CN105143388B - Ultraviolet curable adhesive composition and adhesive - Google Patents

Abstract

The problem to be solved in the present invention is to provide the ultraviolet-curing adhesive composition that bonding force, wet-heat resisting albefaction and wet-heat resisting xanthochromia are excellent.The present invention provides ultraviolet-curing adhesive composition and the binding agent using said composition to obtain, described ultraviolet-curing adhesive composition is characterised by, it contains carbamate (methyl) acrylate (X), (methyl) acrylic monomer (Y) and Photoepolymerizationinitiater initiater (Z), described carbamate (methyl) acrylate (X) is the polyhydric alcohol (a) making to comprise Polyethylene Glycol (a1), polyisocyanates (b) and (methyl) acrylic compounds (c) with hydroxyl or NCO react and obtain.The binding agent using the ultraviolet-curing adhesive composition of the present invention to obtain can be suitably used as the binding agent for optics.Especially can be suitably employed in the IT Related products such as manufacture contact panel, liquid crystal display, plasma display, organic EL, PC, mobile phone.

Description

Ultraviolet curable adhesive composition and adhesive

technical field

The present invention relates to an ultraviolet curable adhesive composition and an adhesive having excellent adhesion, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance.

Background technique

Conventionally, acrylic adhesives have been used in a wide variety of applications. In particular, in recent years, applications to IT-related products such as thin TVs have been expanding, and improvements in performance and functionality have been promoted. However, the price of IT-related products is also falling, and not only high performance but also high productivity are required.

Among them, since the drying process of the solvent, which is an essential process in the case of conventional type adhesives (solvent-based and water-based), and the aging time required from processing until performance is expressed, etc., high productivity can be expected UV-curable adhesives have attracted attention. In addition, since it is easier to increase the film thickness of the pressure-sensitive adhesive layer than conventional pressure-sensitive adhesives, advantages such as higher performance can be expected, and future development is expected.

As an ultraviolet curable adhesive that can be used in the above-mentioned IT-related products, for example, an adhesive composition is known, which is characterized in that it contains 5 parts by mass or more of And 200 parts by mass or less of a high molecular weight substance having a weight average molecular weight of 20,000 or more having a urethane bond and an unsaturated double bond at a polymer terminal (see, for example, Patent Document 1).

However, the above-mentioned adhesives have problems such as whitening of the adhesive film or subsequent yellowing when the adhesive is left at room temperature after being used under hot and humid conditions.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2006-104296

Contents of the invention

The problem to be solved by the present invention is to provide an ultraviolet curable adhesive composition excellent in adhesion, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance.

means of solving problems

The inventors of the present invention focused on urethane (meth)acrylates and conducted studies in order to solve the above-mentioned problems.

As a result, they found that the above-mentioned problems can be solved by including polyethylene glycol as a polyhydric alcohol used as a raw material of urethane (meth)acrylate, and completed the present invention.

That is, the present invention provides an ultraviolet curable adhesive composition characterized in that it contains a urethane (methyl) Acrylate (X), (meth)acrylic monomer (Y) and photopolymerization initiator (Z), described urethane (meth)acrylate (X) is made to contain polyethylene glycol (a1) It is obtained by reacting polyol (a), polyisocyanate (b) and (meth)acrylic compound (c) having hydroxyl group or isocyanate group.

Invention effect

The adhesive obtained using the ultraviolet curable adhesive composition of the present invention has excellent adhesive force, holding power, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance.

An adhesive obtained using the ultraviolet curable adhesive composition of the present invention can be suitably used as an adhesive for optical parts. In particular, it can be suitably used for manufacturing IT-related products such as touch panels, liquid crystal displays, plasma displays, organic EL, personal computers, and mobile phones.

detailed description

The ultraviolet curable adhesive composition of the present invention contains urethane (meth)acrylate (X), (meth)acrylic monomer (Y) and photopolymerization initiator (Z), and the urethane The ester (meth)acrylate (X) is obtained by reacting a polyol (a) containing polyethylene glycol (a1), a polyisocyanate (b) and a (meth)acrylic compound (c) having a hydroxyl group or an isocyanate group. And get.

The above-mentioned polyethylene glycol (a1) improves the hydrophilicity of the ultraviolet curable adhesive composition, and since the adhesive film can absorb moisture and moisture uniformly when exposed to hot and humid conditions, it contributes to the inhibition of adhesion. The whitening of the mixture coating after heat and humidity resistance. In addition, by using the above-mentioned polyethylene glycol (a1), the amount of the (meth)acrylic monomer that is prone to yellowing can be reduced or the use of the (meth)acrylic monomer that is prone to yellowing can be eliminated. , so it can also maintain the adhesive force and impart excellent resistance to moist heat yellowing.

