WO2008056751A1

WO2008056751A1 - Actinic radiation curable adhesive composition

Info

Publication number: WO2008056751A1
Application number: PCT/JP2007/071741
Authority: WO
Inventors: Yasuyuki Sanai; Mikihide Osoegawa; Miki Tachibana
Original assignee: Toagosei Co., Ltd.
Priority date: 2006-11-09
Filing date: 2007-11-08
Publication date: 2008-05-15
Also published as: TW200837167A; JPWO2008056751A1

Abstract

[PROBLEMS] To provide an actinic radiation curable adhesive composition which is excellent in bond strength under the condition of any of high temperature and high humidity and is little discolored even after long-time use. [MEANS FOR SOLVING PROBLEMS] An actinic radiation curable adhesive composition characterized by comprising (A) a urethane (meth)acrylate having a polyester or polycarbonate skeleton, (B) a phenol compound having at least one -C(CH3)2R group (wherein R is alkyl or phenyl) in the phenyl group, (C) a sulfur-containing antioxidant, and (D) a compound having an ethylenically unsaturated group except the component (A).

Description

Specification

Active energy ray-curable adhesive composition

Technical field

The present invention relates to an active energy ray-curable adhesive composition capable of adhering various substrates by irradiation with active energy rays such as an electron beam or ultraviolet rays, and the composition of the present invention Is suitable for laminating and bonding thin-layer adherends such as plastic films or plastic sheets used as optical components. Furthermore, liquid crystal display elements, EL (electric aperture luminescence) display elements, projection display elements, FED ( Field emission (field emission) display) It is suitably used for the production of various optical films or sheets used for display elements, plasma display elements, etc., and can be used in these technical fields.

Background art

Conventionally, thin-layer adherends such as plastic films or sheets, or thin-layer adherends such as plastic films or sheets, and thin-layer adherends made of other materials are bonded together. In the laminating method, a solvent-type adhesive composition containing an ethylene acetate butyl copolymer or a polyurethane-based polymer is applied to the first thin layer adherend and dried, and then the second thin layer is added thereto. The dry laminating method is mainly used in which the adherend is pressed with a nip roller.

The adhesive composition used in this method is generally a force that contains a large amount of solvent in order to make the coating amount of the composition uniform, and therefore a large amount of solvent vapor is volatilized during drying, resulting in toxicity, work safety and Environmental pollution is a problem!

As an adhesive composition that solves these problems, a solventless adhesive composition has been studied.

[0003] As a solventless adhesive composition, a two-component adhesive composition and an adhesive composition that is cured by active energy rays such as ultraviolet rays or electron beams are widely used.

The two-component adhesive composition is mainly composed of a polymer having a hydroxyl group at the terminal and a polyisocyanate compound having an isocyanate group at the terminal as a curing agent. A urethane-based adhesive composition is used. However, the composition has the disadvantage that it takes too much time to cure!

On the other hand, active energy ray-curable adhesive compositions have been recently attracting attention because of their high productivity due to their high curing speed.

[0004] On the other hand, thin display devices such as liquid crystal display devices are widely used as display elements for televisions, portable personal computers, mobile phones and mobile phones, as well as simple display devices for digital watches and various electrical appliances. It has been. In recent years, active energy ray-curable adhesives have also been used for bonding various optical films used in the liquid crystal display elements.

The adhesive composition used in the optical film is required to have the ability to maintain its adhesive strength under severe conditions under high temperature and high humidity conditions. However, most of the conventional active energy ray-curable adhesive compositions are excellent in the initial adhesive strength, but the adhesive strength decreases when used for a long time under high temperature or high humidity conditions. May cause peeling or whitening due to moisture absorption.

[0005] The present inventors have previously proposed an adhesive (Patent Document 1) containing a polymer having a glass transition temperature of 40 ° C or higher in the composition, or using a compound having an imide group. Proposes an adhesive (Patent Document 2) that has excellent adhesion at high temperatures and high humidity! In addition, the present inventors have proposed an adhesive between a polymethylmetatalylate (PMMA) plate and a film, but when used as a laminate adhesive between films, the adhesive strength is insufficient. (Patent Document 3).

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2000-072833 (Claims)

Patent Document 2: Japanese Patent Laid-Open No. 2001-064594 (Claims)

Patent Document 3: Japanese Patent Laid-Open No. 2005-272775 (Claims)

Disclosure of the invention

Problems to be solved by the invention

[0007] However, in recent years, there has been a demand for products that are used under severe conditions such as higher temperatures and higher humidity, used outdoors under sunlight, and have a longer product life. With adhesives that have been used, problems such as reduced adhesive strength and coloration over time Has occurred and is no longer satisfactory.

The present inventors have found an adhesive composition having an active energy ray-curable adhesive composition that is excellent in adhesive strength under both high temperature and high humidity conditions, and has little coloring even when used for a long time! For this reason, we conducted an intensive study.

Means for solving the problem

[0008] As a result of various studies, the present inventors have found that a composition comprising a urethane (meth) acrylate having a specific structure, a phenol compound having a specific structure, and a phenolic antioxidant has either high temperature or high humidity. It was found that the adhesive strength was excellent even under conditions, and there was little coloring, and that it was at a practical level, and the present invention shown in <1> below was completed.

