JP2016204513A - Adhesive composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition having excellent adhesiveness to a polycarbonate substrate.SOLUTION: There is provided an adhesive composition which comprises an alicyclic epoxy compound(A), a (meth)acrylic compound (B) containing a (meth)acrylic monomer (b) having a cyclic ether structure and a photopolymerization initiator (C). In addition, there is provided a laminate which sequentially has a polycarbonate substrate and an adhesive layer obtained by curing the adhesive composition. The adhesive composition has excellent adhesiveness to a polycarbonate substrate. Thus, the adhesive composition can be suitably used as an adhesive used for various applications such as automotive, optical component and construction applications.SELECTED DRAWING: None

Description

  The present invention relates to an adhesive composition having excellent adhesion to a polycarbonate substrate.

  In recent years, plastic materials have been used in many fields such as automobiles and optical materials for the purpose of weight reduction. Among these, polycarbonates having high durability are expected to be used in the future. At that time, a polycarbonate molded product may be fixed and used by adhesion. In addition to solvent-based and water-based adhesives, many studies have been made on UV-curable adhesives.

  Examples of the ultraviolet curable adhesive include a glycidyl ether group-containing compound obtained by distilling cyclohexanedimethanol diglycidyl ether and a glycidyl ether group-containing compound obtained by distilling bisphenol F type diglycidyl ether. An adhesive containing a hydrolyzable silyl group and epoxy group-containing compound and a photopolymerization initiator and having a chlorine content of 500 ppm is disclosed (for example, see Patent Document 1).

  However, the adhesive is not sufficiently adhesive to the polycarbonate substrate, and has not yet reached a practical level.

JP 2010-32766 A

  The problem to be solved by the present invention is to provide an adhesive composition having excellent adhesion to a polycarbonate substrate.

  The present invention contains an alicyclic epoxy compound (A), a (meth) acrylic compound (B) containing a (meth) acrylic monomer (b) having a cyclic ether structure, and a photopolymerization initiator (C). An adhesive composition is provided.

  Moreover, this invention provides the laminated body characterized by having a polycarbonate base material and the adhesive bond layer which hardened the said adhesive composition one by one.

  The adhesive composition of this invention is excellent in the adhesiveness to a polycarbonate base material. Therefore, the adhesive composition of the present invention can be suitably used as an adhesive used in various applications such as automobiles, optical parts, and architectural applications.

  The adhesive composition of the present invention includes an alicyclic epoxy compound (A), a (meth) acrylic compound (B) containing a (meth) acrylic monomer (b) having a cyclic ether structure, and a photopolymerization initiator ( C).

  As the alicyclic epoxy compound (A), for example, a compound having 1 to 4 alicyclic epoxy groups can be used.

  As the alicyclic epoxy compound having one alicyclic epoxy group, for example, an alicyclic epoxy compound represented by the following general formula (1) can be used.

（式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して水素原子又はメチル基を表す。）

(In formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group.)

  As an alicyclic epoxy compound shown by the said General formula (1), "Celoxide 3000" (made by Daicel Chemical Industries Ltd.) etc. are marketed, for example.

  Examples of the alicyclic epoxy compound having two alicyclic epoxy groups include 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate represented by the following general formula (2) (general formula (2)). Wherein a is 0 compound), its caprolactone-modified product (in general formula (2), a is 1 compound), its trimethylcaprolactone-modified product (Structural Formula (3 and Structural Formula (4)), and A valerolactone modified product (Structural Formula (5) and Structural Formula (6)) or a compound represented by Structural Formula (7) can be used.

（一般式（２）中のａは０または１を表す。）

(A in the general formula (2) represents 0 or 1)

  Moreover, as an alicyclic epoxy compound which has two said alicyclic epoxy groups, a compound as shown by following General formula (8) can be used.

