitrile group at a single terminal. At this time, in order to stabilize the reaction in a short time, it is preferred to add a catalyst for promoting the reaction and a polymerization inhibitor.

As the compound having a (meth)acryl fluorenyl group and an isocyanate group, for example, 2-isocyanate ethyl (meth)acrylate, 2-(2-isocyanate ethoxy)ethyl (meth)acrylate, (A) Base) acrylonitrile isocyanate or the like. Among these, a compound having an acrylonitrile group is preferred from the viewpoint of the curing rate, and among them, 2-isocyanate ethyl acrylate is most preferable in terms of a side reaction.

The amount of the compound having a (meth)acryl fluorenyl group and an isocyanate group is preferably from 0.8 to 1.2 mol equivalents based on the single terminal hydroxyl group.

The catalyst for promoting the reaction is exemplified by a metal compound, a tertiary amine, a quaternary ammonium salt, a phosphine compound, a phosphonium salt, etc., but is preferably a metal compound having a high effect in a small amount.

Specific examples of the metal-based compound are di-n-butyltin oxide, di-n-butyltin dilaurate, di-n-butyltin, di-n-butyltin diacetate, di-n-octyltin oxide, di-n-octyltin dilaurate, and three. Organotin compounds such as monobutyltin chloride, di-n-butyltin dialkyl mercaptan, di-n-octyltin dialkyl mercaptan; lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octate Such as organic lead compounds; organic bismuth compounds such as bismuth octoate.

When the amount of the catalyst used is 100 parts by weight or more based on the total amount of the polymer having a hydroxyl group at one terminal and the compound having a (meth)acryl fluorenyl group and an isocyanate group, it is preferably 0.05 parts by weight or less. When using 0.05 parts by weight or more There are problems such as the coloring caused by the catalyst.

The polymerization inhibitor is exemplified by hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene or the like.

When the polymerization inhibitor is used in an amount of 100 parts by weight based on the total amount of the polymer having a hydroxyl group at one terminal and the compound having a (meth)acryl fluorenyl group and an isocyanate group, it is preferably 0.002 to 0.02 parts by weight. When the amount is 0.002 parts by weight or less, the polymerization inhibiting effect is not sufficiently exhibited, and when it is 0.02 parts by weight or more, the coloring due to the polymerization inhibitor is caused, and the subsequent curing rate is slowed down.

○Other

When the organic solvent is used in the synthesis of the component (B), it is preferred to have a solvent removal step for drying and removing the organic solvent after the first step and the second step. By removing the organic solvent by this step, problems such as danger or odor caused by the ignition of the organic solvent can be avoided.

The conditions of the solvent removal step are determined depending on the type of the organic solvent to be used, etc., but the organic solvent is removed and dried by heating at about 50 to 200 ° C under normal pressure or reduced pressure. It is recommended to perform dry decompression heating at a lower temperature and a shorter time.

The weight average molecular weight of the component (B) of the present invention is preferably from 5,000 to 20,000. By setting the weight average molecular weight to 5,000 or more, the adhesion and retention force when the subsequent cured product is used as the adhesive can be combined to a high degree. Further, when the weight average molecular weight is 20,000 or less, the cured product is less likely to be turbid due to its excellent compatibility. Also, the weight average molecular weight system The value measured by gel permeation chromatography (GPC) and polystyrene conversion.

Further, the glass transition temperature (Tg) of the component (B) in the present invention is 30 ° C or higher, preferably 55 ° C or higher, more preferably 90 ° C or higher. By setting the Tg to 30 ° C or higher, the holding power when the obtained cured product is used as an adhesive is improved. In the present invention, the glass transition temperature is measured by the midpoint of the endothermic peak detected in the differential scanning calorimeter.

When the mass ratio of the component (A) to the component (B) is 100 parts by mass based on the total of the components (A) and (B), the component (B) is preferably 2 parts by mass or more and 10 parts by mass or less. When the holding strength of the cured product is increased by 2 parts by mass or more, the adhesive force of the cured product is maintained by 10 parts by mass or less.