<1> (A) Urethane (meth) acrylate having a polyester skeleton or a polycarbonate skeleton, (B) at least one group in the phenyl group — C (CH 2) R (R represents an alkyl group or a phenyl group) An active energy ray-curable adhesive comprising: a phenolic compound having a hydrogen atom; (C) a thio-based antioxidant; and (D) a compound having an ethylenically unsaturated group other than the component (A). Composition.

The invention's effect

[0009] According to the active energy ray-curable adhesive composition of the present invention, it is possible to maintain an excellent adhesive force even under high temperature or high humidity! Few . Therefore, the active energy ray-curable adhesive composition of the present invention is effective for adhesion of thin-layer adherends such as plastic films used as various optical members, and particularly for the production of optical films used for liquid crystal display devices and the like. Can be suitably used.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

In the present specification, attalylate and / or metatalylate is referred to as (meth) atalylate, attalyloyl group and / or methacryloylole group is referred to as (meth) atalyleunole group, acrylic acid and / or methacrylic acid as (meth) acrylic acid. Expressed as acid.

[0011] The active energy ray-curable adhesive composition of the present invention includes (A) a urethane (meth) acrylate (hereinafter referred to as component (A)) having a polyester skeleton or a polycarbonate skeleton, and (B) a phenyl. At least one group in the group — C (CH 2) R (R represents an alkyl group or a phenyl group. ) Phenol compounds (hereinafter referred to as component (B)), (C) xio antioxidants (hereinafter referred to as component (C) and! /, U), and (D) ethylene other than component (A). And a compound having an unsaturated group (hereinafter referred to as component (D)).

Hereinafter, each component will be described.

In addition, as the components (A) to (D), each compound described later is used alone or in combination of two or more.

[0012] 1. Component (A)

Component (A) is a urethane (meth) acrylate having a polyester skeleton or a polycarbonate skeleton. In the present invention, by including the component (A), the cured product obtained has excellent adhesion even if it is subjected to high temperature or high humidity!

On the other hand, in the composition containing urethane (meth) acrylate having a skeleton other than the polyester skeleton or the polycarbonate skeleton different from the component (A), the adhesive strength of the obtained cured product under high temperature conditions and high humidity conditions decreases. End up.

As the component (A), both oligomers and polymers can be used, and those having a weight average molecular weight of 500 to 50,000 are more preferable, and those having 3,000 to 40,000 are more preferable.

In the present invention, the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.

[0013] As the component (A), various compounds can be used. A compound in which a polyol having a polyester skeleton or a polycarbonate skeleton and an organic polyisocyanate reaction product are reacted with a hydroxyl group-containing (meth) acrylate. Etc.

In addition, as the component (A), a polyester skeleton or polycarbonate that is preferably a urethane (meth) atrelate (hereinafter referred to as a bifunctional urethane (meth) acrylate) having two (meth) attaroyl groups. It is more preferable that the reaction product of a diol having a skeleton and an organic diisocyanate is a bifunctional urethane (meth) acrylate in which a hydroxyl group-containing (meth) acrylate is reacted.

[0014] Here, examples of the polyol having a polyester skeleton include an esterification reaction product of a diol such as a low molecular weight diol or polyprolacton diol and an acid component such as a dibasic acid or an anhydride thereof. . Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexane dimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and the like.

Examples of the dibasic acid or its anhydride include adipic acid, succinic acid, phthalic acid, tetrahidrphthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.

Examples of the polycarbonate polyol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.

[0015] Examples of organic polyisocyanates include tolylene diisocyanate, 1,6-hexanediisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, 1,6 San diisocyanate trimer, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylene diisocyanate, paraphenol dirange Isocyanate, Tolylene diisocyanate dimer, 1,5-Naphthalene diisocyanate, Hexamethylene diisocyanate cross-adduct, 4, 4'-dicyclohexylmethane diisocyanate, Trimethylolpropane Examples include tris (tolylene diisocyanate) adduct and isophorone diisocyanate. Organic diisocyanates are preferred as organic polyisocyanates.

[0016] Hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) atereloxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy octyl (meth) acrylate, pentaerythritol Examples thereof include hydroxyalkyl (meth) acrylates such as tri, di or mono (meth) acrylate and trimethylolpropane di or mono (meth) acrylate.

[0017] In these, in the presence of an addition catalyst such as dibutyltin dilaurate, the organic isocyanate to be used and the polyol component are subjected to an addition reaction by heating and stirring, and further, a hydroxyalkyl (meth) acrylate is added, followed by heating and stirring to cause an addition reaction. Can be obtained.

[0018] As the component (A), the adhesive strength under high humidity is particularly excellent, and the adhesive after curing is time-dependent. Urethane acrylate using non-aromatic polyester polyols and polycarbonate polyols is preferred because it is less colored!

[0019] 2. Component (B)

Component (B) is a phenol compound having at least one group — C (CH 2) R (wherein R represents an alkyl group or a phenyl group) in the phenyl group. In the present invention, by including the component (B), coloring over time can be remarkably suppressed.

Examples of the alkyl group for R include those having 1 to 10 carbon atoms, and more preferred is a methyl group, preferably an alkyl group having carbon atoms;!

The number of the group C (CH 3) 2 R in the phenyl group is preferably 1 or 2.

[0020] The component (B) preferably contains a compound represented by the following formula (1), more preferably only one or more compounds represented by the formula (1). .