（一般式（８）中Ｒ^１〜Ｒ^６は、それぞれ独立して、水素原子または炭素原子数1〜６のアルキル基を示す。）
前記一般式（８）に示される化合物としては、具体的には、ジシクロヘキシル−３，３’−ジエポキシドを用いることができる。

(In formula (8), R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
As the compound represented by the general formula (8), specifically, dicyclohexyl-3,3′-diepoxide can be used.

  Moreover, as an alicyclic epoxy compound which has three alicyclic epoxy groups, the compound shown by following General formula (9) can be used.

（一般式（９）中、ａ及びｂは、それぞれ独立して０又は１であり、それらは同一であっても異なっていてもよい。）

(In general formula (9), a and b are each independently 0 or 1, and they may be the same or different.)

  As the alicyclic epoxy compound represented by the general formula (9), for example, Epolide GT301, Epolide GT302 (manufactured by Daicel Chemical Industries, Ltd.) and the like are commercially available.

  Moreover, as an alicyclic epoxy compound which has four alicyclic epoxy groups, the compound shown, for example by following General formula (10) can be used.

（前記一般式（１０）中、ａ〜ｄは、それぞれ独立して０又は１を示し、それらは同一であっても異なっていてもよい。）

(In the general formula (10), a to d each independently represent 0 or 1, and they may be the same or different.)

  As the alicyclic epoxy compound represented by the general formula (10), for example, Epolide GT401, Epolide GT403 (manufactured by Daicel Chemical Industries, Ltd.) and the like are commercially available.

  The alicyclic epoxy compound (A) has two alicyclic epoxy groups because it has the best ultraviolet curability and can form a good crosslink density to further improve the adhesion to the polycarbonate substrate. It is preferable to use an alicyclic epoxy compound, and it is more preferable to use 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

  The alicyclic epoxy compound (A) may be used in combination with other cationically polymerizable compounds as necessary.

  As said other cationically polymerizable compound, aliphatic glycidyl ether, aromatic glycidyl ether, an oxetane compound etc. can be used, for example. These compounds may be used alone or in combination of two or more.

  As content of the said alicyclic epoxy compound (A), it is preferable that it is the range of 5-40 mass% in an adhesive composition from the point which can achieve ultraviolet sclerosis | hardenability and adhesive force, and 8-30 mass%. The range of is more preferable.

  The (meth) acrylic monomer (b) having the cyclic ether structure is an essential component for obtaining excellent adhesion to a polycarbonate substrate. The reason why the adhesiveness to the polycarbonate base material is improved by using the monomer (b) is an improvement in adhesive force by cation curing and an interaction such as hydrogen bonding with the base material surface by ether oxygen. I guess that.

  As the (meth) acrylic monomer (b), it is preferable to use a (meth) acrylic monomer having a cyclic ether structure in the range of a three-membered ring to a six-membered ring. These monomers may be used alone or in combination of two or more.

  Examples of the (meth) acrylic monomer having a three-membered cyclic ether structure include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, 5-hydroxypentyl (meth) acrylate glycidyl, 6-hydroxyhexyl (meth) acrylate glycidyl ether, OO and the like can be used. These monomers may be used alone or in combination of two or more.

  Examples of the (meth) acrylic monomer having a four-membered cyclic ether structure include (3-methyloxetane-3-yl) methyl (meth) acrylate, (3-propyloxetane-3-yl) methyl ( (Meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, (3-butyloxetane-3-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) ethyl (meth) Acrylate, (3-ethyloxetane-3-yl) propyl (meth) acrylate, (3-ethyloxetane-3-yl) butyl (meth) acrylate, (3-ethyloxetane-3-yl) pentyl (meth) acrylate, (3-Ethyloxetane-3-yl) hexyl (meth) acrylate or the like can be used. These monomers may be used alone or in combination of two or more.