The above-mentioned polyethylene glycol (a1) is used as a raw material for urethane (meth)acrylate (X), but from the viewpoint of adhesive force, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance, straight-chain Any one of polyethylene glycol and branched polyethylene glycol, the polyethylene glycol (a1) can be in the form of a grafted chain in the above-mentioned urethane (meth)acrylate (X) Exist, also can exist in the form of block chain.

The number average molecular weight of the above-mentioned polyethylene glycol (a1) is preferably in the range of 200 to 5,000 from the viewpoint of further improving the moisture-heat whitening resistance and the moisture-heat yellowing resistance, and further improving the reaction during synthesis. From the viewpoint of easiness of property control, storage stability at low temperature, etc., it is more preferably in the range of 200 to 2,000, and still more preferably in the range of 200 to 1,000. In addition, the number average molecular weight of the said polyethylene glycol (a1) shows the value measured by the gel permeation chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)

Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

"TSKgel G5000" (7.8mmI.D.×30cm)×1

"TSKgel G4000" (7.8mmI.D.×30cm)×1

"TSKgel G3000" (7.8mmI.D.×30cm)×1

"TSKgel G2000" (7.8mmI.D.×30cm)×1

Detector: RI (differential refractometer)

Column temperature: 40°C

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0mL/min

Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

Standard sample: A calibration curve was prepared using the following standard polystyrene.

(standard polystyrene)

"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation

"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

The amount of polyethylene glycol (a1) used is preferably 1 to 60% of the polyol (a) above, from the viewpoint of further improving adhesive force, holding power, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance. The range of mass % is more preferably the range of 3-50 mass %, the range of 5-40 mass % is still more preferable, and the range of 10.5-33 mass % is especially preferable.

In addition, as the content of the above-mentioned polyethylene glycol (a1) in the urethane (meth)acrylate (X), it is possible to further improve the adhesive force, holding power, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance. From the point of view, it is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 5 to 35% by mass, and still more preferably in the range of 9 to 25% by mass.

As the above-mentioned polyol (a) that can be used other than the above-mentioned polyethylene glycol (a1), for example, polyether polyols other than polyethylene glycol, polyester polyols, polycarbonate polyols, and acrylic polyols can be used. , butadiene polyols, etc. These polyhydric alcohols can be used individually or in combination of 2 or more types. Among these, it is preferable to use the above-mentioned polyether polyol and polycarbonate polyol from the point which can further improve adhesive force, holding power, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance.

As the above-mentioned polyether polyol, for example, one or more kinds of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are added and polymerized to a compound having two or more active hydrogens. products; polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran; modified polytetramethylene glycol obtained by copolymerizing tetrahydrofuran and alkyl-substituted tetrahydrofuran; modified polytetramethylene glycol obtained by copolymerizing neopentyl glycol and tetrahydrofuran; etc. Wait.

As the compound having two or more active hydrogens, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, triethylene glycol, Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, 11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-bisphenol and other lower molecular weight dihydroxy compounds; 1,2 -Cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, 1,4-cyclohexanedimethanol, hydroxypropylcyclohexanol , tricyclo[5,2,1,0,2,6]decanedimethanol, bicyclo[4,3,0]nonanediol, dicyclohexanediol, tricyclo[5,3,1,1] Dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecanediethanol, hydroxypropyltricyclo[5,3,1,1] Dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-biscyclohexylene glycol, cyclohexanetriol, hydrogenated bisphenol A, 1,3-adamantanediol, etc. Alicyclic polyols; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyesters such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone polyols; etc.

The number average molecular weight of the polyether polyol is preferably in the range of 200 to 3,000, more preferably in the range of 500 to 2,000, and still more preferably in the range of 500 to 1,500. In addition, the number average molecular weight of the said polyether polyol shows the value measured similarly to the number average molecular weight of the said polyethylene glycol (a1).

As said polycarbonate polyol, the polycarbonate polyol obtained by making carbonate ester and/or phosgene, and the said compound which has two or more active hydrogens react can be used, for example.

As the aforementioned carbonate, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

The hydroxyl value of the polycarbonate polyol is preferably in the range of 30 to 230 mgKOH/g, and more preferably in the range of 50 to 230 mgKOH/g, from the viewpoint of further improving the adhesive force. In addition, the hydroxyl value of the said polycarbonate polyol shows the value measured based on JISK0070-1992.

As the above polyisocyanate (b), for example, aromatic diisocyanates such as xylylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, Lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate and other fatty acids Family or diisocyanate with alicyclic structure, etc. These polyisocyanates can be used individually or in combination of 2 or more types. Among these, it is preferable to use diisocyanate having an alicyclic structure, more preferably to use 4,4'-dicyclohexylmethane diisocyanate, isofor Alone diisocyanate, cyclohexane diisocyanate, methyl cyclohexane diisocyanate.

The above-mentioned (meth)acrylic compound (c) having a hydroxyl group or an isocyanate group is used for the purpose of introducing a (meth)acryloyl group into the urethane (meth)acrylate (X).

