KR20200026741A - Active energy ray-curable adhesive composition, cured product and adhesive sheet - Google Patents

Abstract

The present invention relates to an active energy ray-curable adhesive composition, a cured product, and an adhesive sheet. The purpose of the present invention is to provide an active energy ray-curable adhesive composition which can be also used without solvent, is compatible with high step cushioning properties and processability and has excellent adhesiveness even in case of a single layer; a cured product, and an adhesive sheet. The active energy ray-curable adhesive composition comprises: (A) polyurethane, i.e., a reactant of (a1) polyol, (a2) aliphatic polyisocyanate, (a3) a hydroxyl group-containing mono(meth)acrylate, and (a4) a hydroxyl group-containing photopolymerization initiator; (B) one or more alkylmono(meth)acrylates selected from (b1) an alkylmono(meth)acrylate having 4 to 18 carbon atoms of a linear alkyl group which does not contain an alicyclic structure, an alkylmono(meth)acrylate having 4 to 18 carbon atoms of a branched alkyl group which does not contain an alicyclic structure, and (b2) an alkylmono(meth)acrylate having 6 to 15 carbon atoms of an alkyl group which contains an alicyclic structure; and (C) a primary hydroxyl group-containing mono(meth)acrylate, wherein 10 to 90 mol% of the component (a3) and 10 to 90 mol% of the component (a4) are introduced with respect to an isocyanate group at the end of a urethane prepolymer comprised of the component (a1) and the component (2).

Description

ACTIVE ENERGY RAY-CURABLE ADHESIVE COMPOSITION, CURED PRODUCT AND ADHESIVE SHEET}

  TECHNICAL FIELD This invention relates to an active energy ray hardening-type adhesive composition, hardened | cured material, and an adhesive sheet.

Recently, display devices such as touch panels have been used in digital information devices such as mobile phones, portable game consoles, and car navigation systems. Moreover, many optical members, such as a liquid crystal element, a light emitting diode element, and an organic electroluminescent element, are used for such a display apparatus.

In manufacturing the display device, a transparent double-sided adhesive sheet is used for the purpose of bonding the display device and the optical member or the optical member to each other. Such a double-sided adhesive sheet is required to have performances such as transparency, weather resistance, and metal corrosion resistance.

In addition, in the touch panel, in order to improve the design (cosmeticity), the make-up printing (printing on the back of the periphery of the display (such as the white part of the glass cover on the surface)) is applied to the frame portion. Some are implemented. Since the cosmetic printing generates a step between the printed part and the non-printed part, the adhesive layer of the double-sided adhesive sheet has a followability (hereinafter referred to as "step difference tracking") to fill such a printing step. Required. If the step tracking ability is insufficient, the adhesive layer may be lifted in the vicinity of the step, thereby causing a reflection loss of light.

On the other hand, when processing an adhesive sheet, there exists a process of cutting | disconnection and it is calculated | required that the adhesive layer of a cut part does not adhere to a blade after cutting. Moreover, it is also necessary that cross-sectional roughness does not generate | occur | produce in the adhesion layer of a cut part. In the case where the elastic modulus at room temperature in the adhesive layer is low, after the punching process, the adhesive layer of the cut portion adheres to the punching blade and there is a fear that the cross-section roughness of the cut portion of the adhesive layer may occur. This gets worse.

As an adhesive layer which improved the step | following tracking property and flexibility, the thermosetting ultraviolet curable adhesive composition containing the base polymer containing a methacrylic acid ester monomer, and a plasticizer is proposed (refer patent document 1). Moreover, as an adhesive sheet which improved the step | following | tracking followability and the punching processability, it is an adhesive layer provided with the polymerizable urethane polymer (A) which has ethylenically unsaturated group in the both ends of a molecule | numerator, and one hydroxyl group in the one terminal of a molecule | numerator. Moreover, the ultraviolet curable adhesive composition containing the polymeric urethane polymer (B) and monofunctional acrylate which have one ethylenically unsaturated group in the other terminal is proposed (refer patent document 2).

