TW201446918A - Ultraviolet light-curing adhesive agent composition and adhesive agent - Google Patents

Abstract

The problem to be solved by the present invention is to provide an ultraviolet light-curing adhesive agent composition with excellent adhesive strength, heat and moisture whitening resistance, and heat and moisture yellowing resistance. The present invention provides an ultraviolet light-curing adhesive agent composition containing: a urethane (meth)acrylate (X) obtained by reacting a polyol (a) including polyethylene glycol (a1), a polyisocyanate (b), and a (meth)acrylic compound (c) having a hydroxyl group or an isocyanate group; a (meth)acrylic monomer (Y); and a photopolymerization initiator (Z). The present invention also provides an adhesive agent obtained using this composition. The adhesive agent obtained using this ultraviolet light-curing adhesive agent composition can be suitably used as an adhesive agent that is used for optical members. In particular, the adhesive agent can be suitably used for manufacturing IT related products such as touch panels, liquid crystal displays, plasma displays, organic EL, personal computers, mobile phones, and the like.

Description

UV curing adhesive composition and adhesive

The present invention relates to an ultraviolet curing adhesive composition and an adhesive which are excellent in adhesion, moisture and heat whitening resistance, and moisture and heat yellowing resistance.

Acrylic adhesives have been used in a wide range of applications since. In particular, in recent years, the use of IT-related products such as thin televisions has expanded, and high performance and high performance have progressed. However, the price of IT-related products has also declined, requiring not only high performance but also high productivity.

In this case, the ultraviolet curable adhesive is highly valued because it does not require a conventional adhesive (solvent system, water system) as a solvent drying step of the necessary step, or must wait for the curing time after processing until the performance is exhibited. Etc., can expect high productivity. In addition, it is easy to increase the thickness of the adhesive layer by a binder of a conventional type, and it is expected that high performance can be expected, and development in the future is expected.

The ultraviolet-curable adhesive which can be used for the above-mentioned IT-related product, for example, the following adhesive composition is known to contain 5 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the monomer having an unsaturated double bond. A high molecular weight body having a urethane bond and having an unsaturated double bond at a polymer terminal and having a weight average molecular weight of 20,000 or more (see, for example, Patent Document 1).

However, the above-mentioned adhesive has the following problems: after the adhesive is used under moist heat conditions, if it is left at room temperature, problems such as whitening of the adhesive coating film or yellowing over time may occur. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-104296

(The subject to be solved by the invention)

An object of the present invention is to provide an ultraviolet curable adhesive composition which is excellent in adhesion, moisture and heat whitening resistance, and wet heat yellowing resistance. (method of solving the problem)

In order to solve the above problems, the inventors of the present invention have diligently studied and focused on urethane (meth) acrylate.

As a result, it has been found that the above problems can be solved by containing polyethylene glycol as an essential component of a polyol which is a raw material of a urethane (meth) acrylate, and the present invention has been completed.

That is, the present invention provides an ultraviolet curable adhesive composition characterized by comprising: a urethane (meth) acrylate (X), which is a polyol containing polyethylene glycol (a1) (a) A polyisocyanate (b), and a (meth)acrylic compound (c) having a hydroxyl group or an isocyanate group are obtained by reaction; a (meth)acrylic monomer (Y); and a photopolymerization initiator (Z). An adhesive obtained using the composition is provided. (Effect of the invention)

The adhesive obtained by using the ultraviolet curable adhesive composition of the present invention has excellent adhesion, retention, moisture and heat whitening resistance, and resistance to moist heat yellowing.

The adhesive obtained by using the ultraviolet curable adhesive composition of the present invention can be suitably used as an adhesive for use in an optical member. In particular, it is suitable for manufacturing IT related products such as touch panels, liquid crystal displays, plasma displays, organic ELs, personal computers, and mobile phones.

The ultraviolet curable adhesive composition of the present invention comprises: a urethane (meth) acrylate (X), which is a polyol (a) containing polyglycol (a1), and a polyisocyanate (b) And (meth)acrylic-based monomer (Y) obtained by reacting a hydroxyl group or an isocyanate group-containing compound (c); and a photopolymerization initiator (Z).

The polyethylene glycol (a1) improves the hydrophilicity of the ultraviolet curable adhesive composition, and can uniformly absorb moisture or moisture when the adhesive coating film is exposed to moist heat conditions, thereby contributing to The adhesive coating is resistant to whitening after moist heat. Further, by using the polyethylene glycol (a1), the amount of the (meth)acrylic monomer which is easily yellowed can be reduced or it can be used, so that the adhesion can be maintained while imparting excellent moisture resistance and yellowness. transsexual.

The polyethylene glycol (a1) is used as a raw material of the urethane (meth)acrylate (X), but a linear or branched shape can be used in consideration of adhesion, heat and whitening resistance, and resistance to moist heat yellowing. The urethane (meth) acrylate (X) may be present as a graft chain or as a block chain.