As the above-mentioned (meth)acrylic compound having a hydroxyl group that can be used as the above-mentioned compound (c), there can be used, for example: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, acrylic acid 3 Alkyl (meth)acrylates with hydroxyl groups such as hydroxypropyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl acrylate, hydroxyethyl acrylamide, etc. Esters; trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and other polyfunctional (meth)acrylates with hydroxyl groups; polyethylene glycol Monoacrylate, polypropylene glycol monoacrylate, etc. Among these, it is more preferable to use an acrylic compound having a hydroxyl group from the viewpoint of further improving curability by ultraviolet rays, and it is more preferable to use a As the alkyl acrylate having a hydroxyl group, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly preferably used.

In addition, as the (meth)acrylic compound having an isocyanate group that can be used as the above-mentioned compound (c), for example, 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(methyl) ) acryloyloxyethoxy)ethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate and the like. Among these, 2-(meth)acryloyloxyethyl isocyanate is preferably used, and 2-acryloyloxyethyl isocyanate is more preferably used from the viewpoint of the ease of obtaining raw materials.

As the method for producing the above-mentioned urethane (meth)acrylate (X) in the case of using a (meth)acrylic compound having a hydroxyl group as the above-mentioned compound (c), for example, in the absence of a solvent, A method of producing the above-mentioned polyol (a) and the above-mentioned (meth)acrylic compound (c) after being put into the reaction system, supplying the above-mentioned polyisocyanate (b), mixing and reacting them; in the absence of a solvent, A urethane prepolymer having an isocyanate group is obtained by reacting the above-mentioned polyol (a) with the above-mentioned polyisocyanate (b), and then, the above-mentioned (meth)acrylic compound (c) having a hydroxyl group is supplied to make it Mixing, reacting, methods of making thereby; etc. In any case, it is preferable to carry out the reaction at 20 to 120° C. for approximately 30 minutes to 24 hours.

In addition, as the production method of the urethane (meth)acrylate (X) in the case of using a (meth)acrylic compound having an isocyanate group as the above-mentioned compound (c), for example: , put in the above-mentioned polyol (a) and the above-mentioned polyisocyanate (b) to react to obtain a urethane prepolymer having a hydroxyl group, and then supply the above-mentioned (meth)acrylic compound (c) having an isocyanate group , making it mix and react, and the method of making it, etc. In any case, it is preferable to carry out the reaction at 20 to 120° C. for approximately 30 minutes to 24 hours.

Production of the above-mentioned urethane (meth)acrylate (X) can be performed in the presence of an organic solvent or an aqueous medium. In addition, instead of an organic solvent or an aqueous medium, it can also be produced in the presence of a (meth)acrylic monomer (Y) to be described later.

The reaction between the above-mentioned polyol (a) and the above-mentioned polyisocyanate (b) and the above-mentioned (meth)acrylic compound (c) is performed in the reaction between the hydroxyl group of the above-mentioned polyol (a) and the above-mentioned (meth)acrylic compound (c) The total amount of the hydroxyl groups it has, and the equivalent ratio between the isocyanate groups that the polyisocyanate (b) has [the total amount of isocyanate groups/hydroxyl groups] = 0.75 to 1. The viewpoint of the molecular weight of ester (meth)acrylate (X) is preferable, and it is more preferable that it is the range of 0.79-0.995. In addition, it is also possible to make it react when the above-mentioned equivalent ratio exceeds 1, but in this case, for the purpose of deactivating the isocyanate group of the urethane (meth)acrylate (X), it is preferable to use an alcohol such as methanol . At this time, it is preferable to adjust so that the total amount of the hydroxyl group of the polyol (a), the hydroxyl group of the (meth)acrylic compound (c), and the hydroxyl group of alcohol, and the polyisocyanate group are adjusted. The equivalent ratio [the total amount of isocyanate group/hydroxyl group] is within the above range.

In addition, as an alcohol that can be used for the purpose of deactivating the isocyanate group of the above-mentioned urethane (meth)acrylate (X), for example, monofunctional alcohols such as methanol, ethanol, propanol, butanol can be used; 1 , 2-propanediol, 1,3-butanediol and other difunctional alcohols containing primary and secondary hydroxyl groups.

Moreover, when producing a urethane (meth)acrylate (X), you may use a polymerization inhibitor, a urethanization catalyst, etc. as needed.

As the above-mentioned polymerization inhibitor, for example, 3,5-di-tert-butyl-4-hydroxytoluene, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether (p-methoxyphenol), p-tert- Butylcatechol methoxyphenol, 2,6-di-tert-butylcresol, phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene, etc.

As the above-mentioned urethanization catalyst, for example, nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine; metal salts such as potassium acetate, zinc stearate, and tin octoate; dibutyltin laurate; , zirconium acetylacetonate and other organometallic compounds.