Japanese Patent Laid-Open No. 2015-105329 Japanese Patent Laid-Open No. 2012-251030

In patent document 1, since the plasticizer of a low softening point is used, the fall of a holding force at high temperature is anxious. Moreover, since the plasticizer of a low softening point is used, the elasticity modulus at room temperature will become low, and a cutting part may adhere to a punching blade after a punching process, and the cross-section roughness of the cut part of an adhesion layer may arise. Moreover, since the said ultraviolet curable adhesive composition contains many solvents, the process of removing a solvent is needed when producing an adhesive sheet.

Only the combination of the polyfunctional urethane acrylate and the monofunctional urethane acrylate of Patent Literature 2 is insufficient in adhesion to the substrate and step comparability. In addition, although patent document 2 does not perform an endurance test (heat resistance, heat-and-moisture resistance test, etc.), even if it carries out an endurance test, peeling off and a step tracking followability may fall after a test.

An object of this invention is to provide the active energy ray hardening-type adhesive composition, hardened | cured material, and an adhesive sheet which can be used also as a solvent-free, even if it is a single layer, is compatible with high step | following | following traceability, workability, and excellent also in adhesive force.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said subject can be solved by using the predetermined | prescribed active energy ray hardening-type adhesive composition, its hardened | cured material, and the adhesive sheet provided with this hardened | cured material, and this invention Completed.

That is, the present invention relates to the following items 1 to 8.

(Item 1)

(A) Polyurethane which is a reaction product of (a1) polyol, (a2) aliphatic polyisocyanate, (a3) hydroxyl-containing mono (meth) acrylate, and (a4) hydroxyl-containing photoinitiator,

(B) (b1) Alkyl mono (meth) acrylate having 4 to 18 carbon atoms of a linear alkyl group containing no alicyclic structure, Alkyl mono (meth) having 4 to 18 carbon atoms of a branched alkyl group containing no alicyclic structure One or more alkyl mono (meth) acrylates selected from alkylmono (meth) acrylates having 6 to 15 carbon atoms in the alkyl group containing a) acrylate and (b2) an alicyclic structure,

(C) containing a primary hydroxyl group containing mono (meth) acrylate,

10 mol% or more and 90 mol% or less of (a3) component is introduce | transduced into the isocyanate group in the terminal of the urethane prepolymer which (A) component consists of (a1) component and (a2) component, and (a4) component is 10 mol% More than 90mol%

Active energy ray curable pressure-sensitive adhesive composition.

(Item 2)

When the sum total of (A) component, (B) component, and (C) component is 100 mass%, (A) component is 20 mass% or more and 70 mass% or less, and (B) component is 25 mass% or more The active energy ray-curable adhesive composition described in item 1 which is 75 mass% or less and (C) component is 5 mass% or more and 55 mass% or less.

(Item 3)

The active energy ray-curable pressure-sensitive adhesive composition according to item 1 or 2, wherein the number average molecular weight of the component (a1) is 700 or more and 10,000 or less.

(Item 4)

The active energy ray-curable pressure-sensitive adhesive composition according to any one of items 1 to 3, wherein the component (a3) is a hydroxyl group-containing mono (meth) acrylate having 5 to 10 carbon atoms.

(Item 5)

The active energy ray-curable pressure-sensitive adhesive composition according to any one of items 1 to 4, wherein the weight average molecular weight of the component (A) is 10,000 or more and 90,000 or less.

(Item 6)

Hardened | cured material of the active-energy-ray-curable adhesive composition in any one of items 1-5.

(Item 7)

Hardened | cured material of item 6 whose storage elastic modulus G 'in 25 degreeC and 1 Hz is 8 * 10 <^4> Pa or more, and the loss coefficient TAδ in 50 degreeC and 1Hz is 0.4 or more.

(Item 8)

An adhesive sheet comprising the cured product described in item 6 or 7 on at least one side of the surface of the substrate.