The number average molecular weight of the polyethylene glycol (a1) is preferably in the range of 200 to 5,000 from the viewpoint of further improving the moist heat whitening resistance and the resistance to moist heat yellowing, and considering the ease of reactivity control during synthesis or The range of 200 to 2,000 is better in terms of preservation stability at low temperatures, and the range of 200 to 1,000 is more desirable. Further, the number average molecular weight of the polyethylene glycol (a1) represents a ruthenium measured by a gel permeation chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Pipe column: The following pipe strings manufactured by Tosoh Corporation are connected in series. "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 Dissolution: tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (sample Standard concentration of 0.4% by mass of tetrahydrofuran solution) 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 manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation ("TK") "TSK" Standard Polystyrene F-2" "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation. "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation. "Tokyo Co., Ltd." TSKgel Standard Polystyrene F-20" "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation. "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation (Dongcao Co., Ltd.) "TSKgel Standard Polystyrene F-280" manufactured by Tosoh Corporation ("TSKgel Standard Polystyrene F-288") "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

The polyethylene glycol (a1) is preferably used in an amount of from 1 to 60% by mass in the polyol (a) from the viewpoint of further improving adhesion, retention, moisture and heat whitening resistance, and resistance to moist heat yellowing. Preferably, the range of 3 to 50% by mass is better, the range of 5 to 40% by mass is better, and the range of 10.5 to 33% by mass is particularly preferable.

Further, from the viewpoint of further improving the adhesion, retention, wet heat whitening resistance, and resistance to moist heat yellowing, the content of the aforementioned polyethylene glycol (a1) in the urethane (meth) acrylate (X) is preferably The range of 0.1 to 50% by mass is better, the range of 5 to 35% by mass is better, and the range of 9 to 25% by mass is more desirable.

The above polyol (a) which can be used other than the polyethylene glycol (a1), for example, a polyether polyol other than polyethylene glycol, a polyester polyol, a polycarbonate polyol, an acrylic polyol, and a dibutyl alcohol Alkenyl polyol and the like. These polyols may be used singly or in combination of two or more. Among these, it is preferred to use the above polyether polyol or polycarbonate polyol from the viewpoint of further improving the adhesion, the holding power, the wet heat whitening resistance, and the moist heat yellowing resistance.

The polyether polyol is obtained by, for example, adding one or more kinds of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to a compound having two or more active hydrogens. The product, or the polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, the modified polytetramethylene glycol synthesized by copolymerization of tetrahydrofuran and alkyl-substituted tetrahydrofuran, or the copolymerization of neopentyl glycol and tetrahydrofuran Polytetramethylene glycol and the like.

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-propanediol, dipropylene glycol, or tripropylene glycol can be used. 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 a lower molecular weight dihydroxy compound such as methyl-1,8-octanediol, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-bisphenol; 1,2-cyclobutane Glycol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, 1,4-cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclic [5,2,1,0,2,6]decane-dimethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,1] Dialkyl glycol, bicyclo[4,3,0]decane dimethanol Tricyclo[5,3,1,1]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1]dodecyl alcohol, spiro[3,4]octanediol, butylcyclohexane Alicyclic polyols such as diol, 1,1'-biscyclohexylene glycol, cyclohexanetriol, hydrogenated bisphenol A, 1,3-adamantanediol; polyethylene glycol, polypropylene glycol, polytetrazol A polyether polyol such as methyl glycol; a polyester polyol such as polyhexamethylene adipate, polyhexamethylene succinate or polycaprolactone.

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 more preferably in the range of 500 to 1,500. Further, the number average molecular weight of the polyether polyol is measured in the same manner as the number average molecular weight of the polyethylene glycol (a1).

The polycarbonate polyol can be obtained, for example, by reacting a carbonate and/or phosgene with a compound having two or more active hydrogens.

As the above carbonate, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, diphenyl carbonate or 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 adhesion. Further, the hydroxyl value of the above polycarbonate polyol represents the enthalpy measured in accordance with JIS K0070-1992.

As the polyisocyanate (b), for example, an aromatic diisocyanate such as xylene diisocyanate, phenyl diisocyanate, methylphenyl diisocyanate, diphenylmethane diisocyanate or naphthalene diisocyanate; hexamethylene group can be used; Diisocyanate, diazonic acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanoxymethylcyclohexane, tetramethyl arylene A diisocyanate having an aliphatic or alicyclic structure such as toluene diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion, retention, and resistance to dampness and heat yellowing, it is preferred to use a diisocyanate having an alicyclic structure, and 4,4'-dicyclohexylmethane diisocyanate or isophorone is used. Diisocyanate, cyclohexane diisocyanate, diisocyanate methylcyclohexane are more preferred.

The (meth)acrylic compound (c) having a hydroxyl group or an isocyanate group is used for introducing a (meth)acrylonitrile group into the urethane (meth)acrylate (X).

The above-mentioned (meth)acrylic compound having a hydroxyl group which can be used as the above compound (c), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl acrylate a hydroxyl (meth)acrylic acid alkyl ester such as ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl acrylate or hydroxyethyl acrylamide; Hydroxy-terminated poly(meth)acrylates such as methylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate; polyethylene glycol monoacrylate , polypropylene glycol monoacrylate, and the like. Among these, from the viewpoint of improving the curability by ultraviolet rays, it is preferable to use an acrylic compound having a hydroxyl group, and it is preferable to use a hydroxyl group from the viewpoint of easiness in obtaining raw materials, improvement in curability and adhesion properties. The alkyl acrylate is more preferably used, and 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate is particularly preferred.