[0021] [Chemical 1]

[In the formula (1), R represents an alkyl group or a phenyl group, R ¹ represents a hydrogen atom, an alkyl group or a phenyl group, R ² and R ³ represent a hydrogen atom or a methyl group, X Represents an m-valent group, and m represents an integer of 1 to 4. ]

In the formula (1), X is preferably a monovalent or divalent group, and m is preferably an integer of 1 or 2.

In addition, the alkyl group for R ¹ in formula (1) is preferably an alkyl group having 1 to 20 carbon atoms.

As the compound of the formula (1), a compound represented by the following formula (1) ′ or / and the formula (1) ″ is preferable.

[0023] [Chemical 2]

In the formula (1), specific examples of X include the following monovalent to tetravalent groups.

Examples of the monovalent group include an alkyl group, a group having one or more ester bonds (COO and / or OCO), a benzotriazol group, and a group containing a hindered amino skeleton.

As the alkyl group, an alkyl group having 2 or more carbon atoms is preferred, and the cured product is preferably prevented from being colored.

Examples of the group having one or more ester bonds include an alkoxycarbonylalkyl group, and a group represented by I ^ COOR ¹ is preferable. Here, R ⁷ is an alkylene group having 1 to 12 carbon atoms such as an ethylene group, and R ¹ represents an alkyl group having 1 to 20 carbon atoms.

R ⁷ is preferably an alkylene group having 2 to 6 carbon atoms! /.

Examples of the divalent group include an alkylene group and a group having one or more ester bonds. The group having one or more ester bonds includes two or more structures selected from the group consisting of monovalent to tetravalent alkyl groups, ester bonds, and ether bonds, and one or more ester bonds. And a divalent group having a spiro orthoether ring and one or more ester bonds is preferable.

Examples of the trivalent group include isocyanur groups (1, 3, 5 triazine 1, 2, 4, 6 (1H, 3H, 5H) -trione 1, 3, 5-triyl group).

Examples of the tetravalent group include groups having one or more ester bonds, and two or more structures selected from the group consisting of monovalent to tetravalent alkyl groups, ester bonds, and ether bonds are linked. And tetravalent groups having one or more ester bonds are preferred. More specifically, C (CH OCOR ⁷ ) and the like can be mentioned. R ⁷ has the same carbon number as described above!

twenty four

It represents 12 alkylene groups, and the same as described above is preferable.

[0025] In the compound represented by the formula (1), X has one or more ester bonds. The compound (Bl) which is a group [hereinafter referred to as component (B1)] is more preferred.

In the component (B1), preferred examples of the monophenol compound include a compound represented by the following formula (2).

[0027] [Chemical 3]

[In the formula (2), R ⁴ represents an alkyl group having 1 to 20 carbon atoms.] ]

In the formula (2), if the carbon number of R ⁴ is 1 or more, the solubility in the composition is sufficient, and if the carbon number is 20 or less, a desired effect can be obtained with a small amount. A uniform composition can be obtained.

As a specific example of the monophenol compound, a compound in which R ⁴ is —CH 2 is

18 37

It is easy to obtain because it is sold under the product name AO-50 by the industry.

[0030] In the component (B1), preferred examples of the diphenol compound include compounds represented by the following formula (3).

[0031] [Chemical 4]

[0032] As the component (B), in addition to the compounds other than those described above, at least one group in the phenyl group known as an ultraviolet absorber — C (CH 2) R (R is an alkyl group or a phenyl group)

3 2

And a benzotriazole group (B2) (hereinafter referred to as component (B2)), a known light stabilizer, at least one group C ( CH) R

3 2

(R represents an alkyl group or a phenyl group) and a compound having a hindered amino group The product (B3) [hereinafter referred to as the component (B3)] can also be mentioned.

As the component (B2), various compounds can be used as long as they are compounds having at least one group C (CH 3) R in the phenyl group and further having a benzotriazole group. Such compounds are commercially available, and examples thereof include TINUVIN series manufactured by Ciba Specialty Chemicals.

As the component (B2), a compound represented by the following formula (4) is more preferable!

[0034] [Chemical 5]

[Wherein R ⁷ represents an alkyl group or a phenyl group having carbon atoms;! -10]. ]

In the above formula (4), as R ⁷ , an alkyl group having 4 carbon atoms or a phenyl group is commercially available and can be suitably used.

As the component (B3), various compounds can be used as long as they are compounds having at least one group C (CH 3) R in the phenyl group and further having a hindered amino group. Such compounds are commercially available and can mention the TINUVIN series manufactured by Chino 'Specialty' Chemicals.

As the component (B3), a compound of the following formula (5) is more preferable!

[0037] [Chemical 6]

[0038] As the component (B), any of the components (B1) to (B3) described above can be used.

As a preferred form of use of the component (B), the component (B1) is essential, and the combination of the component (B2) and / or the component (B3) can be used by transmitting light through the adhesive layer to the substrate. When it reaches, it is preferable because coloring of the substrate can be suppressed.

[0039] 3. Component (C)

Component (C) is a xio antioxidant.

In the present invention, by including the component (C), there is an effect of suppressing coloring particularly when light and heat are simultaneously applied to the laminate.

As the component (C), various compounds can be used as long as they have a thio atom and have an antioxidant function, and the diester-type thioether compound and / or the tetraester-type thiocarbonate are excellent because of excellent coloring suppression effect. Compounds are preferred.