Since the active energy ray-curable pressure-sensitive adhesive composition of the present invention can be used even without a solvent, the solvent removal step can be omitted when producing the pressure-sensitive adhesive sheet. Moreover, even if it is a single layer, the adhesion layer (henceforth "hardened | cured material") of the active-energy-ray-curable adhesive composition of this invention is a high step | following traceability (namely, flexibility at the time of heating), and workability (namely, toughness at room temperature). )) Is compatible and exerts excellent adhesion. In addition, the adhesive layer is colorless and transparent, and excellent in high temperature, high humidity heat environment.

The present invention,

(A) (a1) polyol (henceforth "the (a1) component"), (a2) aliphatic polyisocyanate (henceforth "the (a2) component"), (a3) hydroxyl-containing mono (meth) acrylate (Hereinafter also referred to as "(a3) component") and polyurethane (which is also referred to as "(A) component") which is a reactant of (a4) hydroxyl-containing photoinitiator (hereinafter also called "(a4) component") ,

(B) (b1) Alkyl mono (meth) acrylate of 4 to 18 carbon atoms of straight chain alkyl group not containing alicyclic structure, 4 to 18 carbon atoms of branched alkyl group not containing alicyclic structure Alkyl mono (meth) acrylate (hereinafter, also referred to as "(b1) component") and an alkyl group containing 6 to 15 carbon atoms of the alkyl group containing an alicyclic structure (hereinafter referred to as "(b2) One or more alkyl mono (meth) acrylates (hereinafter referred to as "(B) component") selected from "components";

(C) contains a primary hydroxyl group-containing mono (meth) acrylate (hereinafter also referred to as "(C) component"),

10 mol% or more and 90 mol% or less of (a3) component is introduce | transduced into the isocyanate group in the terminal of the urethane prepolymer which (A) component consists of (a1) component and (a2) component, and (a4) component is 10 mol% More than 90mol%

It relates to an active energy ray hardening-type adhesive composition (henceforth an "adhesive composition").

Each component is explained in full detail below. In addition, in this specification, a (meth) acrylate is an acrylate and / or a methacrylate.

<(A) component>

The component (A) is a polyurethane that is a reactant of the component (a1), the component (a2), the component (a3) and the component (a4).

<(a1) component>

The component (a1) is a polyol. By using a polyol as a component (a1), the adhesion layer of this invention is excellent in transparency and flexibility. In the present specification, the polyol refers to a substance having two or more hydroxyl groups. (a1) A component is not specifically limited, Various well-known things may be sufficient. (a1) A component may be used independently and may use 2 or more types together. The component (a1) may be a crystalline polyol or an amorphous polyol.

In this specification, a crystalline polyol becomes like this. Preferably it is 20 degreeC or more and 60 degrees C or less, More preferably, it is 20 degreeC or more and 40 degrees C or less, Most preferably, it refers to the substance in which a polyol has a crystal structure. .

Examples of the component (a1) include polyether polyols, polyester polyols, polymer polyols, poly (meth) acryl polyols, polycarbonate polyols, castor oil-based polyols, and polyolefin polyols. In addition, in this specification, a (meth) acryl refers to an acryl and / or methacryl.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polytetramethylene glycol, and the like.

The polyether polyol may be a commercially available product. As the said product, polyetherdiol (product name "adeca polyether P series", ADAA Co., Ltd. product), polyether triol (product name "adeca polyether G series", ADBEA Co., Ltd. product), polyether tetra All (product name "adeca polyether EDP series", product made by ADAA Co., Ltd.), polyether polyol (product name "adeca polyether P1000", "adeca polyether P2000", product made by ADCA Co., Ltd., polyethylene glycol ( Product name "Polyethylene glycol # 1,540", product of Nakarai Tesque Co., Ltd. (NACALAI TESQUE, INC.), Dipropylene glycol (Product name "Dipropylene glycol", Pure Chemicals Co., Ltd. (JUNSEI CHEMICAL CO., LTD.) ), Polypropylene glycol (Product name "Polypropylene glycol 400", Pure Chemical Co., Ltd.), Polytetramethylene ether glycol (Product name "PMM650", "PMM1000", "PMM2000", "PMM3000", US TBI Chemical Co., Ltd. product (Mitsubishi Chemical Corporation) etc. are mentioned.