Further, as the (meth)acrylic compound having an isocyanate group which can be used as the compound (c), for example, 2-(meth)acryloxyethyl isocyanate or 2-(2-(methyl)) can be used. Acryloxyethoxy)ethyl isocyanate, 1,1-bis((meth)acryloxymethyl)ethyl isocyanate, and the like. Among these, from the viewpoint of easiness of obtaining raw materials, 2-(meth)acryloxyethyl isocyanate is preferred, and 2-propenyloxyethyl isocyanate is more preferred.

When a (meth)acrylic compound having a hydroxyl group is used as the compound (c), the method for producing the urethane (meth)acrylate (X) may be the following method, for example, the solvent is used as described above. After the polyol (a) and the (meth)acrylic compound (c) are added to the reaction system, the polyisocyanate (b) is supplied and mixed, and reacted to produce the same, or the above-mentioned plural is obtained without a solvent. The alcohol (a) is reacted with the polyisocyanate (b) to obtain a urethane prepolymer having an isocyanate group, and secondly, the (meth)acrylic compound (c) having a hydroxyl group is supplied, mixed, and reacted. In terms of manufacturing methods, etc. It is preferred that the above reaction be carried out at a temperature of from 20 to 120 ° C for about 30 minutes to 24 hours.

Further, in the case where a (meth)acrylic compound having an isocyanate group is used as the compound (c), the method for producing the urethane (meth) acrylate (X) may be, for example, in the absence of a solvent. Adding the aforementioned polyol (a) and the above polyisocyanate (b) to react to obtain a urethane prepolymer having a hydroxyl group, and secondly, supplying the aforementioned (meth)acrylic compound (c) having an isocyanate group, A method of mixing, reacting, and the like. The above reaction is preferably carried out at a temperature of from 20 to 120 ° C for about 30 minutes to 24 hours.

The production of the urethane (meth) acrylate (X) described above can also be carried out in the presence of an organic solvent or an aqueous medium. Further, it may be produced in the presence of a (meth)acrylic monomer (Y) to be described later without using an organic solvent or an aqueous medium.

The reaction of the polyol (a) with the polyisocyanate (b) and the (meth)acrylic compound (c), the hydroxyl group possessed by the polyol (a) and the (meth)acrylic compound (c) The total amount of the hydroxyl groups possessed, and the equivalent ratio of the isocyanate groups possessed by the polyisocyanate (b) [the total amount of isocyanate groups/hydroxy groups] = 0.75 to 1 is controlled, and the obtained carbamate (methyl group) is controlled. The molecular weight of the acrylate (X) is ideal, and the range of 0.79 to 0.995 is better. Further, when the equivalent ratio exceeds 1, the reaction can be carried out. However, in order to inactivate the isocyanate group of the urethane (meth) acrylate (X), it is preferred to use an alcohol such as methanol. In this case, the hydroxyl group possessed by the polyol (a) and the hydroxyl group possessed by the (meth)acrylic compound (c) and the hydroxyl group possessed by the alcohol, and the equivalent ratio of the polyisocyanate group (isocyanate group / hydroxyl group) It is desirable to adjust to the above range.

Further, in order to use the alcohol used for the isocyanate group of the urethane (meth) acrylate (X), for example, a monofunctional alcohol such as methanol, ethanol, propanol or butanol, or 1,2-propanediol or A bifunctional alcohol composed of a first-order and a second-order hydroxyl group such as 1,3-butanediol.

Further, when the urethane (meth) acrylate (X) is produced, a polymerization inhibitor or an urelate catalyst or the like may be used as needed.

The aforementioned polymerization inhibitors, for example, 3,5-bis-tert-butyl-4-hydroxytoluene, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), p-tert-butyl tea Phenol methoxy phenol, 2,6-di-t-butyl cresol, phenothi- sulphate, tetramethyl thiuram disulfide, diphenylamine, dinitrobenzene, and the like.

As the urethane-based catalyst, for example, a nitrogen-containing compound such as triethylamine, triethylenediamine or N-methyl porphyrin, a metal salt such as potassium acetate, zinc stearate or tin octylate, or a dibutyl group can be used. An organometallic compound such as tin laurate or zirconium tetrakisylpyruvate.

The urethane (meth) acrylate (X) has a (meth) acrylonitrile group which undergoes radical polymerization by light irradiation or heating. In view of the fact that the adhesion or the followability of the height difference can be further improved, the equivalent of the (meth)acryl fluorenyl group is preferably in the range of 1,000 to 200,000 g/eq., and the range of 5,000 to 100,000 g/eq. is more preferable. . Further, the equivalent of the (meth)acrylonitrile group is obtained by dividing the total mass of the polyol (a) and the polyisocyanate (b) and the (meth)acrylic compound (d) by the aforementioned carbamate ( The equivalent of the (meth)acrylic group present in the methyl acrylate (X) is obtained. In the present invention, the "(meth)acrylic compound" means one or both of a methacrylic compound and an acrylic compound, and "(meth)acrylate" means methacrylate and acrylic acid. One or both of the esters, "(meth)acrylonitrile" means one or both of a methacryloyl group and an acryl group, and "(meth)acrylic" means methacrylic acid and One or both of acrylic acid, "(meth)acrylic monomer" means one or both of a methacrylic monomer and an acrylic monomer.