In the present invention, the component (B) must be a macromonomer having a (meth)acryl fluorenyl group at one terminal. When a macromonomer having a (meth)acryl fluorenyl group at the both ends and a (meth)acryl fluorenyl group in the middle of the main chain other than the terminal is used, the adhesion and cohesive force of the cured product cannot be balanced. Further, from the viewpoint of good hardenability of the irradiation active energy ray, it is more preferably a macromonomer having an acrylonitrile group.

About <Photopolymerization Initiator (C)>

In the present composition, it is necessary to add a photopolymerization initiator (C) (hereinafter also referred to as "C component") for the purpose of curing by an active energy ray such as ultraviolet light or visible light.

The components (C) are exemplified by benzyldimethylketal, benzil, benzoin, benzoin ethyl ether, benzoin isopropyl ether, Benzene isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)- Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]acetone , 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl]-2-methylpropan-1-one, 2-methyl 1-[4-(methylthio)]phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) Butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, ADEKAOPTOMER N -1414 (made by ADEKA), aromatic ketone compounds such as phenylglyoxylate, ethyl hydrazine, phenanthrenequinone; benzophenone, 2-methylbenzophenone, 3-methyl bis Benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane , methyl-2-benzophenone, 1-[4-(4-benzylidenylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl) Propane-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, N,N'- Methyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylamine Benzophenone-based compound such as benzophenone; bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzimidylbenzene Phosphine oxide, ethyl-(2,4,6-trimethylbenzylidene)phenylphosphonate and bis(2,6-dimethoxybenzylidene)-2,4,4- Thiol-based phosphine oxide compounds such as trimethylpentylphosphine oxide; thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propanol Thiophenone, 3-[3,4-dimethyl-9-oxo-chloride a thioxanthone compound such as 9H-thioxanthone-2-yl]oxy]-2-hydroxypropyl-N,N,N-trimethylammonium or fluorothioxanthone; acridone, 10 - acridine ketone compound such as butyl-2-chloroacridone; 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoguanidino)] and Ketone 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethenylhydrazine) and other oxime esters; 2-( o-Chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2- (o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxy Phenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethyl 2,4,5-triarylimidazole dimer such as oxyphenyl)-4,5-diphenylimidazole dimer; and 9-phenyl acridine and 1,7-bis (9,9' An acridine derivative such as -pyridyl)heptane.

These compounds may be used alone or in combination of two or more.

The blending ratio of the component (C) is preferably 0.01 to 3 parts by mass based on 100 parts by mass of the total of the components (A) and (B). When the blending ratio of the component (C) is 0.01 parts by mass or more, the composition can be cured by an appropriate amount of ultraviolet rays or visible light to improve productivity, and when it is 3 parts by mass or less, the cured product can be improved. The force can be excellent in weather resistance or transparency.

<Other ingredients>

In the composition of the present invention, other components described later than those described above may be blended as needed. Specific examples thereof include an inorganic material, a leveling agent, a decane coupling agent, a polymerization inhibitor or/and an antioxidant, a light resistance improving agent, an organic solvent, and/or water.

The components are described below.

(1) Photopolymerization starter

In the composition of the present invention, in order to further improve the reactivity, a photopolymerization initiation aid may be added.

The photopolymerization initiation aid is exemplified by an aliphatic amine or an aromatic amine such as diethylaminobenzophenone, ethyl dimethylaminobenzoate or isodecyl dimethylaminobenzoate.

The blending ratio of the photopolymerization starting aid is preferably from 0 to 10% by weight, more preferably from 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.

(2) Leveling agent

The leveling agent is exemplified by a polyfluorene-based compound, a fluorine-based compound, and the like.

When the blending ratio of the leveling agent is 0.5% by weight or less based on 100 parts by weight of the solid content of the composition, it is preferable because the adverse effect on the subsequent properties is small.

(3) decane coupling agent

The decane coupling agent can also be based on the improvement of glass, metal, metal oxides It is added for the purpose of the subsequent performance of the inorganic substance or the like.

The decane coupling agent is a compound having one or more alkoxyalkyl groups and one or more organic functional groups in one molecule, and the organic functional group is preferably a (meth) acryl fluorenyl group, an epoxy group, an amine group, a thiol group. More preferably, it is a (meth) acrylonitrile group.

When the blending ratio of the decane coupling agent is 5% by weight or less based on 100 parts by weight of the solid content of the composition, it is preferable from the viewpoint of reducing gas evolution.

