CN103540288A - Resin composition for uv-cured adhesive and adhesive - Google Patents

Abstract

The problem to be solved by the present invention is to provide a resin composition for an ultraviolet curable adhesive that has excellent properties such that no peeling occurs over time with respect to substrates made of various materials. Adhesive force and excellent yellowing resistance. Therefore, the present invention provides a resin composition for ultraviolet curable adhesives, which is characterized in that it contains polyol (a), polyisocyanate (b) and (meth)acrylic compound (c) having a hydroxyl group. In the ultraviolet curable adhesive resin composition of the urethane (meth)acrylate resin (A) obtained by reaction, (meth)acrylic monomer (B), and the photopolymerization initiator (C), there is also The light stabilizer (D) and antioxidant (E) are contained in the range of 95/5-5/95 by mass ratio.

Description

Resin composition for ultraviolet curable adhesive and adhesive

technical field

The present invention relates to a resin composition for an ultraviolet curable adhesive and an adhesive having excellent adhesive force and yellowing resistance.

Background technique

In optics-related products represented by touch panels and liquid crystal displays, many optical members having various types of materials and shapes are used along with their high functionality.

Adhesives have been conventionally used for lamination of optical members as described above, but the industry needs an adhesive having excellent adhesive force regardless of the material or shape of parts.

In addition, in the manufacture of the aforementioned optical-related products, in recent years, improving the productivity of final products has become a major issue. This is due to the following reasons: the adhesives that have been used in the past usually contain solvents such as solvents and water. Therefore, after applying the adhesive to the surface of a substrate, etc., A large amount of time is required in the process, which becomes a cause of lowering the production efficiency of the final product.

As an adhesive that can improve the production efficiency of the above-mentioned products, an ultraviolet curable adhesive is known. The above-mentioned ultraviolet-curable adhesive is characterized in that it generally does not contain solvents such as solvents and water, and therefore does not require a step of removing these solvents when forming the adhesive layer.

As an adhesive that has such a level of adhesive force that can be used in the manufacture of the above-mentioned products and the like, and can improve the production efficiency of the final product compared with conventional ones, for example, the following adhesive composition is known, that is, the The adhesive composition is characterized by containing, with respect to 100 parts of monomers having an unsaturated double bond, a monomer having a weight average molecular weight of 20,000 or more having a urethane bond and an unsaturated double bond at a polymer terminal. 5 mass parts or more and 200 mass parts or less of high molecular weight body (for example, refer patent document 1.)

However, the above-mentioned pressure-sensitive adhesive composition may not exhibit sufficient adhesive force for practical use depending on the material of the substrate, and may cause peeling over time depending on the material and shape of the substrate. Dislocation of the substrate caused by lateral forces on the surface of the substrate, or yellowing over time.

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 invention

The problem to be solved by the present invention is to provide a resin composition for an ultraviolet curable adhesive that has a level that does not cause peeling over time to substrates made of various materials. Excellent adhesion and excellent yellowing resistance.

method used to solve the problem

The inventors of the present invention have focused on the types of additives while conducting intensive studies to solve the above-mentioned problems.

As a result, it discovered that the adhesive agent excellent in adhesive force and anti-yellowing property can be obtained by containing a light stabilizer and an antioxidant in a specific ratio.

That is, the present invention provides an ultraviolet curable adhesive resin composition characterized in that it contains polyol (a), polyisocyanate (b) and a (meth)acrylic compound (c) having a hydroxyl group. In the ultraviolet curable adhesive resin composition of the urethane (meth)acrylate resin (A) obtained by reaction, (meth)acrylic monomer (B), and the photopolymerization initiator (C), there is also The light stabilizer (D) and the antioxidant (E) are contained in the range of 95/5-5/95 in terms of mass ratio; the present invention also provides an adhesive.

The effect of the invention

The adhesive obtained by using the resin composition for ultraviolet-curable adhesives of this invention is a material which has excellent adhesive force and holding power, and is excellent in yellowing resistance. In particular, yellowing resistance (light yellowing resistance, heat yellowing resistance) is excellent even after prolonged light exposure or heat exposure.

The adhesive obtained using the resin composition for ultraviolet-curable adhesives of this invention can be used suitably as an adhesive used for an optical member. In particular, it can be favorably used in the production of touch panels, liquid crystal displays, plasma displays, organic EL, personal computers, mobile phones, and the like.

Detailed ways

First, the urethane (meth)acrylate resin (A) used in the present invention will be described.

Examples of the above-mentioned polyol (a) include polyester polyol, polyether polyol, polycarbonate polyol, polyacrylic polyol, polybutadiene polyol, etc., and these may be used alone or in combination. 2 or more. Among them, polyether polyols and polycarbonate polyols are preferably used from the viewpoint of further improving adhesive strength, holding power, step followability, whitening resistance, and the like.

Examples of the above polyether polyol include polyaddition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide with a compound having two or more active hydrogens. The products obtained are polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, modified polytetramethylene glycol obtained by copolymerizing tetrahydrofuran and alkyl-substituted tetrahydrofuran, and modified polytetramethylene glycol obtained by copolymerizing neopentyl glycol and tetrahydrofuran. diol, etc.