The weight average molecular weight of the urethane (meth) acrylate (X) is preferably in the range of 5,000 to 200,000 from the viewpoint of achieving excellent adhesion and retention and imparting good coating workability. The range of 10,000 to 100,000 is more ideal. Further, the weight average molecular weight of the urethane (meth) acrylate (X) represents a ruthenium obtained by measuring the same as the number average molecular weight of the polyethylene glycol (a1).

As the (meth)acrylic monomer (Y), for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, or isopropyl (meth)acrylate can be used. Butyl (meth)acrylate, second butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-amyl (meth)acrylate, (A) Ethyl acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate , 3-methylbutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, (A) An aliphatic (meth) acrylate such as neopentyl acrylate, hexadecyl (meth) acrylate or isoamyl (meth) acrylate; isodecyl (meth) acrylate or cyclomethacrylate Alicyclic (meth) acrylate such as ester, tetrahydrofuran (meth) acrylate; 3-methoxybutyl (meth) acrylate), 2-methoxyethyl (meth) acrylate, (methyl) ) 3-methoxypropyl acrylate, (meth) propylene 2-methoxybutyl acrylate, oxyethylene, methoxypolyethylene glycol acrylate, ethoxy diethylene glycol (meth) acrylate, carbene in the range of 1 to 15 Ethyl (meth) acrylate such as ethyl alcohol (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy (meth) acrylate a hydroxyl group-containing (meth) acrylate such as butyl ester; benzyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol acrylate, An aromatic (meth) acrylate such as phenyl (meth) acrylate or 2-hydroxy-3-phenoxypropyl (meth) acrylate; (meth) acrylamide, dimethyl (meth) propylene Indoleamine, acrylonitrile porphyrin, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, hydroxyethyl (A A (meth)acrylic monomer having a nitrogen atom such as acrylamide or diacetone (meth) acrylamide. These (meth)acrylic monomers may be used singly or in combination of two or more.

In addition, in order to provide excellent moisture heat whitening resistance, the (meth)acrylic monomer (Y) may be a (meth)acrylic monomer having a nitrogen atom. In this case, since the moisture-resistant heat yellowing may be lowered, it is preferably added in a small amount, and the total amount of the (meth)acrylic monomer (Y) is preferably 40% by mass or less, more preferably 35% by mass or less. . In the present invention, since the hydrophilicity of the adhesive coating film can be improved by using the polyethylene glycol (a1), it is possible to exhibit moist heat whitening resistance in a small amount.

The amount of the (meth)acrylic monomer (Y) to be used is preferably in the range of 30 to 200 parts by mass based on 100 parts by mass of the urethane (meth)acrylate (X). Preferably, the range of 50 to 150 parts by mass is more preferably, and the range of 70 to 130 parts by mass is particularly preferable.

The photopolymerization initiator (Z) is a radical generated by light irradiation or heating, and the aforementioned urethane (meth) acrylate (X) or the aforementioned (meth) acryl monomer (Y) The initiator of free radical polymerization.

The photopolymerization initiator (Z), for example, 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-(2-hydroxyethoxy)-phenyl (2 -hydroxy-2-propyl)one, 2-methyl-[4-(methylthio)phenyl]-2-oxalino-1-propanone, 2,2-dimethoxy-2-phenyl Acetophenone compound such as acetophenone; benzoin, benzoin methyl ether, benzoin isoether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; diphenyl ketone, benzene Mercaptobenzoic acid, methyl benzylidenebenzoate, 4-phenyldiphenyl ketone, hydroxydiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3, Diphenyl ketone compound such as 3'-dimethyl-4-methoxydiphenyl ketone; thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthene a thioxanthone compound such as a ketone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone or 2,4-diisopropylthioxanthone; 4'-dimethylamino thioxanthone (alias = michler's ketone), 4,4'-diethylaminodiphenyl Anthracene compounds such as ketone, α-mercaptodecyl ester, benzil, methyl benzhydrazide (“Vicure 55”), 2-ethylhydrazine; 2, 4, 6 Sulfhydryl oxidation such as trimethylbenzhydryldiphenylphosphine oxide ("Lucirin TPO") or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide ("IRGACURE 819") Phosphine compound; 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone ["BTTB" manufactured by Nippon Oil & Fats Co., Ltd.], benzoated diphenyl ketone, and the like.

The photopolymerization initiator (Z) is preferably 2-hydroxy-2-methyl-1-phenylpropan-1-one from the viewpoint of further improving the adhesion, retention, moisture resistance, heat yellowing resistance, and hardenability. 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethyl benzhydryl diphenyl phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide good.