(4) Polymerization inhibitors or/and antioxidants

When a polymerization inhibitor or/and an antioxidant is added to the composition of the present invention, the storage stability of the composition of the present invention and the photocurable filler resin sheet can be improved.

The polymerization inhibitor is preferably hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, and various phenolic antioxidants, but may also be added with a sulfur-based secondary antioxidant, phosphorus. It is a secondary antioxidant, a cupferron antioxidant, and the like.

The total blending ratio of the polymerization inhibitor or/and the antioxidant is preferably 0.001 to 3% by weight, more preferably 0.01 to 0.5% by weight based on 100 parts by weight of the solid content of the composition.

(5) Light resistance enhancer

The composition of the present invention may be added with an ultraviolet absorber or a light stabilizer depending on the use.

The blending ratio of the light fastness improving agent is preferably from 0 to 10% by weight, more preferably from 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.

(6) Organic solvents

The composition of the present invention preferably contains no organic solvent in terms of productivity and environmental surface, but may contain an organic solvent for the purpose of improving coatability. As the organic solvent, for example, the above organic solvent related to the production of the component (B) can be used.

<Adhesive Composition>

The composition of the present invention is obtained by mixing the above raw materials by a conventional method at normal temperature or under heating. The viscosity of the composition is not particularly limited, and is preferably 200 to 20,000 mPas at 25 °C. By making the viscosity into this range, it can be smoothly applied.

Further, the glass transition temperature (Tg) of the cured product obtained by the active energy ray irradiation of the adhesive composition of the present invention is -20 ° C or lower, preferably -30 ° C or lower, more preferably -40 ° C or lower. By setting the aforementioned Tg to -20 ° C or lower, good adhesion can be exhibited. Further, the Tg of the adhesive composition was also measured by the intermediate point of the endothermic peak detected by the differential scanning calorimeter, similarly to the component (B).

<Active Energy Ray Irradiation Method>

The adhesive composition of the present invention can be applied to substrates such as paper, various plastics, metals, inorganic materials, and various films or formed articles such as wood. Further, it can also be used for bonding (fixing) various members such as a film or a glass plate.

Specific examples of the plastics include polyethylene terephthalate, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polycarbonate resin, epoxy resin, and polyurethane resin.

The inorganic materials are exemplified by mortar, concrete, and the like.

The coating method of the composition of the present invention on the substrate may be, for example, bar coating, roll coating, spin coating, dip coating, gravure coating, nozzle coating, flow coating, spray coating, or the like.

The thickness of the adhesive composition for the substrate may be appropriately set according to the purpose, but the state after the irradiation of the active energy ray is about 5 to 100 μm.

The active energy ray for hardening the composition of the present invention is exemplified by electron beam, ultraviolet light, visible light, X-ray, etc., but ultraviolet light is preferable because an inexpensive device can be used.

The ultraviolet irradiation device is exemplified by a high pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, an LED, or the like.

The irradiation condition can be appropriately set depending on the kind of the active energy ray or the composition of the blending, but it is preferably from 0.1 to 200 mW/cm ² , more preferably from 0.5 to 100 mW/cm ² in terms of the irradiation intensity. Further, the irradiation energy is preferably from 10 to 5,000 mJ/cm ² , more preferably from 100 to 2,000 mJ/cm ² .

When electron beam curing is used, various electron beam (EB) irradiation devices can be used, and are exemplified by, for example, a Cockcroft-Walton type, a Van de Graaff type, and a resonance transformer type. It has a energy of 50 to 1,000 eV, preferably 100 to 300 eV.

<Adhesive product and method of manufacturing the same>

The adhesive article of the present invention may be provided with a cured product of the active energy ray-curable adhesive composition of the present invention. In the present specification, the adhesive product is not particularly limited as long as it retains the adhesive state of the cured product of the present invention. In general, the adhesive article is a cured product of the present invention which has one or more base materials and is held relative to at least a part thereof. The hardened material is provided by an adhesive portion or an adhesive layer.

The substrate is not particularly limited, and is exemplified by all the substrates, parts, and products that are useful when the adhesiveness is provided. Further, the material of the substrate is also not particularly limited as described above.