[0040] As the diester type thioether compound and / or the tetraester type carbonate compound in the component (C), various compounds can be used, and the diester type thioether compound is represented by the formula because it has low volatility. As the tetraester-type carbonate compound in which the compound represented by (6) is preferred, a compound represented by the formula (7) is preferred.

[0041] [Chemical 7]

[In the formula (6), R ⁵ represents an alkyl group having 1 to 20 carbon atoms. ]

[0043] [Chemical 8]

[In the formula (7), R ⁶ represents an alkyl group having 1 to 20 carbon atoms. ]

In the above formulas (6) and (7), R ⁵ and R ⁶ are alkyl groups having 1 to 20 carbon atoms. R When the carbon number of R ⁶ is 1 or more, the solubility in the composition is sufficient, and when the carbon number is 20 or less, the desired effect can be obtained with a small amount, and a uniform composition can be obtained. can get.

[0046] Specific examples of the diester type thioether compound include dioctylthiodipropionate, dimyristyl-3,3-thiodipropionate, and the like.

Specific examples of the tetraester type thiocarbonate compound include pentaerythritol tetrakis (/ 3-laurylthiopropionate).

[0047] By the way, it is a fact widely known in the field of plastic molding materials that the heat-resistant oxidative degradation of plastic materials can be suppressed by using a phenol compound and a thioether compound in combination (Non-patent Document 1). .

[0048] Non-patent literature l: JETI (Japan Energy & Technology Intelligence), Vol. 44,

No. 5, 92-97 (1996)

[0049] However, such knowledge is not applied to the purpose of keeping coloring low in an active energy ray-curable composition, and moreover, in an active energy one-line curable adhesive composition, and further differs from the present invention. In combination, coloring is greatly promoted by heat and light.

[0050] 4. Component (D)

In the composition of the present invention, a compound having an ethylenically unsaturated group is blended for the purpose of adjusting the viscosity of the composition or adjusting the desired physical properties.

As the component (D), various compounds can be used as long as they are compounds having an ethylenically unsaturated group other than the component (A). Component (D) includes monomers, oligomers and polymers.

[0051] 4-1 Monomer

Examples of the monomer include a compound having one (meth) attalyloyl group. Such compounds include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate and 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate; hydroxyl-containing (meth) acrylates such as hydroxy ethyl (meth) acrylate and hydroxypropyl (meth) acrylate; benzyl (meth) acrylate, o—Fueyurphenyle Aromatic group-containing (meth) acrylates such as chill (meth) acrylate and P-tamylphenylethyl (meth) acrylate; and cycloaliphatic (meth) acrylates such as isobornyl (meth) acrylate Can be mentioned.

In addition to (meth) atalylate, (meth) acrylamide derivatives such as N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide and attalyloylmorpholine N-Bureformamide, N-Buyl N-Methylformamide, N-Bulucecetamide, N-Buyl N-Methylacetamide, N-Buylpyrrolidone and N-Buyl Force Prolatatum, etc. Can be mentioned.

[0052] Among these, a hydroxyl group-containing (meth) acrylate is preferable because adhesion to the substrate can be improved. In addition, when the composition is applied to an optical member or the like, the aromatic compound-containing (meth) acrylate has two aromatic groups (meta) which is preferable in that the cured product has an excellent refractive index. ) Atari rate is preferred!

[0053] Examples of the compound having two or more (meth) atalyloyl groups include ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and tripropylene glycol di Alkylene Dalicol Di (meth) atarylate such as (meth) atallylate; 1,6-Hexanediol di (meth) talylate and glycol di (meth) atalylate such as neopentylglycol di (meth) attalylate; Enolole A Di (meth) atarylate or its halogen aromatic nucleus substitution and bisphenol F di (meth) atalylate or its halogen aromatic nucleus substitution bisphenol type di (meth) talylate; dimethylol tricyclodecandi (Meta) Atarilate, Trimethylo Polyol poly, such as lepropantri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hex (meth) acrylate (Meth) acrylate; Poly (meth) acrylate of the alkylene oxide adduct of the above-mentioned polyol; Di- or tri (meth) acrylate of isocyanuric acid alkylene oxide; Examples include compounds as described on pages 53-56 of the Japan Printing Information Association (published in 1991). [0054] 4-2 oligomer

Examples of the oligomer include polyester (meth) acrylate, epoxy (meth) acrylate and polyether (meth) acrylate.

[0055] 4-2-1. Polyester (meth) acrylate oligomer

Examples of the polyester (meth) acrylate oligomer include a dehydration condensate of polyester polyol and (meth) acrylic acid.

Here, examples of the polyester polyol include a reaction product of a carboxylic acid with a polyol or an anhydride thereof.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol monoole, tetraethylene glycol monoole, polyethylene glycol mononore, propylene glycol monole, dipropylene glycol monole, tripropylene glycol monole, polypropylene glycol monole, butylene glycol monole, polybutylene glycol monole. , Tetramethylene glycol, hexamethylene glycol, neopentino glycol, cyclohexane dimethanol, 3-methanol, 1,5-pentanediol, 1,6-hexanediol, trimethylone lepronone, Examples thereof include low molecular weight polyols such as glycerin, pentaerythritol and dipentaerythritol, and adducts thereof with these alkylene oxides.

Carboxylic acids or anhydrides include dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid. The anhydride etc. are mentioned.