The above-mentioned urethane (meth)acrylate (X) has a (meth)acryloyl group radically polymerized by light irradiation, heating, or the like. The equivalent of the (meth)acryloyl group is preferably in the range of 1,000 to 200,000 g/eq., more preferably 5,000 to 100,000 g/eq, from the viewpoint of further improving the adhesive force, step adhesion, etc. The range of . It should be noted that the equivalent of the above-mentioned (meth)acryloyl group represents the total mass of the above-mentioned polyol (a) and polyisocyanate (b) and (meth)acrylic compound (d) divided by the above-mentioned carbamate The value after the equivalent of the (meth)acryloyl group which exists in (meth)acrylate (X). In addition, in the present invention, "(meth)acrylic compound" refers to one or both of methacrylic compound and acrylic compound, and "(meth)acrylate" refers to methacrylate and acrylate. One or both of them, "(meth)acryloyl" refers to one or both of methacryloyl and acryloyl, "(meth)acrylic acid" refers to one or both of methacrylic acid and acrylic acid, " The "(meth)acrylic monomer" refers to one or both of a methacrylic monomer and an acrylic monomer.

The weight average molecular weight of the above-mentioned urethane (meth)acrylate (X) is preferably 5,000 to 200,000 from the viewpoint of achieving both excellent adhesive force and holding force and imparting good coating workability. range, more preferably in the range of 10,000 to 100,000. In addition, the weight average molecular weight of the said urethane (meth)acrylate (X) shows the value measured similarly to the number average molecular weight of the said polyethylene glycol (a1).

As the (meth)acrylic monomer (Y), for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate can be used. , Butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-pentyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate ester, 3-methylbutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, ( Aliphatic (meth)acrylates such as neopentyl methacrylate, cetyl (meth)acrylate, isopentyl (meth)acrylate; isobornyl (meth)acrylate, cyclic (meth)acrylate Alicyclic (meth)acrylates such as hexyl ester, tetrahydrofurfuryl (meth)acrylate; 3-methoxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, ( 3-methoxypropyl methacrylate, 2-methoxybutyl (meth)acrylate, methoxypolyethylene glycol acrylate in which the number of added moles of ethylene oxide is in the range of 1 to 15, ethyl Oxydiethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate and other (meth)acrylates with ether groups; 2-hydroxyethyl (meth)acrylate, (meth)acrylate ) 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate and other (meth)acrylates with hydroxyl groups; benzyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Aromatic (meth)acrylates such as phenoxyethyl ester, phenoxy polyethylene glycol acrylate, phenyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate; (meth)acrylamide, dimethyl (meth)acrylamide, acryloyl morpholine, dimethylaminopropyl (meth)acrylamide, isopropyl (meth)acrylamide, diethyl (methyl) (meth)acrylic monomers having a nitrogen atom, such as ) acrylamide, hydroxyethyl (meth)acrylamide, diacetone (meth)acrylamide, etc. These (meth)acrylic monomers can be used individually or in combination of 2 or more types.

In addition, as said (meth)acrylic-type monomer (Y), in order to provide the outstanding moist-heat-resistant whitening property, the (meth)acrylic-type monomer which has the said nitrogen atom may be used. In this case, the heat-and-moisture yellowing resistance may decrease, so the addition amount is preferably small, preferably 40% by mass or less, more preferably 35% by mass or less, based on the total amount of the (meth)acrylic monomer (Y). In the present invention, since the hydrophilicity of the adhesive coating can be improved by using the above-mentioned polyethylene glycol (a1), it is possible to express moist heat whitening resistance with a small amount of addition.

The amount of the above-mentioned (meth)acrylic monomer (Y) used is preferably 30 to 200 parts by mass relative to 100 parts by mass of the above-mentioned urethane (meth)acrylate (X) from the viewpoint of adhesive force. It is used in the range of mass parts, More preferably, it is the range of 50-150 mass parts, Especially preferably, it is the range of 70-130 mass parts.

The above-mentioned photopolymerization initiator (Z) generates radicals by light irradiation, heating, etc., and initiates the radicals of the above-mentioned urethane (meth)acrylate (X) and the above-mentioned (meth)acrylic monomer (Y) polymerization.

As the photopolymerization initiator (Z), for example, 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- Ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 4-(2-hydroxyethoxy)-phenyl (2-Hydroxy-2-propyl)ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2,2-dimethoxy-2- Acetophenone compounds such as phenylacetophenone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'- Dimethyl-4-methoxybenzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone compounds; 4,4'- Dimethylaminothioxanthone (alias: Minera-zuketon), 4,4'-diethylaminobenzophenone, α-acyl oxime ester, benzil, methyl benzoylformate ("Baiacyua 55"), Anthraquinone compounds such as 2-ethylanthraquinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“LucirinTPO”), bis(2,4,6-trimethylbenzoyl)benzene Acyl phosphine oxide compounds such as phosphine oxide ("IRGACURE 819"); Acrylated benzophenone, etc.