For example, the adhesive article may be one having a cured product on at least a part of a substrate such as a sheet or a film of a conventional material. The form is typically exemplified by conventional adhesive tapes or films. Moreover, it is also possible to provide a cured product for parts of various shapes. This form is typically exemplified by various parts including an adhesive layer, for example, an optical film having an adhesive layer, a surface protective film, a foam, and the like. Furthermore, it is also possible to provide a cured product between two or more types of parts. This form is, for example, a part or article in which a surface protective film or an optical film is fixed to an adherend of an object to be adhered through an adhesive layer. The adhesive article is not particularly limited except for electronic materials and optical materials.

The thickness of the cured product in the adhesive product is not particularly limited and may be appropriately set depending on the purpose, and may be, for example, 5 to 100 μm.

The manufacturing method of the adhesive article of the present invention can be provided with 1 or 2 The above-mentioned substrate is supplied with the active energy ray-curable adhesive composition of the present invention, and the step of applying the active energy ray to the composition to be hardened and exhibiting adhesiveness. The supply step can be carried out by supplying the composition to the substrate in accordance with a usual method as described above, and the adhesion-promoting step can be carried out under various conditions as described above.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples. In addition, the "part" in the following means the mass part.

○ Manufacture of macromonomer (B) having a (meth) acrylonitrile group at one end

<Manufacturing Example 1>

Into a glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a nitrogen inlet tube, and a thermometer, 100 parts of methyl methacrylate (hereinafter referred to as "MMA") as a vinyl monomer was fed as a chain transfer agent. 1.3 parts of 2-mercapto glycolic acid and 80 parts of butyl acetate (hereinafter referred to as "BAC") as a polymerization solvent were heated and stirred to 90 ° C under a nitrogen stream. In a separate container, 0.5 part of 2,2'-azobis(2-methylbutyronitrile) (manufactured by Nippon Precision Chemical Co., Ltd., trade name "ABN-E") was added and dissolved in 20 parts of BAC to prepare a polymerization initiation. The solution solution was maintained at 90 ° C in the flask and the polymerization initiator solution was added dropwise to the flask over 3 hours. Heating was further continued for 3 hours to complete the polymerization, and a polymer having a hydroxyl group at one terminal was obtained.

The nitrogen flow was switched to open air, and then 0.02 parts of methoxyphenol and dioctyltin dilaurate were added to the same flask (Nitto Chemical Co., Ltd. In the case of the product name "NEOSTAN U-810", 2.3 parts of 2-isocyanate ethyl acrylate (manufactured by Showa Denko Co., Ltd., trade name "KARENZ AOI"), which is a modifier, was cooled to room temperature by heating at 90 ° C for 3 hours. A BAC solution of a macromonomer B1 having a propylene fluorenyl group at one end.

The solution was heated to 100 ° C under a reduced pressure of 3 kPa to remove the BAC to obtain a white powder of the macromonomer B1.

After measuring the molecular weight of the obtained macromonomer B1, the weight average molecular weight (Mw) = 11,000 and the number average molecular weight (Mn) = 6,000. Moreover, the Tg of the macromonomer B1 was 96 °C.

<Production Examples 2 to 8 and Comparative Production Examples 1, 4 to 7>

Except that the monomer, the chain transfer agent, and the modifier were used as shown in Tables 1 and 2, the same operations as in Production Example 1 were carried out to obtain macromonomers B2 to B8, and polymers P1 and P4 to 7.

Here, the polymers P6 and P7 are macromonomers obtained by introducing four or one acrylonitrile groups per molecule on the molecular chain of the polymer.

The physical properties of the macromonomers B2 to B8 and the polymers P1 and P4 to 7 are shown in Tables 1 and 2.

<Comparative Manufacturing Example 2, 3>

In addition to the monomer, chain transfer agent and modifier as shown in Table 2, after the end of the polymerization, 0.01 parts of dioctyltin dilaurate was substituted with 1.0 part of tetrabutylammonium bromide, and reacted at 110 ° C. The same operations as in Production Example 1 were carried out except for the hour, to obtain polymers P2 and P3.

The physical property values of the polymers P2 and P3 are shown in Table 2.

<Comparative Manufacturing Example 8>

The monomer and the chain transfer agent were used as shown in Table 2. After the completion of the polymerization, the modification was carried out and the BAC was removed by heating to 100 ° C under a reduced pressure of 3 kPa to obtain a polymer P8.