Other examples of the polyester poly (meth) acrylate include compounds described on pages 74 to 76 of the above-mentioned document “UV'EB Curing Material”.

[0056] 4-2-2. Epoxy (meth) acrylate oligomer

Epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin, and is described in pages 74 to 75 of the above-mentioned document “UV'EB Curing Material”. Etc.

Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

[0057] Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; Di- or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adducts; nopolac epoxy resins such as phenol novolac epoxy resin and cresol nopolac epoxy resin Glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like. In addition to these, the document “Epoxy Resins—Recent Progress 1” (Shisodo, published in 1990) Chapter 2 and the document “Polymer Processing” separate volume 9 · Volume 22 Special Issue Epoxy Resins (Polymer Publications, Examples of compounds described on pages 4-6, 9-;

[0058] Specific examples of the aliphatic epoxy resin include ethylene glycol, propylene glycol, 1,4-monobutanediol and alkyleneglycol such as 1,6-hexanediol; Diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of glycolenole and polypropylene glycolenoles; diglycidyl ethers of neopentinoleglycolanol, dibromoneopentylglycol and its alkylene oxides; trimethylolethane, trimethylolpropane , Di- or triglycidyl ethers of glycerin and its alkylene oxide adducts, and divalent, tri- or tetraglycidinyl ethers of pentaerythritol and its alkylene oxide adducts Polyglycidyl ethers of alcohols; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene O sulfoxide adduct; tetrahydrofuran barrel acid diglycidyl ether; Nono id port quinone diglycidyl ether, and the like. In addition to these, the compounds described in pages 3 to 6 of the above-mentioned document “Polymer Processing”, Epoxy Resin, can be mentioned. In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus as a skeleton, for example, TEPIC (Nissan Chemical Co., Ltd.), Denacol EX-310 (Nagase Kasei Co., Ltd.) and the like can be mentioned. In addition, compounds such as those described on pages 289 to 296 of the above-mentioned document “Polymer Processing”, separate volume epoxy resin, may be mentioned.

In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide, propylene oxide, or the like.

[0059] 4-2-3. Polyether (meth) acrylate oligomer

Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) di There are atarylates, such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate.

[0060] 4-3. Polymer

Examples of the polymer include a (meth) acrylic polymer having a (meth) acryloyloxy group, a (meth) acrylic polymer having a functional group, and a (meth) acryloyl group introduced into the side chain. Examples include compounds described on pages 78 to 79 of the document “UV'EB Curing Material”.

[0061] 5. Mixing ratio

In the present invention, as the proportion of the components (A), (B), (C) and (D), the total amount of the components (A), (B), (C) and (D) is 100% by weight. (A) component 5 to 50% by weight, (B) component 0.0;! To 5% by weight, (C) component 0.0;! To 5% by weight, (D) component 50 to 95% by weight preferable. More preferable ranges are (A) component 15 to 40% by weight, (B) component 0.05 to;!% By weight, (C) component 0.05 to;!% By weight, and (D) component 50 to 80% by weight. is there. When the proportion of component (A) is 5% by weight or more, the adhesive strength is excellent at high temperatures, and when it is 50% by weight or less, the initial adhesive strength or adhesive strength under high humidity is excellent. It becomes. When the component (B) and the component (C) are each 0.01% by weight or more, in the cured product obtained by curing the composition, the coloring by heat or light is less than 5% by weight. A uniform composition is obtained and the curability is excellent. When the component (D) is 90% by weight or less, the initial adhesive strength and the adhesive strength at high temperature or high humidity are excellent.

[0062] In addition, the composition of the present invention contains 2 to 30 wt.% Of the metatalylate compound in the total amount of the components (A) and (D) in order to prevent appearance defects such as wrinkles and warpage of the base film for shelling. % Is preferable. By containing these metatalylate compounds in the composition, the curing rate of the composition can be adjusted. When it is 2% by weight or more, it has excellent adhesive strength, and when it is 30% by weight or less, it has excellent curability and productivity.

The metatalylate compound may be appropriately selected from the aforementioned components (A) and (D).

[0063] In applications that require a small initial coloration, the components (A) and (D) The total amount of the component is less than 50% by weight of the compound having an aromatic group and an ethylenically unsaturated group, preferably S, more preferably less than 30% by weight, most preferably including the compound. There is nothing.

On the other hand, in applications where the refractive index of the cured product is required, 50% by weight or more of the compound having an aromatic group and an ethylenically unsaturated group is contained in the total amount of the component (A) and the component (D). It is preferable to be less than% by weight!

The compound having an aromatic group and an ethylenically unsaturated group may be appropriately selected from the components (D) described above.

6. Other ingredients

When the composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator may be combined as necessary.

Examples of photopolymerization initiators include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and their alkyl ethers; acetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2, 2-Diethoxy 2-phenylenoacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1 [4 (methylthio) phenyl] — 2-morpholinopropane-1-acetophenone such as 1-one; 2-methyl haloanthraquinone and 2-amylanthraquinone and other anthraquinones; 2,4 dimethyl thixanthone, 2,4 jetylthioxanthone, 2-clothioxanthone and 2,4-diiso Thioxane such as pyrthioxanthone Down; ketals such as § Seto Hue non dimethyl ketal and base emissions Jill dimethyl ketal; 2, 4, 6 phosphine trimethylbenzoyl I le diphenyl phosphite old Kishido; such as benzophenone benzophenone; and xanthone and the like can be mentioned 'be. These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator.