  Examples of the (meth) acrylic monomer having a five-membered cyclic ether structure include tetrahydrofurfuryl (meth) acrylate, γ-butyrolactone (meth) acrylate, (2,2-dimethyl-1,3-dioxolane-4 -Yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (2-methyl-2-isobutyl-1,3-dioxolane-4 -Il) methyl (meth) acrylate, (2-cyclohexyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, and the like can be used. These monomers may be used alone or in combination of two or more.

  Examples of the (meth) acrylic monomer having a six-membered cyclic ether structure include tetrahydro-2H-pyran-2-yl- (meth) acrylate, 2- {1-[(tetrahydro-2H-pyran- 2-yl) oxy] -2-methylpropyl} (meth) acrylate, cyclic trimethylolpropane formal acrylate, (meth) acryloylmorpholine, and the like can be used. These monomers may be used alone or in combination of two or more.

  As the (meth) acrylic monomer (b), a (meth) acrylic monomer having a tetrahydrofuran structure is used from the viewpoint that the adhesion is further improved by dissolving the polycarbonate surface as an adherend. Of these, tetrahydrofurfuryl (meth) acrylate is more preferably used because it is particularly excellent in solubility and the adhesiveness is further improved.

  The content of the (meth) acrylic monomer (b) is in the range of 20 to 80% by mass in the adhesive composition from the viewpoint of the balance between UV curability and adhesiveness to the polycarbonate substrate. The range of 25 to 75% by mass is more preferable.

  Examples of the (meth) acrylic compound (B) that can be used in addition to the (meth) acrylic monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl ( (Meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, 3-methylbutyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) Chlorate, stearyl (meth) acrylate, neopentyl (meth) acrylate, hexadecyl (meth) acrylate, isoamyl (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Aliphatic (meth) acrylates such as 1,6-hexanediol di (meth) acrylate and neopentylglycol di (meth) acrylate; isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate; Sibutyl (meth) acrylate), 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, and methoxypolyethylene glycol having 1 to 15 moles of oxyethylene added (Meth) acrylates having ether groups such as acrylate, ethoxy-diethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl (meth) acrylate , Aromatic (meth) acrylates such as phenoxypolyethylene glycol acrylate, phenyl (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate; Acrylamide, acryloylmorpholine, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, diacetone (meth) acrylamide and other (meth) acrylamide etc. Can be used. These (meth) acrylic compounds may be used alone or in combination of two or more.

  As the (meth) acrylic compound (B) that can be used in addition to the (meth) acrylic monomer (b), the flexibility of the adhesive film can be controlled to further improve the adhesion to the adherend substrate. In view of this, it is preferable to use a (meth) acrylic monomer capable of forming a homopolymer having a glass transition temperature of −15 ° C. or lower, and methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl. It is more preferable to use one or more (meth) acrylic monomers selected from the group consisting of acrylate, isooctyl acrylate, isononyl acrylate, tridecyl acrylate, and isostearyl acrylate. In addition, the glass transition temperature at the time of homopolymer formation of the said (meth) acryl monomer can be obtained from a polymer handbook (4th ed.) And the manufacturer homepage of a (meth) acryl monomer.

  As content of the said (meth) acryl monomer (B), it is preferable that it is the range of 20-93 mass% in an adhesive composition, and the range of 50-90 mass% is more preferable.

  As the photopolymerization initiator (C), a cationic polymerization initiator (C-1), a radical polymerizable initiator (C-2), or the like can be used.

The cationic polymerization initiator (C-1) refers to a compound that generates an acid capable of initiating cationic polymerization upon irradiation with energy rays such as ultraviolet rays. As the cationic polymerization initiator (C-1), for example, the cation moiety may be aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrhenium, thioxanthonium, (2,4-cyclopentadiene). -1-yl) [(1-methylethyl) benzene] -Fe cation, and the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (where X is at least two or more Or an onium salt composed of a phenyl group substituted with a fluorine or trifluoromethyl group), or two or more of them can be used in combination.

  Examples of the aromatic sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- ( Diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenyl) Thio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- ( Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimony Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate and the like can be used.

  Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and bis (dodecylphenyl) iodonium hexafluorophosphate. Bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyl Iodonium hexafluorophosphate, 4-methylphenyl-4- (1-methyl Ruethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Etc. can be used.

  Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.

  Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl 2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-Cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate, and the like can be used.

  Moreover, S-biphenyl 2-isopropyl thioxanthonium hexafluorophosphate etc. can be used as said thioxanthonium salt.

  The (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene. ] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, 2,4-cyclopentadiene-1- Yl) [(1-methylethyl) benzene] -Fe (II) tetrafluoroborate, 2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) ) Borate or the like can be used.

Examples of the cationic polymerization initiator (C-1), from viewpoint of further improving the ultraviolet-curable, cationic portion aromatic sulfonium, anionic moiety, PF 6 ^_- it is preferable to use a.

  Examples of the cationic polymerization initiator (C-1) include CPI-100P, CPI-101A, CPI-110P, CPI-200K, CPI-210S (manufactured by San Apro Co., Ltd.), and Cyracure photocuring initiator UVI-. 6990, Syracure photocuring initiator UVI-6922, Syracure photocuring initiator UVI-6976 (above, manufactured by Dow Chemical Japan Co., Ltd.), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP -170, Adekaoptomer SP-172, Adekaoptomer SP-300 (above, manufactured by ADEKA Corporation), Esacure 1064, Esacure 1187 (above, manufactured by Lamberti), Omnicat 550 (produced by IG Resin), Irgacure 250 (BASF Baking Co., Ltd.), etc. Rodoshiru photo initiator 2074 (RHODORSIL PHOTOINITIATOR 2074 (manufactured by Rhodia Japan Co., Ltd.) are commercially available.

  Examples of the radical polymerizable initiator (C-2) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl. -1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone, oligo {2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl) Acetophenone compounds such as l-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one; benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyl- Benzophenone compounds such as diphenylsulfide; methyl benzoylformate, oxy-phenyl-acetic acid 2- (2-oxo-2-phenyl-acetoxy-ethoxy) -ethyl ester and oxy-phenyl-acetic acid 2- (2 Α-ketoester compounds such as -hydroxy-ethoxy) -ethyl ester; thioxanthone compounds such as 2-isopropylthioxanthone and 2,4-diethylthioxanthone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxa Phosphine oxide compounds such as id, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide; Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; N- (2-hydroxyethyl) maleimide, N- (2-hydroxyethyl) citraconimide, N- (2-hydroxyethyl) dimethyl Maleimide compounds such as maleimide, N- (2-hydroxyethyl) -3,4,5,6-tetrahydrophthalimide, N- (2-acryloxyethyl) -3,4,5,6-tetrahydrophthalimide; titanosenation Acetophenone / benzophenone hybrid photoinitiators such as 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 1,2-octane Oxime ester compounds such as dione and 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] can be used. These initiators may be used alone or in combination of two or more.

  The total amount of the photopolymerization initiator (C) used is preferably in the range of 0.1 to 10% by mass in the adhesive composition from the viewpoint of further improving ultraviolet curability. More preferably, it is in the range of mass%.

  The adhesive composition of the present invention contains the alicyclic epoxy compound (A), the (meth) acrylic compound (B), and the photopolymerization initiator (C) as essential components. Other additives can be included.

  Examples of the other additives include silane coupling agents, thixotropic agents, leveling agents, antioxidants, thermal stabilizers, light stabilizers, antistatic agents, foam stabilizers, antifoaming agents, and the like. Can do. These additives may be used alone or in combination of two or more.

  The viscosity of the adhesive composition of the present invention is preferably in the range of 5 to 3,000 mPa · s. The viscosity of the adhesive composition is a value measured at 25 ° C. with a B-type viscometer.