Examples of the compound having two or more active hydrogens include 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 Alcohol, 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- Propylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol Alcohol, 2-methyl-1,8-octanediol, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-bisphenol and other dihydroxy compounds with relatively low molecular weight, 1 , 2-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, 1,4-cyclohexanedimethanol, hydroxypropyl cyclo Hexanol, tricyclo[5,2,1,0,2,6]decane-dimethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3 , 1,1] dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecane-diethanol, hydroxypropyl tricyclo[5 , 3,1,1] dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol (1,1'-Bicyclohexylidenediol), cyclohexanetriol , hydrogenated bisphenol A, 1,3-adamantane diol and other alicyclic polyols, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and other polyether polyols, polyhexamethylene adipate, polybutylene Polyester polyols such as hexanediol dioate and polycaprolactone.

Among them, it is more preferable to use an aliphatic polyether polyol, and it is particularly preferable to use polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran from the viewpoint of being able to impart good adhesive properties.

The number average molecular weight of the polyether polyol is preferably in the range of 500 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 is the value calculated|required by polystyrene conversion using gel permeation chromatography (GPC).

As said polycarbonate polyol, what made carbonate ester and/or phosgene, and the compound which has 2 or more active hydrogens mentioned above react is mentioned, for example.

As said carbonate, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, etc. are mentioned, for example.

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

Examples of the above-mentioned polyisocyanate (b) include aromatic diisocyanates such as xylylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; Isocyanate, Lysine Diisocyanate, Cyclohexane Diisocyanate, Isophorone Diisocyanate, 4,4'-Dicyclohexylmethane Diisocyanate, Diisocyanatomethylcyclohexane, Tetramethylxylylene Dimethyl Aliphatic or diisocyanates having an alicyclic structure, such as aliphatic diisocyanate, may be used alone or in combination of two or more. Among them, it is preferable to use diisocyanate having an alicyclic structure, more preferably to use 4,4'-dicyclohexylmethane diisocyanate, Isophorone diisocyanate, cyclohexane diisocyanate, diisocyanatomethylcyclohexane.

The above-mentioned (meth)acrylic compound (c) having a hydroxyl group is a compound used for introducing a (meth)acryloyl group into the above-mentioned urethane (meth)acrylate resin (A), and has a compound capable of reacting with an isocyanate group. of hydroxyl.

Examples of (meth)acrylic compounds having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl acrylate, (meth) Alkyl (meth)acrylates having a hydroxyl group such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl acrylate, trimethylolpropane di(meth)acrylate, Polyfunctional (meth)acrylates having a hydroxyl group such as pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and the like. Among them, from the viewpoint of curability by ultraviolet light, it is more preferable to use an acrylic compound having a hydroxyl group, and it is particularly preferable to use acrylic acid 2- Hydroxyethyl ester or 4-hydroxybutyl acrylate.

Examples of the method for producing the urethane (meth)acrylate resin (A) include a method in which the polyol (a) and the (meth)acrylic compound (c) are added without a solvent. Into the reaction system, the above-mentioned polyisocyanate (b) is then supplied, and they are mixed and reacted to produce a method; in the absence of a solvent, the above-mentioned polyol (a) is reacted with the above-mentioned polyisocyanate (b) to obtain A method of producing a polyurethane prepolymer having an isocyanate group at a molecular terminal, then supplying the above-mentioned (meth)acrylic compound (c), mixing and reacting them. In either method, the above-mentioned reaction is preferably carried out at 20 to 120° C. for approximately 30 minutes to 24 hours.

Production of the above-mentioned urethane (meth)acrylate resin (A) can also be performed in the presence of an organic solvent or an aqueous medium. Moreover, instead of an organic solvent or an aqueous medium, it may manufacture in presence of the (meth)acrylic-type monomer (B) mentioned later. Among them, when producing a laminate, it is not necessary to remove the organic solvent or the aqueous medium, and the production process can be simplified. Therefore, it is preferably carried out in the absence of a solvent, or from the viewpoint of suppressing the viscosity in the reaction system, it is preferable to use (methyl) Carried out in the presence of an acrylic monomer (B).

Regarding the reaction of the above-mentioned polyol (a), the above-mentioned polyisocyanate (b) and the above-mentioned (meth)acrylic compound (c), from the viewpoint of controlling the molecular weight of the obtained polyurethane (meth)acrylate resin (A), Preferably, the total amount of the hydroxyl groups of the polyol (a) and the hydroxyl groups of the (meth)acrylic compound (c) and the equivalent ratio of the isocyanate groups of the polyisocyanate (b) [isocyanate group/ Total amount of hydroxyl groups] = 0.75 to 1.00, more preferably 0.79 to 0.95. In addition, these may be reacted when the above-mentioned equivalent ratio exceeds 1, but in this case, for the purpose of inactivating the terminal isocyanate group of the urethane (meth)acrylate resin (A), it is preferable to use methanol Wait alcohol. In this case, it is preferable to calculate the equivalent ratio of the total amount of the hydroxyl groups of the polyol (a), the hydroxyl groups of the (meth)acrylic compound (c), and the hydroxyl groups of the alcohol to the polyisocyanate group [The total amount of isocyanate group/hydroxyl group] is adjusted to be within the above-mentioned range.