The amount of the photopolymerization initiator (Z) to be used is preferably from 0.1 to 20 parts by mass, and from 0.5 to 15 parts by mass, per 100 parts by mass of the urethane (meth)acrylate (X). The range is better, and the range of 1 to 5 parts by mass is particularly preferable.

The ultraviolet curable adhesive composition of the present invention contains the urethane (meth) acrylate (X), the (meth) acryl monomer (Y), and the photopolymerization initiator (Z) described above. As an essential component, it may contain other additives as needed.

As the other additives, for example, a decane coupling agent, an antioxidant, a photostabilizer, a solvent, a rust inhibitor, a thixotropic agent, a sensitizer, a polymerization inhibitor, a leveling agent, an adhesion-imparting agent, and an antistatic agent can be used. Agent, flame retardant, etc. Among these, it is preferable to contain a decane coupling agent from the viewpoint of improving the performance of the adhesive after heat and humidity resistance. Further, from the viewpoint of further improving the resistance to moisture, heat and yellowing, it is preferred to contain an antioxidant and a photostabilizer.

As the aforementioned decane coupling agent, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyl group can be used. a decane coupling agent having an epoxy group such as methyl diethoxy decane or 3-glycidoxy propyl methyl dimethoxy decane; 2-(3,4-epoxycyclohexyl)ethyl three Ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxydecane, 2-(3 , 4-epoxycyclohexyl)ethylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)propane Methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)propyltriethoxydecane, 2-(3,4-epoxycyclohexyl)propylmethyldiethoxydecane a decane coupling agent having an alicyclic epoxy group; vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, p-styryl trimethoxy decane, 3-methyl propylene oxime Propylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethyl Baseline, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxy A decane, an anthranyl alkoxy oligomer or the like. These decane coupling agents may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion after moisture and heat resistance, etc., it is preferred to use an epoxy group-containing decane coupling agent or an alicyclic epoxy group-containing decane coupling agent, and it is preferably selected from 2 -(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxy One or more of the group consisting of decane and 3-glycidoxypropyltriethoxydecane is more preferable.

The amount of the decane coupling agent used is from 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth) acrylate (X) from the viewpoint of further improving the adhesion after moisture and heat resistance. Preferably, the range of 0.05 to 5 parts by mass is better, and the range of 0.05 to 1 part by mass is more desirable.

As the antioxidant, a hindered phenol compound (primary antioxidant) which traps a radical generated by thermal deterioration, a phosphorus compound which decomposes by a peroxide which is thermally degraded, a sulfur compound (secondary antioxidant), or the like can be used.

The aforementioned hindered phenol compound, for example, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4hydroxyphenyl)propionate], 肆[3-(3,5-di) -Pentaerythritol ester of tert-butyl-4-hydroxyphenyl)propionate, octadecyl [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, thiodiethylidene [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], phenylpropanate-3,5-bis(1,1-dimethylethyl)-4-hydroxyl -C ₇ -C ₉ side alkanoate, 4,6-bis(dodecylthiomethyl)-o-cresol, reaction product of N-phenylaniline and 2,4,4-trimethylpentene, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 3,9-bis[2-[3-( Third butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane , 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,5-di-third Amyl hydroquinone and the like.

The aforementioned phosphorus compound, for example, triphenylphosphine, bis(2,4-di-t-butyl-6-methylphenyl)=ethyl=phosphite, triphenyl phosphite, decylphenyl Phosphite, ginseng (2,4-dibutylphenyl) phosphite, ginseng (2,4-dibutyl-5-methylphenyl) phosphite, ginseng [2-tert-butyl- 4-(3-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite , decyl phosphite, octyl diphenyl phosphite, bis(indenyl)monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphoric acid 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-diisopropylphenylphenyl)pentaerythritol diphosphite, tetrakis(trisyl)isopropylidene diphenol diphosphite, Tetrakis(tridecyl)-4,4'-n-butylene bis(2-butyl-5-methylphenol) diphosphite, tert-trisyl-1,1,3-parade (2- Methyl-4-hydroxy-5-butylphenyl)butane triphosphorous acid , (2,4-dibutylphenyl)biphenyldiphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 2'-methylenebis(4,6-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-butylphenyl)-octadecyl Phosphite, 2,2'-ethylenebis(4,6-dibutylphenyl)fluorophosphite, ginseng (2-[(2,4,8,10-decylbutyldibenzo[ d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 2-ethyl-2-butylpropanediol and 2,4,6 - a phosphite of tributyl phenol or the like.

As the sulfur compound, for example, di(t-dodecyl) 3,3'-thiopropionate, dilauryl 3,3'-thiodipropionate, dilauryl thiodisulfide, 3,3 can be used. '-Di(tridecyl) thiodipropionate, bis(myristyl) 3,3'-thiodipropionate, bis(stearyl) 3,3'-thiodipropionate, hydrazine- Methylene-3-lauryl thiopropionate methane, 3,3'-methyl-3,3'-thiodipropionate bis(stearyl)ester, 3,3'-thiodipropionate lauryl Stearyl ester, bis[2-methyl-4-(3-n-alkylthiopropoxy)-5-tert-butylphenyl] sulfide, β-lauryl thiopropionate, 2-mercapto Benzimidazole, 2-mercapto-5-methylbenzimidazole, 3,3'-thiodipropionate di(octadecyl) ester, and the like.