As the above-mentioned photopolymerization initiator (Z), it is preferable to use 2-hydroxy-2-methyl-1-phenylpropane-1 - Ketone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

The usage-amount of the said photoinitiator (Z) is used preferably in the range of 0.1-20 mass parts with respect to 100 mass parts of said urethane (meth)acrylates (X), More preferably, it is 0.5-15 mass parts. range, particularly preferably in the range of 1 to 5 parts by mass.

The ultraviolet curable adhesive composition of the present invention contains the above-mentioned urethane (meth)acrylate (X), the above-mentioned (meth)acrylic monomer (Y) and the above-mentioned photopolymerization initiator (Z) as essential Components and other additives may be contained as needed.

As the above-mentioned other additives, for example, silane coupling agents, antioxidants, light stabilizers, solvents, rust inhibitors, thixotropy imparting agents, sensitizers, polymerization inhibitors, leveling agents, tackifiers, antistatic agents can be used , flame retardants, etc. Among these, it is preferable to contain a silane coupling agent from the point which can further improve the adhesive property after heat-and-moisture resistance. Moreover, it is preferable to contain an antioxidant and a photostabilizer from a point which can further improve heat-and-moisture yellowing resistance.

As the above-mentioned silane coupling agent, for example: 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidoxypropylmethylsilane, Diethoxysilane, 3-glycidyl etheroxypropylmethyldimethoxysilane and other silane coupling agents with epoxy groups; 2-(3,4-epoxycyclohexyl)ethyltriethyl Oxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3, 4-Epoxycyclohexyl)ethylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)propyl Methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)propyltriethoxysilane, 2-(3,4-epoxycyclohexyl)propylmethyldiethoxysilane, etc. Silane coupling agent with alicyclic epoxy group; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxy Propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxy 3-Acryloxypropyltriethoxysilane, 3-Acryloyloxypropyltrimethoxysilane, 3-Mercaptopropylmethyldimethoxysilane, 3-Mercaptopropyltrimethoxysilane, Alkoxysiloxane alkane oligomers, etc. These silane coupling agents can be used alone or in combination of two or more. Among these, it is preferable to use a silane coupling agent having an epoxy group and a silane coupling agent having an alicyclic epoxy group from the viewpoint of further improving the adhesive force after heat and humidity resistance, and it is more preferable to use a silane coupling agent selected from the group consisting of 2 -(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxy One or more of silane and 3-glycidyloxypropyltriethoxysilane.

As the usage-amount of the said silane coupling agent, it is preferable to use 0.01 mass parts with respect to 100 mass parts of said urethane (meth)acrylates (X) from the point which can further improve the adhesive force after heat-and-moisture resistance. -10 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.05 to 1 part by mass.

As the antioxidant, hindered phenolic compounds (primary antioxidants) that capture radicals generated by thermal degradation, phosphorus compounds and sulfur compounds (secondary antioxidants) that decompose peroxides generated by thermal degradation, and the like can be used.

As the hindered phenol compound, for example, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl) propionate], 3-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, thiodiethylenebis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], phenylpropanoic acid-3,5-bis(1,1-dimethylethyl)-4-hydroxy-C ₇ -C ₉ side chain alkyl ester, 4,6-bis(dodecylthiomethyl)-o-cresol, reaction product of N-phenylaniline and 2,4,4-trimethylpentene, acrylic acid 2 -tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, 3,9-bis[2-[3-(tert-butyl- 4-Hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane, 2,6- Di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,5-di-tert-amylhydroquinone, etc.

As the above-mentioned phosphorus compound, for example, triphenylphosphine, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, triphenyl phosphite, trinonylphenyl phosphite , three (2,4-dibutylphenyl) phosphite, three (2,4-dibutyl-5-methylphenyl) phosphite, three (2-tert-butyl-4-( 3-Butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecane Diphenyl phosphite, octyl diphenyl phosphite, bis(decyl) monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite ester, bis(2,4-dibutylphenyl)pentaerythritol diphosphite, bis(2,6-dibutyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6 -Tributylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis(tridecyl)isopropylidene diphenol diphosphite, tetrakis (Tridecyl)-4,4'-n-butylene bis(2-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tri(2 -Methyl-4-hydroxy-5-butylphenyl)butane triphosphite, tetrakis(2,4-dibutylphenyl)biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-butylphenyl)-2-ethylhexyl phosphite, 2,2'- Methylenebis(4,6-butylphenyl)-octadecylphosphite, 2,2'-ethylenebis(4,6-dibutylphenyl)fluorophosphite, tri( 2-[(2,4,8,10-tetrabutyldibenzo[d,f][1,3,2]dioxaphosphorin-6-yl)oxy]ethyl) Amine, phosphite ester of 2-ethyl-2-butylpropanediol and 2,4,6-tributylphenol, etc.