In addition, as the alcohol that can be used for the purpose of deactivating the terminal isocyanate group of the above-mentioned urethane (meth)acrylate resin (A), for example, monofunctional alcohols such as methanol, ethanol, propanol, and butanol can also be used, 1 , bifunctional alcohols such as 2-propanediol or 1,3-butanediol containing primary and secondary hydroxyl groups, and the like.

Moreover, when manufacturing a urethane (meth)acrylate resin (A), 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 (methoquinone), p-tert-butyl Catechol methoxyphenol, 2,6-di-tert-butylcresol, phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene, etc.

As the above-mentioned urethanization catalyst, nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine, metal salts such as potassium acetate, zinc stearate, and tin octoate, dilauric acid, etc., can be used, for example. Organometallic compounds such as dibutyltin, etc.

The urethane (meth)acrylate resin (A) has a (meth)acryloyl group that undergoes radical polymerization by light irradiation, heating, or the like. The equivalent of the (meth)acryloyl group is preferably in the range of 1,000 to 20,000, more preferably in the range of 5,000 to 17,000, and still more preferably in the range of 6,000 to 16,000 from the viewpoint of adhesive properties or other physical properties. In addition, the equivalent of the above-mentioned (meth)acryloyl group means dividing the total mass of the above-mentioned polyol (a), polyisocyanate (b) and (meth)acrylic compound (c) by the amount present in the above-mentioned urethane (meth)acrylic acid The value obtained by the equivalent of the (meth)acryloyl group in ester resin (A), and the unit is g/eq.

Moreover, in the present invention, the so-called "(meth)acrylic compound" refers to one or both of methacrylic compound and acrylic compound, and the so-called "(meth)acrylate" refers to methacrylate and One or both of acrylate, the so-called "(meth)acryl" refers to one or both of methacryl and acryl, the so-called "(meth)acrylic" refers to one of methacryl and acrylic Or both, the so-called "(meth)acrylic monomer" refers to one or both of a methacrylic monomer and an acrylic monomer.

The weight-average molecular weight of the urethane (meth)acrylate resin (A) is preferably in the range of 5,000 to 50,000 from the viewpoint of achieving both excellent adhesive force and holding force and imparting good coating workability. , more preferably in the range of 7,000 to 45,000, still more preferably in the range of 10,000 to 40,000, particularly preferably in the range of 12,000 to 3,5000. In addition, the weight average molecular weight of the said urethane (meth)acrylate resin (A) is the value calculated|required by polystyrene conversion using gel permeation chromatography (GPC).

Next, the (meth)acrylic monomer (B) used in the present invention will be described.

Examples of the (meth)acrylic monomer (B) include methyl acrylate (glass transition temperature (Tg): 10°C), ethyl acrylate (-24°C), and propyl acrylate (-37°C). , isopropyl acrylate (-6°C), butyl acrylate (-49°C), sec-butyl acrylate (-22°C), isobutyl acrylate (-24°C), 2-ethylbutyl acrylate (-50 ℃), n-pentyl acrylate (-57 ℃), hexyl acrylate (-57 ℃), 2-ethylhexyl acrylate (-50 ℃), heptyl acrylate (-60 ℃), octyl acrylate (-65 ℃), 2-octyl acrylate (-45 ℃), nonyl acrylate (-58 ℃), dodecyl acrylate (-3 ℃), 3-methoxybutyl acrylate (-56 ℃), acrylic acid 2-methoxyethyl (-50°C), 3-methoxypropyl acrylate (-75°C), 2-methoxybutyl acrylate (-32°C), 3-methylbutyl acrylate (- 45°C), benzyl acrylate (6°C), pentyl methacrylate (-5°C), hexyl methacrylate (-5°C), 2-ethylhexyl methacrylate (-10°C) (above Tg values reproduced from Polmer Handbook (4th ed.), 2-hydroxyethyl acrylate (HEA; -15°C), 2-hydroxypropyl acrylate (HPA; -7°C), 4-hydroxybutyl acrylate (4HBA ; -32℃), isooctyl acrylate (IOAA; -58℃), lauryl acrylate (LA; 15℃), stearyl acrylate (STA; -58℃), tetrahydrofurfuryl acrylate (Viscoat#150 ; -12°C), Benzyl Acrylate (Viscoat #160; 6°C), Ethyl Carbitol Acrylate (Viscoat #190; -67°C), Phenoxyethyl Acrylate (Viscoat #192; -22°C) (The above is manufactured by Osaka Organic Chemical Industry Co., Ltd., and the Tg value is reproduced from HP of the same company), methoxypolyethylene glycol acrylate (EO9mol, AM-90G; -71°C), phenoxypolyethylene glycol Acrylate (AMP-20GY; -8°C) (the above is manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and the Tg value is reproduced from HP of the same company), isoamyl acrylate (IAA; -45°C), ethoxy acrylate- Diethylene glycol ester (EC-A; -70°C) (the above are made by Kyoeisha Chemical Co., Ltd., and the Tg value is reproduced from HP of the same company), neopentyl acrylate (22°C), cyclohexyl acrylate (19 ℃), cetyl acrylate (35 ℃), isobornyl acrylate (94 ℃), phenyl acrylate (57 ℃), acrylamide (165 ℃), benzyl methacrylate (54 ℃), methyl Methyl acrylate (105°C), ethyl methacrylate (65°C), propyl methacrylate (35°C), isopropyl methacrylate (81°C), butyl methacrylate (20°C), methyl Isobutyl acrylate (53°C), sec-butyl methacrylate (60°C), tert-butyl methacrylate ( 118°C), cyclohexyl methacrylate (83°C), 2-hydroxyethyl methacrylate (85°C), isobornyl methacrylate (110°C) (above from Polymer Handbook (4 ^th ed.) Tg value reproduced), tert-butyl acrylate (TBA; 41°C) (manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg value reproduced from HP of the same company), 2-hydroxy-3-phenoxypropyl acrylate ( M-600A; 17°C) (the above are made by Kyoeisha Chemical Co., Ltd., and the Tg values are reproduced from HP of the same company), dimethylacrylamide (DMAA; 119°C), acryloylmorpholine (ACMO; 145°C ), Dimethylaminopropylacrylamide (DMAPAA; 134°C), Isopropylacrylamide (NIPAM; 134°C), Diethylacrylamide (DEAA; 81°C), Hydroxyethylacrylamide (HEAA; 98°C °C) (the above are Tg values reproduced from HP of the same company, manufactured by Kosei Co., Ltd.), etc. These monomers may be used alone or in combination of two or more. In addition, the above-mentioned Tg value represents the Tg value of the homopolymer of the above-mentioned (meth)acrylic monomer, and the value described in the Polymer Handbook (4th ed.) and the homepage of the (meth)acrylic monomer manufacturer is used. value.