A preferable blending ratio of the photopolymerization initiator is 0.1% by weight or more and 10% by weight or less, more preferably 0.5% by weight or more and 5% by weight or less with respect to 100% by weight of the composition. An α-hydroxyacetophenone-based or phosphine oxide-based photopolymerization initiator is preferred because of less coloring over time.

[0065] Further, the composition of the present invention contains other antioxidants in an amount of up to 5% by weight per 100% by weight of the total of the components (A) to (D) and, if necessary, the component (i). , UV absorbers other than the component (B2), light stabilizers other than the component (B3) (HALS (hindered amine light stabilizer), etc.) Leveling agents and antifoaming agents to suppress foaming can be added.

[0066] 7. Production and Use

The production method of the composition of the present invention is not particularly limited, and can be obtained by stirring or mixing the essential components of the present invention, or the essential components and other components as necessary, by a commonly performed method.

[0067] The glass transition temperature (hereinafter referred to as Tg) after curing of the composition is preferably 10 ° C or higher and 70 ° C or lower. When Tg is 10 ° C or higher, sufficient adhesive strength can be obtained during the heat resistance test, and Tg is 7

When the temperature is 0 ° C. or lower, sufficient initial peel strength can be obtained.

In the present invention, Tg means a temperature at which the main peak of the loss tangent (tan δ) of the viscoelastic spectrum of the cured product measured at 1 Hz becomes maximum.

[0068] The composition of the present invention can be used for adhesion of various substrates, and as a method of use, a method of irradiating active energy rays after applying to a good substrate according to a conventional method, etc. Is mentioned.

As the active energy ray, ultraviolet rays are preferable because an inexpensive device including ultraviolet rays, X-rays, and electron beams can be used. Various light sources can be used for curing with ultraviolet rays, such as pressurized or high-pressure mercury lamps, methano, ride lamps, xenon lamps, electrodeless discharge lamps, and carbon arc lamps. . When curing with an electron beam, various devices can be used as an irradiation device such as a Cockloft-Walton type, a bandegraph type, and a resonance transformer type device. 1 and those having an energy of OOOeV are preferred, and more preferably 100 to 300 eV.

[0069] The composition of the present invention can be preferably used in the production of a laminate. What is necessary is just to follow the method currently performed normally. For example, there is a method in which the composition is applied to a first base material, and a second base material is bonded to the first base material, and then V, an active energy ray is irradiated from the surface of one of the base materials. In this case, at least one of the first base material and the second base material is transparent.

[0070] The composition of the present invention can be preferably used as an adhesive composition for optical materials, and more preferably used as an adhesive composition for optical film lamination.

In this case, as the substrate, a thin layer adherend used as an optical member can be used, and a laminate can be produced according to the same method as described above.

[0071] Here, the thin-layer adherend used as the optical member is mainly made of a plastic film and must be capable of transmitting active energy rays. The thin-layer adherend to be used is used as the film thickness. The thickness may be selected depending on the body and application, but preferably has a thickness of 0.1 lm or more and 1 mm or less.

Examples of the plastic in the plastic film include polychlorinated bur resin, polyvinylidene chloride, cellulosic resin, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), polyamide, polyester, polycarbonate, polyurethane, and polybule. Examples thereof include alcohol, ethylene acetate butyl copolymer, and chlorinated polypropylene. Depending on the intended use, it is also possible to use a material whose surface is treated with metal vapor deposition.

As coating methods for thin-layer adherends, Nachi-Yurano coaters, knife benor coaters, floating knives, Nyfor bite nore can be used according to conventionally known methods.

, Knife-on blanket, spray, dip, kisslow nore, squeeze rolle, sroll, air blade, curtain flow coater and gravure coater.

Further, the coating thickness of the composition of the present invention may be selected according to the thin-layer adherend to be used and the use, but is preferably 0 ··· 1,000 m, more preferably; m

[0072] Since the laminate film or sheet obtained from the adhesive composition of the present invention is excellent in adhesive strength under high temperature conditions and high humidity conditions, the polarizing film used in a liquid crystal display device or the like is used. It can be suitably used for optical films or sheets such as films, retardation films, prism sheets, brightness enhancement films, light guide plates, and diffusion plates. Example

[0073] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following examples, “parts” means% by weight.

[0074] ○ Examples 1 to 7

The components (A) to (E) and the photopolymerization initiator shown in Table 1 below were dissolved by heating and stirring at 60 ° C. for 1 hour to produce an active energy ray-curable adhesive composition. Table 2 summarizes the ratio (% by weight) (hereinafter also referred to as “MA ratio”) of metatarates in the total number of components (A) and (D) of each composition.

The obtained composition was evaluated according to the following test method. Table 3 shows the results.

[0075] [Table 1]

In Table 1, each number means the number of copies, and each abbreviation means the following.

M-1200: Urethane acrylate with a non-aromatic polyester skeleton, weight average molecular weight of about 5,000 [Aronix M-1 ²⁰⁰ manufactured by Toagosei Co., Ltd.]