As the above-mentioned sulfur compound, for example: 3,3'-dilauryl thiopropionate, dilauryl 3,3'-thiodipropionate, lauryl thiodithiosulfate (Lauryl thiodithiosulfate) can be used, for example.ルチオジチオネネト), 3,3'-Di(tridecyl)thiodipropionate, 3,3'-Dimyristyl thiodipropionate, 3,3'-Dipropylthiothioate Distearyl acid, tetra-methylene-3-lauryl thiopropionate methane, 3,3'-methyl-3,3'-thiodipropionate distearyl, 3,3' -Lauryl stearyl thiodipropionate, bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-tert-butylphenyl]sulfide, β-lauryl Thiopropionate, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 3,3'-dioctadecyl thiodipropionate, etc.

Among these, it is preferable to use a phosphorus compound, more preferably to use a phosphorus compound selected from the group consisting of triphenylphosphine, bis(2,4-di-tert-butyl-6-methyl, One or more antioxidants among phenyl) ethyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite, particularly preferably triphenylphosphine, bis(2,4-di-tert- Butyl-6-methylphenyl)ethyl phosphite.

As the usage-amount of the said antioxidant, it is preferable that it is the range of 0.01-10 mass parts with respect to 100 mass parts of said urethane (meth)acrylate (X) from the point which can further improve heat-and-moisture yellowing resistance.

The above-mentioned photostabilizer captures radicals generated by photodegradation, and for example, radical scavengers such as thiol compounds, thioether compounds, and hindered amine compounds, and ultraviolet absorbers such as benzophenone compounds and benzoate compounds can be used. Wait. Among these, it is preferable to use a hindered amine compound from the viewpoint of further improving the heat-and-moisture yellowing resistance.

As the aforementioned hindered amine compound, for example, cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3, The reaction product of 5-triazine and 2-aminoethanol, bis(2,2,6,6-tetramethyl-1-(octyloxylated)-4-piperidinyl) sebacate, Hindered amine compounds with amino ether groups such as the reaction product of 1,1-dimethylethylhydroperoxide and octane; N-acetyl-3-dodecyl-1-(2,2,6,6 -Tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione and other N-acetyl hindered amine compounds; sebacic acid bis(1,2,2,6,6-pentamethyl-4 -piperidinyl) ester, bis(1,2,2,6,6,-pentamethyl-4-piperidinyl){[3,5-bis(1,1-dimethylethyl)-4 -Hydroxyphenyl]methyl}butylmalonate, dimethyl succinate·1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate , Malonic acid [{4-methoxyphenyl}methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester N-alkyl hindered amine compound Wait.

As the usage-amount of the said light stabilizer, it is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of said urethane (meth)acrylate (X) from the point which can further improve the anti-yellowing property under heat and humidity. scope.

The viscosity of the ultraviolet curable adhesive composition of the present invention is preferably in the range of 500 to 20,000 mPa·s from the viewpoint of good applicability and good handling properties of the adhesive solution at the time of coating, More preferably, it is in the range of 1,000 to 15,000 mPa·s. In addition, the said viscosity shows the value measured with the B-type viscometer at 25 degreeC.

The ultraviolet curable adhesive composition of the present invention can be cured by irradiation with energy rays such as ultraviolet rays.

As a method of curing the ultraviolet-curable adhesive composition of the present invention, a predetermined ultraviolet light can be irradiated with a known ultraviolet light irradiation device such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, or a low-pressure mercury lamp. UV rays cure it.

The irradiation of the ultraviolet rays is preferably in the range of 0.05 to 5 J/cm ² , more preferably 0.1 to 3 J/cm ² , and particularly preferably 0.3 to 1.5 J/cm ² . In addition, the ultraviolet-ray irradiation amount used the value measured in the wavelength range of 300-390 nm using UV detector (checker) UVR-N1 (made by GS-YUASA Corporation).

As substrates on which the ultraviolet curable adhesive composition of the present invention can be applied to form an adhesive layer, plastic substrates, flexible printing substrates, glass substrates, and ITO deposited on these substrates can be used. base material, etc.

As the above-mentioned plastic substrate, commonly used substrates containing acrylic resins, PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE, etc., can be used. (polyphenylene ether), PET (polyethylene terephthalate), COP (cycloolefin polymer), TAC (cellulose triacetate), antireflective film, antifouling film, transparent conductive film constituting touch panels film etc.

Example

Hereinafter, the present invention will be described in more detail using examples.

[Synthesis Example 1]

<Synthesis of urethane acrylate (X-1)>

In a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer, 410 parts by mass of polytetramethylene glycol (number average molecular weight: 1,000, hereinafter abbreviated as "PTMG1000"), polyethylene glycol (number average molecular weight: 1,000) and polyethylene glycol (number average molecular weight: 400, hereinafter abbreviated as "PEG-1") 27.5 parts by mass, 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA) 6.1 parts by mass, 2,6-di-tert-butylcresol 2 parts by mass, p-methoxyphenol 0.3 parts by mass. After heating up until the temperature in the reaction container reached 40° C., 105 parts by mass of isophorone diisocyanate (hereinafter abbreviated as IPDI) was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. After that, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained urethane acrylate (X-1). The obtained urethane acrylate (X-1) had an equivalent of acryloyl group of 10,441 (rounded up to one decimal place. The molecular weight of 2-hydroxyethyl acrylate was 116.1. The same applies hereinafter) and a weight average molecular weight of 30,000.