As the (meth)acrylic monomer (B), methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferably used from the viewpoint of adhesive force, holding force, and other physical properties. , 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, particularly preferably selected from butyl acrylate, 2-ethylhexyl acrylate, dimethylacrylamide, acryloyl? One or more of morphine, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, hydroxyethylacrylamide, and cyclohexyl acrylate.

The amount of the above-mentioned (meth)acrylic monomer (B) is from the viewpoint of achieving both excellent adhesive force and holding power and imparting coatability based on viscosity, etc., relative to the above-mentioned urethane (meth)acrylic acid 100 parts by mass of the ester resin (A) is preferably used in the range of 30 to 200 parts by mass, more preferably in the range of 50 to 150 parts by mass, and particularly preferably in the range of 70 to 130 parts by mass.

Next, the photoinitiator (C) used for this invention is demonstrated.

The photopolymerization initiator (C) generates radicals by light irradiation, heating, etc., and initiates radical polymerization of the urethane (meth)acrylate resin (A) and the (meth)acrylic monomer (B) above.

Examples of the photopolymerization initiator include 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) ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylbenzene Acetophenones such as ethyl ketone; benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, benzoylbenzene Formic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4 - Benzophenones such as methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone Thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; 4,4'-dimethylaminothioxanthone (alias = Michler's ketone), 4,4'-diethylaminobenzophenone, α-acyl oxime ester, benzil, methyl benzoylformate ("VICURE55"), 2-ethylanthraquinone, etc. Anthraquinones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“LUCIRIN TPO”), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“LUCIRIN TPO”), IRGACURE819") and other acylphosphine oxides; 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone ["BTTB" manufactured by NOF Co., Ltd.], acrylylated benzophenone wait.

As the above-mentioned photopolymerization initiator, it is preferable to use 2-hydroxy-2-methyl from the viewpoint of achieving both excellent adhesive force and holding power, preventing discoloration of the pressure-sensitive adhesive layer over time, and improving curability. -1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzene Formyl)-phenylphosphine oxide.

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

In addition, as the usage-amount of the said photoinitiator (C), from viewpoints, such as initial yellowing resistance (transparency), the mass ratio [(C)/(D) with the photostabilizer (D) mentioned later ] is preferably in the range of 95/5 to 20/80, more preferably in the range of 85/15 to 50/50.

Next, the photostabilizer (D) used in the present invention will be described.

The above-mentioned photostabilizer (D) refers to a substance that traps radicals generated by photodegradation, and examples thereof include free radical scavengers such as thiol compounds, thioether compounds, and hindered amine compounds, as well as benzophenone compounds, benzophenone compounds, and benzophenone compounds. UV absorbers such as ester compounds and the like may be used alone or in combination of two or more. Among them, it is preferable to use hindered amine compounds from the viewpoint of maintaining both excellent adhesive force and holding power and further improving yellowing resistance after light exposure.