  The adhesive composition can be cured by irradiation with energy rays such as ultraviolet rays. In addition, the said adhesive composition expresses adhesiveness only by irradiation of energy rays, such as an ultraviolet-ray.

The irradiation energy of the energy beam, such as the ultraviolet, from the viewpoint of curability, preferably in the range of 0.1~10J / cm ^2, more preferably in the range of 0.2~5J / cm ^2, 0. The range of 25-3 J / cm ² is more preferable.

The illuminance of energy rays such as ultraviolet rays is preferably in the range of 0.001 to ² W / cm ² and more preferably in the range of 0.01 to 1.5 W / cm ² from the viewpoint of adhesiveness and curability. A range of 0.05 to 1 W / cm ² is more preferable.

  For example, a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED can be used as the ultraviolet ray generation source. In addition, the irradiation energy and illuminance of ultraviolet rays are based on values measured in a wavelength range of 320 to 390 nm using a UV checker; UV Power PucK (II) (manufactured by Electronic Instrumentation and Technology).

  As mentioned above, the adhesive composition of this invention is excellent in the adhesiveness to a polycarbonate base material. Therefore, the adhesive composition of the present invention can be suitably used as an adhesive used in various applications such as automobiles, optical parts, and architectural applications.

  When the adhesive composition of the present invention is used for adhesion of a polycarbonate substrate, it has a polycarbonate substrate and an adhesive layer obtained by curing the adhesive composition, a polycarbonate substrate or another substrate in this order. A laminate is obtained.

  As thickness of the said polycarbonate base material, it is the range of 10-5,000 micrometers, for example.

  As a method of applying the adhesive composition to the substrate, for example, a slit coater method such as a curtain flow coater method or a die coater method, a knife coater method, a roll coater method, a gravure coater method, a method of applying by spraying, etc. Is mentioned.

  The thickness of the adhesive layer is, for example, in the range of 0.5 to 50 μm.

  Examples of the other base materials include cycloolefin resin base materials, (meth) acrylic resin base materials, silicon resin base materials, epoxy resin base materials, fluororesin base materials, polystyrene resin base materials, polyester resin base materials, and polysulfone. Resin base material, polyarylate resin base material, polyvinyl chloride resin base material, polyvinylidene chloride base material, amorphous polyolefin resin base material, polyimide resin base material, alicyclic polyimide resin base material, cellulose resin base material, TAC (Triacetylcellulose) substrate, COP (cycloolefin polymer) substrate, PC (polycarbonate) substrate, PBT (polybutylene terephthalate) substrate, modified PPE (polyphenylene ether) substrate, PEN (polyethylene naphthalate) group Material, PET (polyethylene terephthalate) substrate, polylactic acid polymer substrate, Lath, the metal plate can be used wood or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (“Celoxide 2021P” manufactured by Daicel Corporation, Hereinafter, abbreviated as “CEL2021P”) is 20 parts by mass, tetrahydrofurfuryl acrylate (“Osaka Organic Chemical Co., Ltd.“ Biscoat 150 ”, hereinafter abbreviated as“ V150 ”) is 70 parts by mass, ethoxylated pentaerythritol. 10 parts by mass of tetraacrylate (“ATM-35E” manufactured by Shin-Nakamura Chemical Co., Ltd.) was added and mixed with stirring until uniform. Thereafter, as a photopolymerization initiator, 0.8 parts by mass of “Irgacure 184” manufactured by BASF and 0.8 parts by mass of “CPI-100P” manufactured by San Apro Co., Ltd. were added and stirred and mixed. Then, it filtered with a 200 mesh wire mesh, and obtained the adhesive composition.

[Examples 2 to 27, Comparative Examples 1 to 4]
An adhesive composition was obtained in the same manner as in Example 1 except that the compounds and amounts shown in Tables 1 to 3 were changed.