Among these, it is preferred to use a phosphorus compound from the viewpoint of further improving the adhesion and moisture-resistant heat yellowing, and is selected from the group consisting of triphenylphosphine and bis(2,4-di-tert-butyl-6). More preferably, one or more antioxidants in the group consisting of -methylphenyl)=ethyl = phosphite and ginseng (2,4-di-tert-butylphenyl) phosphite are preferred. Triphenylphosphine, bis(2,4-di-tert-butyl-6-methylphenyl)=ethyl = phosphite was used.

The amount of the antioxidant to be used is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth)acrylate (X) from the viewpoint of further improving the resistance to moisture and heat yellowing.

The light stabilizer is trapped in a radical generated by photodegradation, and for example, a radical scavenger such as a thiol compound, a thioether compound or a hindered amine compound, or a UV absorption such as a diphenyl ketone compound or a benzoate compound can be used. Agents, etc. Among these, it is preferable to use a hindered amine compound from the viewpoint of further improving the resistance to moist heat yellowing.

As the hindered amine compound, for example, cyclohexane and N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro 1,3,5 can be used. a reaction product of a trihydric reaction product with 2-aminoethanol, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) decanoic acid, a hindered amine compound having an amine ether group such as a reaction product of 1,1-dimethylethyl hydrogen peroxide and octane; N-ethylindolyl-3-dodecyl-1-(2,2,6,6 N-ethinyl hindered amine compound such as tetramethyl-4-piperidinylpyrrolidine-2,5-dione; bis(1,2,2,6,6-pentamethyl-4-piperidin Pyridyl)=decanedione, 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-tetramethylper Alkene polycondensate, N-alkyl group of [{4-methoxyphenyl}methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) malonate Hindered amine compounds and the like.

The amount of the photo-stabilizer to be used is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth)acrylate (X), from the viewpoint of further improving the resistance to moisture and heat yellowing.

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 viewpoints of good coatability and handling of the adhesive solution at the time of coating, 1,000 The range of ~15,000mPa·s is more ideal. Further, the viscosity was measured at 25 ° C using a B-type viscometer.

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

The method for curing the ultraviolet curable adhesive composition of the present invention can be irradiated with a predetermined ultraviolet ray by using a known ultraviolet light irradiation device such as a xenon lamp, a krypton-mercury lamp, a metal halide lamp, a high pressure mercury lamp or a low pressure mercury lamp. hardening.

Irradiation of the ultraviolet ray is preferably 0.05 ~ 5J / cm ^2, more preferably 0.1 ~ 3J / cm ^2, particularly preferably the range of 0.3 ~ 1.5J / cm ² of. In addition, the amount of ultraviolet ray irradiation was measured using a UV checker UVR-N1 (manufactured by GS Yuasa Co., Ltd.) in the wavelength range of 300 to 390 nm.

As a substrate on which the ultraviolet curable adhesive composition of the present invention can be applied and an adhesive layer is formed, a plastic substrate, a flexible printed substrate, a glass substrate, and a vapor-deposited substrate can be used. A substrate of ITO or the like.

As the plastic substrate, a substrate made of an acrylic resin or the like which is generally used, or PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE ( Polyphenylene ether), PET (polyethylene terephthalate), COP (cycloolefin polymer), TAC (triethyl fluorenyl cellulose) or anti-reflective film, antifouling film, transparent to form a touch panel a film of a conductive film or the like. [Examples]

The invention is described in more detail below using examples.

[Synthesis Example 1] <Synthesis of urethane acrylate (X-1)> Polytetramethylene glycol (number average molecular weight) was added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, and a thermometer; 1,000, hereinafter referred to as "PTMG1000") 410 parts by mass, polyethylene glycol (quantitative average molecular weight; 400, hereinafter abbreviated as "PEG-1") 27.5 parts by mass, 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") 6.1 parts by mass, 2 parts by mass of 2,6-di-t-butyl cresol, and 0.3 parts by mass of p-methoxyphenol. After the temperature in the reaction vessel was raised to 40 ° C, 105 parts by mass of isophorone diisocyanate (hereinafter abbreviated as "IPDI") was added. Then, 0.1 part by mass of dioctyltin dicaptanate was added, and the temperature was raised to 80 ° C for 1 hour. Thereafter, the mixture was kept at 80 ° C for 12 hours, and after confirming that all of the isocyanate groups had disappeared, the urethane acrylate (X-1) was obtained by cooling. The obtained urethane acrylate (X-1) and the acrylonitrile group had an equivalent weight of 10,441 (the decimal point was rounded off. The 2-hydroxyethyl acrylate had a molecular weight of 116.1. The same applies hereinafter), and the weight average molecular weight was 30,000.