Examples of the hindered amine compound include 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 (trade name: Tinuvin (registered trademark) 152 (manufactured by BASF Japan Co., Ltd.)), bis(2,2,6,6-tetramethyl sebacate Dimethyl-1-(octyloxy)-4-piperidinyl) ester (trade name: Tinuvin (registered trademark) 123 (manufactured by BASF Co., Ltd.)), 1,1-dimethylethyl hydroperoxide Hindered amine compounds with amino ether groups such as reaction products with octane, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrole N-acetyl-based hindered amine compounds such as alkane-2,5-dione (trade name: Hostavin (registered trademark) 3058 (manufactured by Clariant Japan Co., Ltd.)), bis(1,2,2,6,6-pentamethyl yl-4-piperidinyl) sebacate (trade name: Tinuvin (registered trademark) 765 (manufactured by BASF Japan Co., Ltd.)), bis(1,2,2,6,6,-pentamethyl-4- Piperidinyl){[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl}butylmalonate (trade name: Tinuvin (registered trademark) 144 (BASF Japan Co., Ltd.)), dimethyl succinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin ( Registered trademark) 622LD (manufactured by BASF Japan Co., Ltd.), malonic acid [{4-methoxyphenyl}methylene]-bis(1,2,2,6,6-pentamethyl-4- N-alkyl hindered amine compounds of piperidinyl) ester (trade name: Hostavin (registered trademark) PR-31 (manufactured by Clariant Japan Co., Ltd.)), etc. Among them, it is preferable to use N-alkyl hindered amine compounds from the viewpoint of maintaining excellent adhesion and holding power, and further improving the yellowing resistance after light exposure. 2,2,6,6-pentamethyl-4-piperidinyl) sebacate and dimethyl succinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6, One or more light stabilizers in the polycondensate of 6-tetramethylpiperidine.

The amount of the light stabilizer (D) used is preferably 0.01 to 100 parts by mass relative to 100 parts by mass of the above-mentioned urethane (meth)acrylate resin (A) from the viewpoint of imparting yellowing resistance after light exposure. It is used in the range of 10 mass parts, More preferably, it is the range of 0.1-5 mass parts.

Next, the antioxidant (E) used in this invention is demonstrated.

Examples of the above-mentioned antioxidant (E) include hindered phenol compounds (primary antioxidants) that capture free radicals generated by thermal degradation, phosphorus compounds and sulfur compounds (disulfur compounds) that decompose peroxides generated by thermal degradation Secondary antioxidants), etc., these may be used alone or in combination of two or more.

Examples of the hindered phenol compound include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX (registered trademark) 245 ( BASF Japan Co., Ltd.)), pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX (registered trademark) 1010 (BASF Japan Co., Ltd.) )), octadecyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX (registered trademark) 1076 (manufactured by BASF Japan Co., Ltd.)), sulfur Diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX (registered trademark) 1035 (manufactured by BASF Japan Co., Ltd.), phenylpropionic acid -3,5-bis(1,1-dimethylethyl)-4-hydroxy-C ₇ -C ₉ side chain alkyl ester (trade name: IRGANOX (registered trademark) 1135 (manufactured by BASF Japan Co., Ltd.) ), 4,6-bis(dodecylthiomethyl)-o-cresol (trade name: IRGANOX (registered trademark) 1726 (manufactured by BASF Japan Co., Ltd.), N-phenylaniline and 2,4,4 -Reaction products of trimethylpentene (trade name: IRGANOX (registered trademark) 5057 (manufactured by BASF Japan Co., Ltd.)), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5- Methylbenzyl)-4-methylphenylacrylate (trade name: Sumilizer (registered trademark) GM (manufactured by Sumitomo Chemical Co., Ltd.)), 3,9-bis[2-[3-(tert-butyl- 4-Hydroxy-5-methylphenyl)propanoyl]-1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer (registered trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), 2,6-di-tert-butyl-4-methylphenol (trade name: Noclac200 (manufactured by Ouchi Shinko Chemical Co., Ltd.)), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Noclac NS-6 (manufactured by Ouchi Shinshin Chemical Co., Ltd.)), 2,5-di-tert Amylhydroquinone (trade name: Noclac DAH (manufactured by Ouchi Shinshin Chemical Co., Ltd.), etc.

Examples of the above-mentioned phosphorus compound include triphenylphosphine, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, triphenyl phosphite, trinonylphenyl Phosphite, Tris(2,4-dibutylphenyl)phosphite, Tris(2,4-dibutyl-5-methylphenyl)phosphite, Tris[2-tert-butyl-4 -(3-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tris(2,4-di-tert-butylphenyl)phosphite, deca Trialkyl phosphite, octyl diphenyl phosphite, bis(decyl) monophenyl phosphite, bis(tridecyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite Phosphite, 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 , Tetra(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 diphosphite, 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylene bis(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]dioxaphospin-6-yl)oxy]ethyl)amine, Phosphite ester of 2-ethyl-2-butylpropanediol and 2,4,6-tributylphenol, etc.

Examples of the aforementioned sulfur compounds include didodecyl 3,3'-thiopropionate, dilauryl 3,3'-thiodipropionate, lauryl thiodithionate ), 3,3'-ditridecyl thiodipropionate, 3,3'-dimyristyl thiodipropionate, distearyl 3,3'-thiodipropionate, Tetra-methylene-3-laurylthiopropionate methane, distearoyl-3,3'-methyl-3,3'-thiodipropionate, laurylstearyl-3, 3'-thiodipropionate, bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-tert-butylphenyl]sulfide, β-laurylthio Propionate, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, dioctadecyl-3,3'-thiodipropionate, etc.