[Adhesion evaluation method]
The adhesive compositions obtained in Examples and Comparative Examples were applied to a polycarbonate plate having a thickness of 800 μm so as to be 2 μm. Thereafter, a polycarbonate plate having a thickness of 800 μm was further bonded. The adhesive composition was cured by irradiating ultraviolet rays at an illuminance of ultraviolet rays of 1 W / cm ² and an integrated light amount of 1 J / cm ² from above the polycarbonate plate by an ultraviolet irradiation device.
The obtained laminate was peeled by hand in the 180 ° direction, and the adhesion to polycarbonate was evaluated as follows.
“○”: Difficult to peel by hand.
“△”: Can be peeled by hand, but is difficult to peel.
“X”: Easy peeling by hand.

Abbreviations in Tables 1 to 3 will be described.
“M-305”; pentaerythritol triacrylate (“Aronix M-305” manufactured by Toagosei Co., Ltd.)
“FA-513AS”; dicyclopentanyl acrylate (“Funkryl FA-513AS” manufactured by Hitachi Chemical Co., Ltd.)
“A-BPE-4”; ethoxylated bisphenol A diacrylate (“A-BPE-4” manufactured by Shin-Nakamura Chemical Co., Ltd.)
“AHD-N”; 1,6-hexanediol diacrylate (“AHD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.)
“DCP-A”; dimethylolpropane tricyclodecane diacrylate (“light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.)
“NOAA”; n-octyl acrylate “2-EHA”; 2-ethylhexyl acrylate “BA”; n-butyl acrylate “KBM-403”; 3-glycidoxypropyltrimethoxysilane (“KBM-” manufactured by Shin-Etsu Silicone Co., Ltd.) 403 ")
“KBM-803”; 3-mercaptopropyltrimethoxysilane (“KBM-803” manufactured by Shin-Etsu Silicone Co., Ltd.)
“CEL2000”; 1,2-epoxy-4-vinylcyclohexane (“Celoxide 2000” manufactured by Daicel Corporation)
“GMA”; glycidyl methacrylate “OXE-10”; (3-ethyloxetane-3-yl) methyl acrylate (“OXE-10” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
“OXT-221”; 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (“OXT-221” manufactured by Toagosei Co., Ltd.)
"PB3600": Epoxidized polybutadiene ("Epolyd PB3600" manufactured by Daicel Corporation)

  It turned out that the adhesive composition of this invention is excellent in the adhesiveness to a polycarbonate base material.

  On the other hand, although the comparative examples 1 and 2 are the aspects which do not use a (meth) acryl compound (B), the laminated body can be peeled easily by hand and the adhesiveness to a polycarbonate base material was unsatisfactory.

  Although the comparative example 3 is an aspect which does not use a (meth) acryl monomer (b), the laminated body could be peeled easily by hand and the adhesiveness to a polycarbonate base material was poor.

  Although the comparative example 4 is an aspect which does not use an alicyclic epoxy compound (A), the laminated body could be peeled easily by hand and the adhesiveness to a polycarbonate base material was poor.

Claims (6)

It contains an alicyclic epoxy compound (A), a (meth) acrylic compound (B) containing a (meth) acrylic monomer (b) having a cyclic ether structure, and a photopolymerization initiator (C). An adhesive composition. The adhesive composition according to claim 1, wherein the content of the (meth) acrylic monomer (b) having an alicyclic ether structure is in the range of 20 to 80% by mass in the adhesive composition. The adhesive composition according to claim 1, wherein the (meth) acrylic monomer (b) having an alicyclic ether structure is a (meth) acrylic monomer having a five-membered cyclic ether structure. The adhesive composition according to claim 1, wherein the content of the alicyclic epoxy compound (A) is in the range of 5 to 40% by mass in the adhesive composition. The adhesive composition according to claim 1, wherein the alicyclic epoxy compound (A) is an alicyclic epoxy compound having two alicyclic epoxy groups. A laminate comprising a polycarbonate substrate and an adhesive layer obtained by curing the adhesive composition according to any one of claims 1 to 5.