The physical property values of the polymer P8 are shown in Table 2.

The abbreviations used in Tables 1 and 2 are shown below.

MMA: Methyl methacrylate

St: Styrene

EA: ethyl acrylate

AN: Acrylonitrile

MAA: Methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

MPA: 3-mercaptopropionic acid

MTG: 2-mercaptoethanol

DM: n-dodecyl mercaptan

MOI: 2-isocyanate ethyl methacrylate ("KARENZ MOI" by Showa Denko)

AOI: 2-isocyanate ethyl acrylate ("KARENZ AOI" by Showa Denko)

GMA: glycidyl methacrylate

4HBAGE: 4-hydroxybutyl acrylate glycidyl ether ("4HBAGE" made by Nippon Kasei)

TMI: dimethylisopropenylbenzyl isocyanate ("TMI" by Mitsui Cytec)

<Examples 1 to 13 and Comparative Examples 1 to 13>

The component (A), the component (B), the photoinitiator (C) and other components were blended in the proportions shown in Table 3, and uniformly mixed to obtain an active energy ray-curable resin composition. Each of the obtained compositions was evaluated for various physical properties by the evaluation methods described below. The results are shown in Table 3.

<Production of Adhesive Sheets>

Each of the compositions was applied to a 50 μm PET film ("LUMIRROR T-60 #50" manufactured by TORAY) so that the film thickness was 25 μm using an applicator. Subsequently, ultraviolet rays were irradiated under the following conditions using an ultraviolet irradiation device (ECS-401GX, manufactured by IGRAFX Co., Ltd.) until the cumulative amount of light became 1000 mJ/cm ^{2 to} obtain a hardened adhesive layer. Subsequently, a 38 μm release film ("SERAPEEL BK" manufactured by TORAY FILM Co., Ltd.) was attached to the adhesive layer to obtain an adhesive sheet for the test.

UV irradiation conditions:

80W/cm collecting light type high pressure mercury lamp

Lamp height 10cm

The conveyor speed was adjusted to be 100 mJ/cm ² per one shot.

(1) Hardenability

In the production of the above-mentioned adhesive sheet, the reaction rate of the polymerizable functional group per one pass was recorded, and the number of passes until the reaction rate of the polymerizable functional group exceeded 95% was recorded, and the hardenability was evaluated. Further, the reaction rate of the polymerizable functional group was measured by using an infrared absorption spectrum apparatus (FT-IR Spectrum 100 manufactured by Perkin Elmer), and the peak of the polymerizable functional group (C=C double bond) from 810 cm ^-1 was relatively The ratio of the reference peak (ester) at 1730 cm ^-1 was calculated and calculated as a reaction rate of 0% before ultraviolet irradiation.

(2) Film turbidity

For the above-mentioned adhesive sheet, the turbidity was measured using a turbidimeter [NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.]. Further, the measured value was obtained by superimposing two pieces of LUMIRROR T-60 #50 and SERAPEEL BK as a blank group.

(3) coloring

For the above-mentioned adhesive sheet, the YI value was measured using a high-speed integrating sphere type spectroscopic transmittance measuring instrument [SPECTROPHOTOMETER DOT-3C manufactured by Murakami Color Research Laboratory Co., Ltd.]. Also, the measured value is to overlap the LUMIRROR T-60 #50 and the SERAPEEL BK The winner is a blank group.

(4) Adhesion

The adhesive sheet was cut into a width of 25 mm, and the release PET film was peeled off and attached to a BA-treated SUS304 plate, and a test piece was produced by pressing back and forth with an automatic roller device at a load of 2 kg × 1. Using this test piece, the 180° peel strength was measured under the conditions of 23° C. and 50% RH in accordance with the method described in JIS Z 0237, and the obtained value was used as the adhesive force.

(5) Retention

The adhesive sheet was cut into a width of 25 mm, and the release-release PET film was attached to a BA-treated SUS304 plate so as to be bonded so as to have a subsequent area of 25 mm × 25 mm, and the automatic roller device was loaded at a load of 2 kg × 1. A test piece was made by pressing back and forth. The test piece was measured for holding power in accordance with the method described in JIS Z 0237 under the conditions of 23 ° C and 50% RH. Further, the load was set to 1 kg, and the time until the application of the load to the peeling was measured, and the holding time [hr] was used as the holding force. Moreover, the offset width from the initial bonding position is described when it is kept for 24 hours or more.