Among them, it is preferable to use a phosphorus compound, more preferably to use a compound selected from triphenylphosphine, bis(2, One or more antioxidants selected from 4-di-tert-butyl-6-methylphenyl) ethyl phosphite and tris(2,4-di-tert-butylphenyl) phosphite, particularly preferably triphenyl Phosphine, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

As the amount of the above-mentioned antioxidant (E) used, the mass ratio [(D)/(E)] to the above-mentioned light stabilizer (D) must be in the range of 95/5 to 5/95, and in the case of exceeding the above-mentioned range , the desired yellowing resistance cannot be obtained. Moreover, as said mass ratio, it is more preferable that it is the range of 80/20-20/80, and it is still more preferable that it is the range of 70/30-30/70 from a viewpoint that thermal yellowing resistance and light yellowing resistance can be further improved.

Next, the resin composition for ultraviolet curable adhesives of this invention is demonstrated.

The resin composition for ultraviolet curable adhesives of the present invention can be produced, for example, by a method in which, after producing the urethane (meth)acrylate resin (A) alone, the (meth)acrylic body (B), photopolymerization initiator (C), photostabilizer (D) and antioxidant (E) mixing method; or in the presence of part or all of (meth)acrylic monomer (B), A method for producing a urethane (meth)acrylate resin (A), and mixing a polymerization initiator (C), a light stabilizer (D) and an antioxidant (E).

The ultraviolet curable adhesive resin composition obtained by the above method is not particularly limited, but from the viewpoint of good applicability and good handling of the adhesive solution during coating, it is preferably 500 to 20,000 The range of mPa·s is more preferably in the range of 1,000 to 15,000 mPa·s, and further preferably in the range of 5,000 to 10,000 mPa·s in order to further improve the step followability. In addition, the said viscosity shows the value measured with the B-type viscometer at 25 degreeC.

In addition, the resin composition for ultraviolet curable adhesives of the present invention may contain other additives in addition to the above-mentioned substances.

As the above-mentioned other additives, for example, rust inhibitors, thixotropic agents, sensitizers, polymerization inhibitors, curing agents, curing accelerators, leveling agents, tackifiers, paraffin waxes, heat stabilizers, antistatic agents, etc. , flame retardant, foam regulator, defoamer, preservative, anti-blocking agent, silane coupling agent, etc.

In addition, the ultraviolet curable adhesive resin composition of the present invention may be a combination of the above-mentioned urethane (meth)acrylate resin (A), the above-mentioned (meth)acrylic monomer (B), the above-mentioned photopolymerization initiator (C), photostabilizer (D), antioxidant (E), and the above-mentioned other additives used as required are dissolved or dispersed in solvents such as organic solvents and aqueous media. However, for the above-mentioned ( In the composition obtained by dissolving or dispersing the above-mentioned urethane (meth)acrylate resin (A) and the above-mentioned photopolymerization initiator (C) in the meth)acrylic monomer (B), since the In combination, the process of removing the solvent contained in the adhesive is unnecessary when producing the laminate, and the production efficiency of the above-mentioned laminate can be improved, so it is preferable.

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

As a method of curing the resin composition for an ultraviolet curable adhesive of the present invention, for example, a predetermined ultraviolet light can be irradiated by using 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 light cures it.

The irradiation of the ultraviolet rays is preferably in the range of 0.05 to 5 J/cm ² , more preferably in the range of 0.1 to 3 J/cm ² , and particularly preferably in the range of 0.3 to 1.5 J/cm ² . In addition, the ultraviolet irradiation amount is based on the value measured using the illuminance meter "UV Power Pak PP2000" (UV-A (320-390nm)) manufactured by EIT company.

In addition, when the ultraviolet curable adhesive resin composition of the present invention contains the above-mentioned other additives, if necessary, after the above-mentioned ultraviolet irradiation, heating can be performed at about 40 to 80° C. to further promote solidify.

Examples of substrates on which the ultraviolet curable adhesive resin composition of the present invention can be applied to form an adhesive layer include plastic substrates, flexographic printing substrates, glass substrates, and vapor-deposited substrates on these substrates. There are substrates such as ITO.

Examples of the above-mentioned plastic substrates include substrates made of acrylic resins and the like commonly used, PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified Non-reactive PPE (polyphenylene ether), PET (polyethylene terephthalate), COP (cycloolefin polymer), TAC (triacetyl cellulose), antireflection film or sheet, antifouling film or sheet, composition A film or sheet of a transparent conductive film of a touch panel, etc.

[Example]

Hereinafter, the present invention will be specifically described using examples.