[Synthesis Example 2] <Synthesis of urethane acrylate (X-2)> A polycarbonate polyol ("Duranol T-5651") was added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer. Asahi Kasei Chemicals Co., Ltd., number average molecular weight; 1000) 390 parts by mass, polyethylene glycol (quantitative average molecular weight; 600, hereinafter referred to as "PEG-2") 43.4 parts by mass, HEA 9 parts by mass, 2,6-two 2 parts by mass of t-butyl cresol and 0.3 parts by mass of p-methoxyphenol. The temperature was raised until the temperature in the reaction vessel became 40 ° C, and then 102 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dicaptanate was added, and the temperature was raised to 80 ° C in 1 hour. Thereafter, the mixture was kept at 80 ° C for 12 hours, and it was confirmed that all the isocyanate groups disappeared, and then cooled to obtain a urethane acrylate (X-2). The acrylamide group of the obtained urethane acrylate (X-2) had an equivalent weight of 7,023 and a weight average molecular weight of 19,000.

[Synthesis Example 3] <Synthesis of urethane acrylate (X-3)> 351 parts by mass of PTMG1000 and 51.4 parts by mass of PEG- were added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer. 1. 5.7 parts by mass of HEA, 2 parts by mass of 2,6-di-t-butyl cresol, and p-methoxyphenol 0.3 parts by mass. The temperature was raised until the temperature in the reaction vessel became 40 ° C, and then 104 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dicaptanate was added, and the temperature was raised to 80 ° C in 1 hour. Thereafter, the mixture was kept at 80 ° C for 12 hours, and it was confirmed that all the isocyanate groups disappeared, and then cooled to obtain a urethane acrylate (X-3). The acrylamide group of the obtained urethane acrylate (X-3) had an equivalent weight of 10,431 and a weight average molecular weight of 21,000.

[Synthesis Example 4] <Synthesis of urethane acrylate (X-4)> Add polypropylene glycol to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer (quantitative average molecular weight; 3,000, hereinafter referred to as "PPG3000") 180 parts by mass, 143 parts by mass of PTMG1000, 109 parts by mass of PEG-1, 6 parts by mass of HEA, 2 parts by mass of 2,6-di-t-butyl cresol, 0.3 parts by mass of p-methoxy Phenolic. After the temperature in the reaction vessel was raised to 40 ° C, 105 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dicaprate was added, and the temperature was raised to 80 ° C in 1 hour. Thereafter, the mixture was kept at 80 ° C for 12 hours, and it was confirmed that all of the isocyanate groups disappeared, and the urethane acrylate (X-4) was obtained by cooling. The acrylamide group of the obtained urethane acrylate (X-4) had an equivalent weight of 10,507 and a weight average molecular weight of 26,000.

[Synthesis Example 5] <Synthesis of urethane acrylate (X-5)> 442 parts by mass of Duranol T-5652, polyethylene glycol was added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer. ("Ymer N120" manufactured by Perstorp Co., Ltd., number average molecular weight; 1,000) 246 parts by mass, HEA 9.5 parts by mass, 2,6-di-t-butyl cresol 2 parts by mass, and p-methoxyphenol 0.3 parts by mass. The temperature was raised until the temperature in the reaction vessel became 40 ° C, and then 102 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dicaptanate was added, and the temperature was raised to 80 ° C in 1 hour. Thereafter, the mixture was kept at 80 ° C for 12 hours, and after confirming that all of the isocyanate groups had disappeared, the urethane acrylate (X-5) was obtained by cooling. The acrylamide group of the obtained urethane acrylate (X-5) had an equivalent weight of 9,771 and a weight average molecular weight of 20,000.

[Synthesis Example 6] <Synthesis of urethane acrylate (X-6)> 467 parts by mass of Duranol T-5651 and 9.6 parts by mass were added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer. 2 parts by mass of HEA, 2,6-di-t-butyl cresol, and 0.3 parts by mass of p-methoxyphenol. After the temperature in the reaction vessel was raised to 40 ° C, 101 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dicaprate was added, and the temperature was raised to 80 ° C in 1 hour. Thereafter, the mixture was kept at 80 ° C for 12 hours, and after confirming that all of the isocyanate groups had disappeared, the urethane acrylate (X-6) was obtained by cooling. The acrylamide group of the obtained urethane acrylate (X-6) had an equivalent weight of 6,985 and a weight average molecular weight of 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 were added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer. 2 parts by mass of 6-di-t-butyl cresol and 0.3 parts by mass of p-methoxyphenol. After the temperature was raised to 40 ° C in the reaction vessel, 105 parts by mass of IPDI was added. Then, 0.1 part by mass of dioctyltin dicaprate was added, and the temperature was raised to 80 ° C in 1 hour. Thereafter, the mixture was kept at 80 ° C for 12 hours, and after confirming that all of the isocyanate groups had disappeared, the urethane acrylate (X-7) was obtained by cooling. The acrylamide group of the obtained urethane acrylate (X-7) had an equivalent weight of 10,208 and a weight average molecular weight of 22,000.