(6) Metal corrosion

The adhesive sheet was cut into a width of 25 mm, and the release-release PET film was attached to an aluminum plate, and then left under high temperature and high humidity conditions of 60 ° C × 90% RH for 48 hr. Subsequently, the sample was peeled off from the aluminum plate, and the surface was visually confirmed, and evaluated according to the following criteria.

○: No discoloration was confirmed on the surface of the aluminum foil

×: The surface of the aluminum foil was confirmed to be discolored

The abbreviations used in Table 3 are shown below.

BA: n-butyl acrylate

HDDA: 1,6-hexanediol diacrylate

MMA: Methyl methacrylate

AA: Acrylic

Examples 1 to 13 are experimental examples of an active energy ray-curable adhesive composition satisfying the requirements of the present invention, which have good hardenability, and the obtained adhesive sheet has a high degree of adhesion and cohesion. Less color and metal corrosion is inhibited.

From the comparison of Examples 1 and 8, it is understood that a macromonomer having a terminal polymerizable functional group having an acrylonitrile group is superior in curability to those having a methacrylium group.

On the other hand, in Comparative Examples 1 and 8 to 11 (B), the component of the present invention satisfies the requirements of the present invention, or the adhesive composition of the component (B) itself is not used, but the balance of adhesion is poor.

Further, in Comparative Examples 2, 3, 5, and 12, since the compound having an acid group was used as the raw material of the component (A) or the component (B), corrosion of the metal was confirmed.

In Comparative Example 4, since the polymerizable functional group of the component (B) was not a (meth) acrylonitrile group, the result of poor hardenability by irradiation with an active energy ray was obtained.

In Comparative Examples 6 and 7, a polymer having an acrylonitrile group in the middle of the molecular chain, which is not the terminal end, but an example of the component (B) was used. In Comparative Example 7, a polymer having an average of one acrylonitrile group was used, and the obtained coating film was foggy. This speculation is due to the influence of polymers without functional groups. Further, in Comparative Example 6, since it had an average of four acrylonitrile groups, the influence of the polymer having no functional group was small, and the coating film did not show haze, but the adhesion was insufficient.

In Comparative Example 13, the glass transition temperature of the cured product exceeded -20 ° C, and as a result, the adhesion was insufficient.

[Industrial availability]

When the active energy ray-curable adhesive composition of the present invention is used, excellent adhesion and cohesive force, turbidity and coloration of the cured product can be obtained. Less adhesive that inhibits metal corrosion. Therefore, various adhesive articles in the field of containing electronic materials and optical materials can be utilized.

Claims (9)

An active energy ray-curing adhesive composition characterized by comprising a vinyl monomer having no acid group (A), a macromonomer having a (meth) acrylonitrile group at one end (B), and a photopolymerization initiation The active energy ray-curable adhesive composition of the agent (C), wherein the glass transition temperature of the above (B) is 30° C. or higher, and the glass transition temperature of the adhesive after curing is not used in the production. It is below -20 °C. The active energy ray-curable adhesive composition according to claim 1, wherein the total of the above (A) and (B) is 100 parts by mass, and the above-mentioned (A), 2 to 10 masses are contained in an amount of 90 to 98 parts by mass. The aforementioned (B). The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the weight average molecular weight of the above (B) is 5,000 to 20,000. The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the terminal polymerizable functional group of the above (B) is an acrylonitrile group. A product which is an adhesive product and which is provided with a cured product of the active energy ray-curable adhesive composition according to any one of claims 1 to 4. A product according to claim 5, which comprises a substrate and a cured product which is provided to at least a part of the substrate. The article of claim 5 or 6, wherein the adhesive article is an electronic material or an optical material. A manufacturing method for manufacturing an adhesive article and having The active energy ray-curable adhesive composition according to any one of claims 1 to 4 is supplied to at least a part of the substrate, and the composition is cured by irradiation of an active energy ray to the composition to cause adhesion. The steps of sex. The manufacturing method of claim 8, wherein the adhesive article is an electronic material or an optical material.