2) UN-9200: Urethane acrylate with a non-aromatic polycarbonate skeleton, weight average molecular weight of about 20,000 [Negami Kogyo Art Resin UN-9200A]

3) AO-50: Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (AO-50 manufactured by Asahi Denka Kogyo Co., Ltd., where R ¹ is an octadecyl group) Compound)

4) AO-80: 3,9bis [2— {3— (3— t-butyl 4-hydroxy-5-methylphenyl] ) Propionyloxy} -1,1-dimethylethyl] —2, 4, 8, 10 Tetraoxaspiro [5 • 5] undecane (AO-80 manufactured by Asahi Denka Kogyo Co., Ltd., compound of formula (4))

5) TV900: 2-(2H benzotriazole 2 yl) 4, 6 bis (1 methyl 1-phenol cinole) fenenore [TINUVIN900, manufactured by Specialty Chemicals,

Compound in which R ⁴ is a phenyl group in 5)]

6) TV928: 2— (2H—Benzotriazole— 2-yl) — 4— (1, 1-Dimethyl— 3, 3—Dimethylbutyl-6 (1-Methanole 1 Phenylethyl) Phenonor [Ciba Special. Chemicals TINUVIN928, a compound that is R ⁴ carbyl group in formula (5)]

7) TV144: t ^ (l, 2, 2, 6, 6 Pentaethinole 4-piperidinole) [3, 5 HI, S (1, 1 dimethyl) -4-hydroxyphenyl] butyl malonate [Tinoku 'Specialty' Chemicals TINUVIN144, compound of formula (6)]

8) Sum: Dimyristyl 3, 3 'thiodipropionate [SumilizerTPM manufactured by Sumitomo Chemical Co., Ltd.]

9) AO-412: Pentaerythritol tetrakis (/ 3-laurylthiopropionate) [AO_412S manufactured by Asahi Denka Kogyo Co., Ltd.]

10) IBX: Isobornyl metatalylate [Kyoeisha Chemical Co., Ltd. Light Ester IB-X]

11) IBXA: Isobornyl attalylate (Kyoeisha Chemical Co., Ltd. Light Atrelay HB-XA)

12) HEMA: Hydroxyethyl methacrylate (Light Ester HO manufactured by Kyoeisha Chemical Co., Ltd.)

13) OPPA: Orthophenylphenol Atarylate [Aronix TO-2 344 manufactured by Toagosei Co., Ltd.]

14) Irgl84: 1-Hydroxycyclohexyl phenyl ketone [Tinoku's Specialty · Inregacure 184, manufactured by Chemicals

15) TPO: 2, 4, 6 Trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO)

[Table 2] Example MA ratio (% by weight)

1 10

2 10

3 25

4 25

5 15

6 10

7 30

[0078] 1) Test method

(1) Manufacture of specimen

The obtained composition was applied to a thickness of 10 m by a bar coater on a 75-am-thick triacetylcellulose (hereinafter abbreviated as TAC) film. A 75-mm thick TAC film was pasted onto this with a nip roll, and this was placed at 120 W / cm, 10 cm from the bottom of the concentrating metal halide lamp, and under the lamp at a conveyor speed of 5 m / min. The laminate film was manufactured by repeatedly passing the film and bonding the films together. This is called Specimen A. A laminate film was produced in the same manner as described above except that the TAC film was changed to a 50 m thick polyethylene terephthalate (hereinafter abbreviated as PET) film and the coating thickness was changed to 50 m. This is called Specimen B. The obtained specimen A was used and allowed to stand under the following conditions, and then the peel strength was evaluated.

• Initial: Leave at room temperature for 30 minutes

• After high temperature test: 500 hours at 90 ° C

• After high humidity test: 500 hours at 70 ° C and 95% RH

In addition, the obtained specimen B was allowed to stand under the following conditions and then evaluated for coloring. • After high temperature test: 500 hours at 90 ° C

• After high humidity test: 500 hours at 70 ° C and 95% RH

'Light resistance test: Using a high-pressure mercury lamp, the laminate film was irradiated with 250j / cm ² (UV A) of UV radiation.

[0079] (2) Peel strength

Specimen A is subjected to a high temperature test or high humidity test under the above conditions and then peeled off under the following conditions The strength was measured with a tensile tester.

Test piece: 25mm X 100mm

Peel angle: 180 degrees

Peeling speed: 200mm / min

In addition, when the base material was torn at the time of peel strength measurement with sufficiently strong adhesive strength, it was described as base material destruction.

The measurement unit of the peel strength: grams / inch (gf / inch) is, l (gf / inch) = 3. 86 X 10 - is ³ (N N m).

[0080] (3) Measurement of coloring

Using an integrating sphere type spectral transmittance measuring device (DOT-3C manufactured by Murakami Color Material Research Laboratory Co., Ltd.), YI value of specimen B before testing, and tests after high temperature test, high humidity test and light resistance test The YI value of body B was measured. In the table below, the coloring after each test is indicated by ΔΥΙ (difference between the YI value of specimen B after each test and the YI value of specimen B before each test).

[0081] [Table 3]

[0082] 〇 Comparative Examples 1 to 7

An active energy one-line curable adhesive composition was produced in the same manner as in the Examples except that the components shown in Table 4 below were used. Table 5 summarizes the MA ratio of each composition.

The obtained composition was evaluated in the same manner as in Example 1. Table 6 shows the results.