[Example 1] <Preparation of ultraviolet curable adhesive composition> 100 parts by mass of the above-mentioned urethane acrylate (X-1) and butyl acrylate were placed in a reaction vessel equipped with a stirrer, a reflux cooling tube, and a thermometer. 105 parts by mass of an ester (hereinafter abbreviated as "BA") and 10 parts by mass of dimethyl methacrylamide (hereinafter abbreviated as "DMAA") were stirred at 80 ° C until uniform. After cooling at room temperature, 3 parts by mass of 2,4,6-trimethylbenzimidylphenylphosphine oxide and bis(2,2,6,6-tetramethyl-1) decanedioic acid were added with stirring. 0.5 parts by mass of (octyloxy)-4-piperidinyl) ester, 0.5 parts by mass of triphenylphosphine, 0.1 parts by mass of 3-glycidoxypropyltriethoxydecane, and stirred until uniformized . Thereafter, it was filtered through a 200 mesh metal mesh to obtain an ultraviolet curable adhesive composition.

[Examples 2 to 6 and Comparative Examples 1 and 2] The types and amounts of the urethane (meth) acrylate and (meth) acryl monomer used were changed as shown in Table 1, and In the same manner as in Example 1, an ultraviolet curable adhesive composition was obtained.

[Method for Producing Adhesive Film] The surface of the polyethylene terephthalate film (released PET 50) having a thickness of 50 μm which was subjected to release treatment on the surface was coated with the ultraviolet curable adhesive obtained in the examples and the comparative examples. The film fat composition was such that the film thickness after UV irradiation was 175 μm, and the release PET 50 was bonded. Thereafter, the ultraviolet light was irradiated with a UV irradiation device so that the cumulative light amount of the wavelength of the UV-A region after the release of the release PET 50 was 1 J/cm ² to form an adhesive film.

[Method for Measuring Adhesive Strength] The single side of the adhesive film prepared by the above method was bonded to a polyethylene terephthalate film (PET75) having a thickness of 75 μm to form a PET75 base on one side. Adhesive film. This was cut into a width of 25 mm and used as a test piece. The test piece was attached to a glass plate or a polycarbonate (PC) plate which is a bonded body in a 2 kg roll × 2 times. One hour after the attachment, the 180-degree peel strength was measured in a gas atmosphere at 23 ° C and a humidity of 50%, and was defined as the adhesion.

[Evaluation Method of Moisture-Resistant Whitening Property] The single-sided surface of the adhesive film prepared by the above method was bonded to a polyethylene terephthalate film (PET100) having a thickness of 100 μm to prepare a PET 100-based film on one side. Bonding film. The test piece was cut into a length of 50 mm and a width of 40 mm, and the glass plate was attached to the glass plate twice with 2 kg rolls. This test piece was measured for haze (%) by a turbidity meter "NDH5000" (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361-17-1, and the enthalpy was used as the initial enthalpy. Then, the test piece was taken out in a gas atmosphere at 85 ° C and a humidity of 85% for 10 minutes, and taken out, and the NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used in accordance with JIS K7361-1 within 10 minutes after the removal. -1997 Determination of haze (%).

[Evaluation Method of Moisture-Resistant Yellow Degeneration] One side of the adhesive film prepared by the above method was attached to a glass plate, and another one of the release PET 50 was peeled off as a test piece. The test piece was measured for yellowness (b*) in accordance with JIS K7105-1981 by a light source C, a field of view of 2°, and a spectrophotometer "CM-5000d" (manufactured by Konica Minolta sensing Co., Ltd.). Further, the test piece was allowed to stand in a gas atmosphere at 80 ° C and a humidity of 85% for 500 hours, and then the yellowing degree (b*) was measured in the same manner.

【Table 1】

Also, the translations in Tables 1 and 2 are explained. ACMO; acrylonitrile porphyrin NOA; n-octyl acrylate IOA; isooctyl acrylate TDA; tridecyl acrylate CHA; cyclohexyl acrylate IBXA; isodecyl acrylate

It is understood that the adhesive obtained by using the ultraviolet curable adhesive composition of the present invention is excellent in adhesion, wet heat whitening resistance, and moist heat yellow resistance.

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

In Comparative Example 2, polyethylene glycol was not used as a raw material of the urethane (meth) acrylate, and a large amount of ACMO having a high yellowing property was used as the (meth)acrylic monomer, and the wet heat yellowing resistance was poor.

no

Claims (5)

An ultraviolet curing adhesive composition characterized by comprising: a urethane (meth) acrylate (X), a polyol (a) containing polyethylene glycol (a1), and a polyisocyanate (b) And a (meth)acrylic-based compound (c) obtained by reacting a hydroxyl group or an isocyanate group; (meth)acrylic monomer (Y); and a photopolymerization initiator (Z). The ultraviolet curable adhesive composition according to claim 1, wherein the polyethylene glycol (a1) has a number average molecular weight of 200 to 5,000. The ultraviolet curable adhesive composition according to the first aspect of the invention, wherein the polyethylene glycol (a1) is used in an amount of from 1 to 60% by mass in the polyol (a). The ultraviolet curable adhesive composition according to the first aspect of the invention, wherein the (meth)acrylic monomer having a nitrogen atom in the (meth)acrylic monomer (Y) is 40 mass %the following. An adhesive agent obtained by using the ultraviolet curable adhesive composition according to any one of claims 1 to 4.