[Synthesis Example 1]

<Synthesis of urethane acrylate resin (A-1)>

Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 706 parts by mass of polycarbonate polyol ("Duranate T5652", manufactured by Asahi Kasei Chemicals, number average molecular weight: 2,000) and 1,4-butyl 8.0 parts by mass of diol, 13.6 parts by mass of 2-hydroxyethyl acrylate, 2 parts by mass of 2,6-di-tert-butyl-cresol, and 0.3 parts by mass of p-methoxyphenol. After raising the temperature in the reaction container to 40°C, 97 parts by mass of isophorone diisocyanate was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. Then, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained the urethane acrylate resin (A-1). The equivalent weight of the acryloyl group of the obtained urethane acrylate resin (A-1) was 7039 (rounded off below the decimal point. The molecular weight of 2-hydroxyethyl acrylate was 116.1. The following is the same.), and the weight average molecular weight was 22000.

[Synthesis Example 2]

<Synthesis of urethane acrylate resin (A-2)>

Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 460 parts by mass of polytetramethylene glycol (number-average molecular weight: 1,000), 6.5 parts by mass of 2-hydroxyethyl acrylate, 2,6-ditertiary 2 parts by mass of butyl-cresol, and 0.3 parts by mass of p-methoxyphenol. After raising the temperature in the reaction container to 40°C, 105 parts by mass of isophorone diisocyanate was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. Then, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained the urethane acrylate resin (A-2). The equivalent weight of the acryloyl group of the obtained urethane acrylate resin (A-2) was 10,208, and the weight average molecular weight was 26,000.

[Synthesis Example 3]

<Synthesis of urethane acrylate resin (A-3)>

Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 465 parts by mass of polycarbonate polyol (“Duranate T5651”, manufactured by Asahi Kasei Chemicals, number average molecular weight: 1,000) and 2-hydroxyethyl acrylate were added. 9.5 parts by mass of ester, 2 parts by mass of 2,6-di-tert-butyl-cresol, and 0.3 parts by mass of p-methoxyphenol. After raising the temperature in the reaction container to 40°C, 102 parts by mass of isophorone diisocyanate was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. Then, it held at 80 degreeC for 12 hours, and after confirming that all the isocyanate groups disappeared, it cooled and obtained the urethane acrylate resin (A-3). The obtained urethane acrylate resin (A-3) had an acryloyl group equivalent of 7,045 and a weight average molecular weight of 20,000.

[Synthesis Example 4]

<Synthesis of urethane acrylate resin (A-4)>

Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 470 parts by mass of polytetramethylene glycol (number-average molecular weight: 1,000), 9.5 parts by mass of 2-hydroxyethyl acrylate, 2,6-ditertiary 2 parts by mass of butyl-cresol, and 0.3 parts by mass of p-methoxyphenol. After raising the temperature in the reaction container to 40°C, 102 parts by mass of isophorone diisocyanate was added. Then, 0.1 part by mass of dioctyltin dineodecanoate was added, and the temperature was raised to 80° C. over 1 hour. Then, after holding|maintaining at 80 degreeC for 12 hours and confirming that all the isocyanate groups disappeared, it cooled and obtained the urethane acrylate resin (A-4). The obtained urethane acrylate resin (A-4) had an acryloyl group equivalent of 7,107 and a weight average molecular weight of 19,000.

[Example 1]

In a container equipped with a stirrer, a reflux condenser, and a thermometer, 100 parts by mass of urethane acrylate resin (A-1), 70 parts by mass of butyl acrylate, 70 parts by mass of butyl acrylate, and cyclohexyl acrylate were added at a temperature of 80° C. in the container. 35 parts by mass of ester, stirred until uniform. Thereafter, after cooling to room temperature, 4 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(1,2,2,6,6-pentamethyl-4- 0.5 parts by mass of piperidinyl) sebacate and 1.5 parts by mass of triphenylphosphine were stirred until uniform. Thereafter, it was filtered through a 200-mesh metal mesh to obtain a resin composition for ultraviolet curable adhesives.

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

The type and amount of the type of polyurethane acrylate resin used, the type and amount of (meth)acrylic monomer, the amount of photopolymerization initiator, the type and amount of light stabilizer, and the type and amount of antioxidant are shown in Table 1 Except having changed, it carried out similarly to Example 1, and obtained the resin composition for ultraviolet-curable adhesives.

[Measuring method of weight average molecular weight]

The weight average molecular weight of the polyol and the urethane acrylate resin used in the Example and/or the comparative example was measured by the gel permeation chromatography (GPC) method on the following conditions.

Measuring device: high-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Co., Ltd.

Column: The following columns manufactured by Tosoh Corporation were used 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

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 Co., Ltd.

"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Co., Ltd.

"TSKgel standard polystyrene A-5000" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Co., Ltd.

"TSKgel standard polystyrene F-80" manufactured by Tosoh Co., Ltd.

"TSKgel standard polystyrene F-128" manufactured by Tosoh Co., Ltd.

"TSKgel standard polystyrene F-288" manufactured by Tosoh Co., Ltd.

"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Co., Ltd.