[0083] [Table 4] Ratio (A) (A) '(B) (C) (C)' (D) Photoinitiator Comparison M-M- AO-AO-TV TV AO-SZ-3

Example Sum IBX IBXA HEMA OPPA TPO 1200 1600 ¹⁶ ) 50 80 900 928 412

1 30 10 60 2 1

2 30 ― ― 0.3 ― ― ― ― One ― ― 10 60 2 1

3 30 ― ― One ― 0.2 ― One 10 ― 15 55 2 1

4 ― 20 10 ― 15 55 2 1

5 ― 20 0.2 1.0 ― 0.2 ― 10 ― 15 55 2 1

6 30 ― ϋ.ο ― 1.0 ― ― ― 0.2 ― ― 10 60 2 1

7 25 45 30 ― 2 1

[0084] In Table 4, each number represents the number of copies, and each abbreviation has the same meaning as in Table 1 except for the following.

16) M-1600: Polyether urethane acrylate, weight average molecular weight of about 3,000 [Aronix M-1600, manufactured by Toagosei Co., Ltd.]

17) SZ-3: 1,2-bis (2-hydroxyethylthio) ethane [SZ-3, Sakai Chemical Co., Ltd.] [0085] [Table 5]

[0086] [Table 6]

Peel strength (gf / inch) Color ratio ■ S

-= Γ: Β Humidity Light resistance

'Display Initial

Example After initial test After test After test After test After test (ΥΙ)

(Δ ΥΙ) (Δ ΥΙ) (ΔΥΙ)

1 880 920 740 1.8 1.4 1.5 2.1

2 870 880 720 1.6 0.9 1.1 1.9

3 890 920 790 1.9 1.6 1.4 2.0

4 230 150 10 1.8 2.7 2.5 3.1

5 220 150 10 1.4 1.7 1.5 1.8

6 890 910 720 1.4 1.6 1.4 2.6

7 930 930 900 1.1 0.8 0.8 0.4 As is clear from the examples, according to the present invention, excellent adhesive force can be maintained even under high temperature and high humidity conditions, and the obtained optical member is made of heat, Humidity and coloring due to light can be kept low, and it can be suitably used particularly for the production of optical films such as liquid crystal display devices.

On the other hand, as is clear from the comparative examples, coloring cannot be suppressed to a low level with a composition that does not contain the components (B) and (C). In addition, when the component (A) is not used, sufficient adhesive strength cannot be obtained.

Claims

The scope of the claims

[1] (A) Urethane (meth) acrylate having a polyester or polycarbonate skeleton

(B) a phenol compound having at least one group — C (CH 2) R (wherein R represents an alkyl group or a phenyl group) in the phenyl group;

(C) Xio antioxidant, and

(D) An active energy ray-curable adhesive composition comprising a compound having an ethylenically unsaturated group other than the component (A).

[2] When the total amount of the components (A), (B), (C) and (D) is 100% by weight, the component (A) is 5 to 50% by weight, the component (B) is 0.0; The active energy ray-curable adhesive composition according to claim 1, comprising 5% by weight, (C) component 0.0;! To 5% by weight and (D) component 50 to 95% by weight.

[3] The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the component (B) contains a compound represented by the following formula (1).

[Chemical 1]

[4] The active energy ray-curable adhesive composition according to claim 3, wherein the component (B) includes a compound (B1) in which X in the formula (1) is a group having one or more ester bonds. .

[5] The active energy ray-curable adhesive composition according to [4], wherein (B1) is a compound represented by the following formula (2).

[Chemical 2] CH ₂ CH ₂ — C 1 0— R ⁴

II

o

(2)

[In the formula (2), R ⁴ represents an alkyl group having 1 to 20 carbon atoms. ]

5. The actinic radiation curable adhesive composition according to claim 4, wherein (B1) is a compound represented by the following formula (3).

[Chemical 3]

[7] The component (B) comprises the component (Bl) and at least one group C (CH) R (R

3 2 represents an alkyl group or a phenyl group and further has a benzotriazol group (B2) or / and at least a group C (CH 2) R (where R is an alkyl group or

3 2

The active energy ray-curable adhesive composition according to any one of claims 4 to 6, further comprising a compound (B3) having a hindered amino group and having a hindered amino group.

[8] The active energy one-line curable adhesive composition according to any one of claims 1 to 7, wherein the component (C) is a diester type thioether compound or / and a tetraester type thiocarbonate compound. .

[9] The active energy ray-curable adhesive composition according to claim 8, wherein the diester type thioether compound is a compound represented by the following formula (6).

[Chemical 4]

[In the formula (6), R ⁵ represents an alkyl group having 1 to 20 carbon atoms. ] 9. The active energy ray-curable adhesive composition according to claim 8, wherein the tetraester type thiocarbonate compound is a compound represented by the following formula (7).

[Chemical 5]

[However, in Formula (7), R ° represents an alkyl group having 1 to 20 carbon atoms. ]

[11] The active energy one-line curable adhesive composition according to any one of claims 1 to 10, further comprising a photopolymerization initiator.

[12] Claims 1 to 11, wherein the total amount of the component (A) and the component (D) contains 2 to 30% by weight of the metatalylate compound. Adhesive composition

Yes

[13] An active energy ray-curable optical film laminating adhesive composition comprising the composition according to any one of claims 1 to 12.

[14] The step of applying the composition according to any one of claims 1 to 12 to the first substrate,

The step of bonding the second substrate to the first substrate coated with the composition, and after bonding the second substrate, the active energy rays from the surface of the misaligned substrate Including the process of irradiation

A manufacturing method of a layered product.