The polyester polyol may be a commercially available product. As the said product, the high refractive index grade polyester polyol (product name "Polylite RV-4800", DC Co., Ltd. product), the polyester polyol of high crystalline grade (product name "Polylite OD-X-2523", "polylite" Od-V-2547, manufactured by DC Co., Ltd., polyester polyol of transparent grade (product name "polylite OD-V-2420", "polylite OD-V-2692", made by DC Co., Ltd.), high Adhesive grade polyester polyol (product name "Polylite OD-X-2108", product made by DC Co., Ltd.), polyester polyol (product name "ETHNACOLL3000 series", product made by Ube Industries, Ltd.) , Polycaprolactone polyol (product name "Polylite OD-X-2155", product made by DC Co., Ltd.), polycaprolactone diol (product name "Placcel 200", Daicel Corporation product) , Polycaprolactone tree (Product name "flat raksel 300", Ltd Daicel Ltd.), polycaprolactone-tetra-ol and the like, etc. (product name "flat raksel 400", Ltd Daicel Ltd.).

The polymer polyol may be a commercially available product. As the said product, polymer polyol (product name "Altiflow series", "Sharpflow series", Sanyo Chemical Industries, Ltd. product), polymer polyol (product name "Exenol series", ABC Co., Ltd.) Products) and the like.

The poly (meth) acrylic polyol may be a commercially available product. As the said product, Acryl polyol (product name "Acrylic polyol # 6000", product made from Taisei Fine Chemical Co., Ltd.), acryl polyol (product name "ETRACC7315-BS-60", Jangheung material industry limited Examples of the company (Eternal Materials Corporation.), Acryl polyol (product name "acrylic polyol PK5984", product made by TOEI KASEI CO., LTD.), Etc. are mentioned.

The polycarbonate polyol may be a commercially available product. As the product, polycarbonate diol (product name "BeneBiOL", Mitsubishi Chemical Co., Ltd.), polycarbonate diol (product name "NIPPOLLAN series", Tosoh Corporation product), Polycarbonate diol (product name "Duranol series", product of Asahi Kasei Corp.), etc. are illustrated.

Castor oil-based polyols may be commercially available products. Examples of the product include castor oil-based polyols (product name "JRIC H series", manufactured by Itoh Oil Chemicals Co., Ltd.), castor oil-based polyols (product name "castor oil-based polyols HS-CPM-025P", " Castor oil-based polyol HSM C-075P, manufactured by Hokoku Corporation, etc.).

Examples of the polyolefin polyol include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene.

The polyolefin polyol may be a commercially available product. As the said product, polybutadiene diol ((product name "ピ ｏｌｙ ｂｄ R-45HTH", "Pｏｌｙ ｂｄ R-15HTH", product of Idemitsu Kosan Co., Ltd.), (product name "NissO-PＢ Ｂ)) -1000 "," Nisso-PPS-2000 "," Nisso-PPS-1000 "," Nisso-PPS-2000 ", Nippon Soda Co., Ltd. product)), hydrogen Addition polybutadiene diol (product name "Nisso-PPI Wi-1000", "Nisso-PPI Wi-2000", the Nippon Soda Co., Ltd. product), etc. are illustrated.

The component (a1) is preferably a polyol having crystallinity at 20 ° C. or higher and 60 ° C. or lower, because the adhesive layer is excellent in toughness and adhesive force at room temperature, and more preferably crystalline polyether polyol. The component (a1) is preferably one or more selected from the group consisting of polyether polyols, polycaprolactone polyols, and polyolefin polyols, from the viewpoint of relatively superior heat and moisture resistance, and more preferably polyether polyols and polyolefins. It is 1 or more types chosen from the group which consists of polyols.

The number average molecular weight of the component (a1) is preferably 700 or more and 10,000 or less, since the adhesive layer is excellent in adhesive force and step tracking ability. If the number average molecular weight of the component (a1) is less than the lower limit, the adhesive layer tends to be hard, and if it exceeds the upper limit, the adhesive layer tends to recede. There is a tendency. In this specification, a number average molecular weight can be calculated | required by the method described in JISK7252-1: 2016.