[Synthesis Example 2]

<Synthesis of urethane acrylate (X-2)>

In a reaction vessel equipped with a stirrer, a reflux cooling pipe, a nitrogen introduction pipe, and a thermometer, 390 parts by mass of polycarbonate polyol (“Duranol T-5651” manufactured by Asahi Kasei Chemicals Co., Ltd., number average molecular weight: 1000) and polyethylene glycol were added. 43.4 parts by mass of alcohol (number average molecular weight: 600, hereinafter abbreviated as "PEG-2"), 9 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butylcresol, and 0.3 parts by mass of p-methoxyphenol. After heating up until the temperature in the reaction container reached 40° C., 102 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. After that, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained urethane acrylate (X-2). The equivalent weight of the acryloyl group of the obtained urethane acrylate (X-2) was 7,023, and the weight average molecular weight was 19,000.

[Synthesis Example 3]

<Synthesis of urethane acrylate (X-3)>

In a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer, 351 parts by mass of PTMG1000, 51.4 parts by mass of PEG-1, 5.7 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butylcresol, 2 parts by mass of p-cresol, and 0.3 parts by mass of oxyphenol. After heating up until the temperature in the reaction container reached 40°C, 104 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. After that, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained urethane acrylate (X-3). The equivalent weight of the acryloyl group of the obtained urethane acrylate (X-3) was 10,431, and the weight average molecular weight was 21,000.

[Synthesis Example 4]

<Synthesis of urethane acrylate (X-4)>

180 parts by mass of polypropylene glycol (number-average molecular weight: 3,000, hereinafter abbreviated as "PPG3000"), 143 parts by mass of PTMG1000, and 109 parts by mass of PEG-1 were added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer. , 6 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butylcresol, and 0.3 parts by mass of p-methoxyphenol. After heating up until the temperature in the reaction container reached 40°C, 105 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. After that, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained urethane acrylate (X-4). The equivalent weight of the acryloyl group of the obtained urethane acrylate (X-4) was 10,507, and the weight average molecular weight was 26,000.

[Synthesis Example 5]

<Synthesis of urethane acrylate (X-5)>

In a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer, 442 parts by mass of Duranol T-5652, 246 parts by mass of polyethylene glycol ("Ymer N120" manufactured by Perstorp, number average molecular weight: 1,000), 9.5 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butylcresol, and 0.3 parts by mass of p-methoxyphenol. After heating up until the temperature in the reaction container reached 40°C, 102 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. After that, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained urethane acrylate (X-5). The obtained urethane acrylate (X-5) had an acryloyl group equivalent of 9,771 and a weight average molecular weight of 20,000.

[Synthesis Example 6]

<Synthesis of urethane acrylate (X-6)>

In a reaction vessel equipped with a stirrer, a reflux cooling pipe, a nitrogen introduction pipe, and a thermometer, add 467 parts by mass of Duranol T-5651, 9.6 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butylcresol, 0.3 parts by mass of p-methoxyphenol parts by mass. After heating up until the temperature in the reaction container reached 40°C, 101 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. After that, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained urethane acrylate (X-6). The equivalent weight of the acryloyl group of the obtained urethane acrylate (X-6) was 6,985, and the weight average molecular weight was 19,000.

[Synthesis Example 7]

<Synthesis of urethane acrylate (X-7)>

460 parts by mass of PTMG1000, 6.5 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butylcresol, and 0.3 parts by mass of p-methoxyphenol were added to a reaction vessel equipped with a stirrer, a reflux cooling pipe, a nitrogen introduction pipe, and a thermometer. After heating up until the temperature in the reaction container reached 40°C, 105 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. After that, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained urethane acrylate (X-7). The equivalent weight of the acryloyl group of the obtained urethane acrylate (X-7) was 10,208, and the weight average molecular weight was 22,000.

[Example 1]

<Preparation of Ultraviolet Curable Adhesive Composition>

Into a reaction vessel equipped with a stirrer, a reflux cooling pipe, and a thermometer, 100 parts by mass of the above-mentioned urethane acrylate (X-1), 105 parts by mass of butyl acrylate (hereinafter abbreviated as "BA"), dimethylpropylene 10 parts by mass of amides (hereinafter abbreviated as DMAA) were stirred at 80° C. until uniform. Afterwards, it was cooled to room temperature, and 3 parts by mass of 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,2,6,6-tetramethyl-1-( 0.5 parts by mass of octyloxylated)-4-piperidinyl) ester, 0.5 parts by mass of triphenylphosphine, and 0.1 part by mass of 3-glycidyloxypropyltriethoxysilane were stirred until uniform. Thereafter, it was filtered through a 200-mesh metal mesh to obtain an ultraviolet curable adhesive composition.