[How to make adhesive film]

The surface of the polyethylene terephthalate film (release PET50) with a thickness of 50 μm on the surface was coated so that the film thickness after ultraviolet irradiation became 175 μm in Examples and Comparative Examples. The obtained resin composition for ultraviolet curable adhesives was bonded with release PET50. Thereafter, UV irradiation was performed using a UV irradiation device so that the cumulative light quantity of the wavelength of the UV-A region after the mold release PET50 had passed through became 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 75-micrometer-thick polyethylene terephthalate film (PET75), and the adhesive film in which the PET75 base material was bonded on one side was produced. This was cut to a width of 25 mm, and the obtained material was used as a test piece. This test piece was attached to a glass plate and a polycarbonate (PC) plate as adherends by a 2 kg roller x 2 times of reciprocation. One hour after sticking, the 180-degree peel strength was measured in an atmosphere of 23°C and 50% RH as the adhesive force.

[Measuring method of holding power]

The test piece produced by the same method as the test piece used in the above-mentioned method of measuring the adhesive force was laminated on a mirror-finished stainless steel plate so that the adhesive area reached 25 mm × 25 mm, and the test piece was tested at 23° C. by 50% These were bonded together by reciprocating a 2 kg roll twice under a RH atmosphere.

Then, in an atmosphere of 70°C, a load of 500 g was applied to the test piece attached to the stainless steel plate in the direction of 0° (shear direction) with respect to the above stainless steel plate, and the thickness of the test piece from the stainless steel plate was measured. The holding time is the holding force.

[Measurement method of initial yellowing degree (b*)]

The adhesive film produced by the above-mentioned method was attached to a glass plate, and then one sheet of release PET50 was peeled off, and what obtained was made into the test piece. The initial yellowing degree (B*) of this test piece was measured according to JISK7105 using light source C, field of view 2°, and "spectrophotometer" CM-5000d (manufactured by Konika Minolta Sensing Co., Ltd.).

[Measurement method of light yellowing resistance (b*(UV))]

The adhesive film produced by the above-mentioned method was attached to a glass plate, and then one sheet of release PET50 was peeled off, and what obtained was made into the test piece. According to JIS A1415, this test piece was left to stand for 250 hours and 500 hours under the conditions of an ultraviolet carbon arc lamp, a black panel temperature of 63° C., and an ultraviolet fading meter “U48AU” (manufactured by Suga Testing Instrument Co., Ltd.). Thereafter, light yellowing resistance (b*(UV)) was measured in accordance with JIS K7105 in the same manner as the aforementioned method.

[Measuring method of resistance to heat yellowing (b*(heat))]

The adhesive film produced by the above-mentioned method was attached to a glass plate, and it left to stand in 85 degreeC*85%RH atmosphere for 250 hours and 500 hours. Thereafter, one sheet of release PET50 was peeled off, and the degree of heat-resistant yellowing (b*(heat)) was measured in accordance with JIS K7105 in the same manner as the above-mentioned method.

【Table 1】

Furthermore, the translated words in Table 1 will be described.

BA: butyl acrylate

ACMO: Acryloylmorpholine

DMAA: Dimethacrylamide

CHA: cyclohexyl acrylate

C-1: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

C-2: 2-Hydroxy-2-methyl-1-phenylpropan-1-one

Tinuvin765: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate

Tinuvin123: bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) sebacate

Tinuvin622LD: Dimethyl succinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate

TPP: Triphenylphosphine

Irgafos38: bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite

Irganox1035; 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

It turns out that the adhesive obtained using the resin composition for ultraviolet curable adhesives of this invention is excellent in adhesive force, initial yellowing property, light yellowing resistance, and heat yellowing resistance.

On the other hand, Comparative Example 1 was an embodiment not containing an antioxidant, and was found to be poor in light yellowing resistance and heat yellowing resistance in particular.

Moreover, comparative example 2 was an aspect which did not contain a light-resistant stabilizer, and it turned out that light yellowing resistance and heat yellowing resistance were not good especially.

Claims (6)

1. a ultraviolet-curing adhesive resin combination, is characterized in that,

Containing (methyl) the acrylic compounds c reaction that makes polyvalent alcohol a and polymeric polyisocyanate b and have hydroxyl, the ultraviolet-curing adhesive of urethane (methyl) acrylate resin A, (methyl) the acrylic monomer B obtaining and Photoepolymerizationinitiater initiater C, with in resin combination, also contains photostabilizer D and antioxidant E by quality ratio in 95/5～5/95 scope.

2. ultraviolet-curing adhesive resin combination according to claim 1, wherein,

Described photostabilizer D is N-alkyl hindered amine compound.

3. ultraviolet-curing adhesive resin combination according to claim 2, wherein,

Described N-alkyl hindered amine compound is to be selected from two (1,2,2,6,6-pentamethyl--4-piperidyl) sebates and dimethyl succinate/1-(2-hydroxyethyl)-4-hydroxyl-2, in 2,6,6-tetramethyl piperidine polycondensate more than a kind.

4. ultraviolet-curing adhesive resin combination according to claim 1, wherein,

Described antioxidant E is phosphorus compound.

5. ultraviolet-curing adhesive resin combination according to claim 4, wherein,

Described phosphorus compound be selected from triphenylphosphine, two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester and three (2,4-di-tert-butyl-phenyl) phosphorous acid ester more than a kind.

6. a tackiness agent, is characterized in that,

That right to use requires the tackiness agent that in 1～5, the ultraviolet-curing adhesive described in any one makes with resin combination.