[Examples 2-6, Comparative Examples 1-2]

As shown in Table 1, except that the types and amounts of the urethane (meth)acrylate and (meth)acrylic monomers used were changed, an ultraviolet curable type was obtained in the same manner as in Example 1. Adhesive composition.

[How to make adhesive film]

On the surface of a polyethylene terephthalate film (release PET50) with a thickness of 50 μm after the release treatment on the surface, it was coated in Examples and Comparative Examples so that the film thickness after UV irradiation was 175 μm. The obtained ultraviolet curable adhesive resin composition was bonded with release PET50. Thereafter, UV irradiation was performed using a UV irradiation apparatus so that the cumulative light intensity of the wavelength in the UV-A region after the mold release PET50 had passed through reached 1 J/cm ² , and an adhesive film was produced.

[Measuring method of adhesive force]

One side of the adhesive film produced by the above-mentioned method was bonded to a polyethylene terephthalate film (PET75) having a thickness of 75 μm, and an adhesive film in which a PET75 substrate was bonded on one side was prepared. This was cut to a width of 25 mm and used as a test piece. The test piece was attached to a glass plate and a polycarbonate (PC) plate as adherends under the conditions of 2 kg roller x 2 reciprocations. One hour after sticking, the 180-degree peel strength was measured in an atmosphere at 23° C. and a humidity of 50%, as the adhesive force.

[Evaluation method of moisture-heat whitening resistance]

One side of the adhesive film produced by the above-mentioned method was bonded to a polyethylene terephthalate film (PET100) with a thickness of 100 μm, and an adhesive film in which the PET100 substrate was bonded on one side was produced. This was cut to 50 mm in length and 40 mm in width, and was attached to a glass plate on the condition of a 2 kg roll x 2 reciprocations to make a test piece. About this test piece, the haze (%) was measured based on JISK7361-1-1997 with a nephelometer "NDH5000" (made by Nippon Denshoku Industries Co., Ltd.), and this value was made into an initial value. Next, the test piece was left to stand in an atmosphere of 85° C. and a humidity of 85% for 10 minutes, and then it was taken out, and within 10 minutes after taking it out, the turbidity meter “NDH5000” (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7361-1- Haze (%) was measured in 1997.

[Evaluation method of damp heat yellowing resistance]

One surface of the adhesive film produced by the above-mentioned method was attached to a glass plate, and one piece of release PET50 was peeled off and it was set as a test piece. About this test piece, the degree of yellowing (b*) was measured based on JISK7105-1981 using light source C, field of view 2 degrees, and a spectrophotometer "CM-5000d" (made by Konica Minolta Sensing Co., Ltd.). Moreover, after leaving the said test piece in the atmosphere of 80 degreeC and 85% of humidity for 500 hours, the degree of yellowing (b*) was measured similarly.

[Table 1]

In addition, translations in Tables 1 and 2 will be described.

ACMO: Acryloylmorpholine

NOA: n-octyl acrylate

IOA: Isooctyl acrylate

TDA: tridecyl acrylate

CHA: cyclohexyl acrylate

IBXA: Isobornyl Acrylate

It turned out that the adhesive obtained using the ultraviolet curable adhesive composition of this invention is excellent in adhesive force, heat-and-moisture whitening resistance, and heat-and-moisture yellowing resistance.

On the other hand, Comparative Example 1 was an aspect in which polyethylene glycol was not used as a raw material of urethane (meth)acrylate, and it was found that the heat-and-moisture whitening resistance was poor.

It can be seen that Comparative Example 2 does not use polyethylene glycol as the raw material of urethane (meth)acrylate and uses a large amount of ACMO with high yellowing property as the (meth)acrylic monomer. bad.

Claims (3)

1. a ultraviolet-curing adhesive composition, it is characterised in that it contains carbamate (methyl) acrylate (X), (methyl) acrylic monomer (Y) and Photoepolymerizationinitiater initiater (Z), described carbamate (methyl) acrylate (X) is Make comprise the polyhydric alcohol (a) of Polyethylene Glycol (a1), polyisocyanates (b) and there is (methyl) propylene of hydroxyl or NCO Acid based compound (c) is reacted and is obtained, and the usage amount of described Polyethylene Glycol (a1) is 1～60 matter in described polyhydric alcohol (a) The scope of amount %, the content of (methyl) acrylic monomer with nitrogen-atoms in described (methyl) acrylic monomer (Y) It is below 40 mass %.

2. ultraviolet-curing adhesive composition as claimed in claim 1, wherein, the number of described Polyethylene Glycol (a1) is divided equally Son amount is the scope of 200～5,000.

3. a binding agent, it is characterised in that it is to use the ultraviolet-curing adhesive combination described in claim 1 or 2 Thing and obtain.