The hydroxyl group number of the component (a1) is preferably 1.5 or more and 3 or less, and more preferably 1.8 or more and 2.5 or less, since the adhesive layer is excellent in step tracking and workability. In the present specification, the hydroxyl group number can be obtained by the method described in JIS K1557-1: 2007. Specifically, in the present invention, the number of hydroxyl groups can be determined by the acetylation method.

<(a2) component>

(a2) A component is aliphatic polyisocyanate. (a2) A component is not specifically limited, Various well-known things may be sufficient. (a2) A component may be used independently and may use 2 or more types together.

As (a2) component, aliphatic diisocyanate, aliphatic triisocyanate, aliphatic tetraisocyanate, etc. are illustrated.

Examples of the component (a2) include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic aliphatic polyisocyanates, and the like.

Examples of the linear aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate and the like.

Examples of the branched aliphatic diisocyanate include methyl 2,6-diisocyanatohexanoate and trimethylhexamethylene diisocyanate.

As alicyclic aliphatic diisocyanate, dicyclohexyl methane 4,4'- diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, cyclohexane-1, 4- diylbis (methylene) Diisocyanate, 1-methylcyclohexane-2, 4- diyl diisocyanate, 1, 4- cyclohexane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate, norbornene diisocyanate, etc. are illustrated.

Lysine triisocyanate etc. are illustrated as linear aliphatic triisocyanate.

The component (a2) is preferably an aliphatic diisocyanate and more preferably a linear aliphatic diisocyanate and / or an alicyclic aliphatic diisocyanate because it is excellent in durability after a heat-and-moisture test and excellent in step tracking in the adhesive layer. to be.

The component (a2) may be a commercially available product. Examples of the product include 1,5-pentamethylene diisocyanate (product name "STABiO PDDI", Mitsui Chemicals, Inc.), hexamethylene diisocyanate (product name "HDDI", doso ( Product), 2,6-diisocyanatohexanoate (product name "LDI", Central Chemicals Co., Ltd. product (product of CHUO KASEIHIN CO., INC)), trimethylhexamethylene diisocyanate (product code "T1176", Tokyo) Manufactured by Tokyo Chemical Industry Co., Ltd., dicyclohexyl methane 4,4'-diisocyanate (product name "H12MDI", Central Chemicals Co., Ltd.), (product name "WEETANAT H12MDI", EBON IVI INDSB TRS IES AB Co., Ltd., isophorone diisocyanate (product name "IPPD", Central Chemicals Co., Ltd.), bis (isocyanatomethyl) cyclohexane (product name "TAKENATE 600", Mitsui Chemical Co., Ltd.) product), Lysine triisocyanate (product name "LTI", the product made by Central Chemicals Co., Ltd.), etc. are illustrated.

The ratio (NCO _(a2) / OH _(a1) ) of the mol number (OH _(a1) ) of the hydroxyl group of the component _(a1) and the mol number (NCO _(a2) ) of the isocyanate group of the component _(a2 ) is usually 1.01 to 2 It is enough.

<(a3) component>

(a3) A component is hydroxyl-containing mono (meth) acrylate. By using (a3) component, it is excellent in sclerosis | hardenability in an adhesive composition and is excellent in workability in an adhesion layer. When the adhesive composition is produced without containing the component (a3), curing failure occurs and the adhesive layer becomes excessively soft at room temperature. Since the adhesive layer easily adheres to the surface of the blade of the cutter when cutting the substrate or the like containing such an adhesive layer, the pressure-sensitive adhesive composition containing no (a3) component is not preferable. The component (a3) is not particularly limited, and various known ones may be used. (a3) A component may be used independently and may use 2 or more types together.

As hydroxyl-containing mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydride Hydroxyethyl phthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like are exemplified.

The component (a3) is excellent in curability in the pressure-sensitive adhesive composition and excellent in workability in the pressure-sensitive adhesive layer, preferably a hydroxyl group-containing mono (meth) acrylate having 5 to 10 carbon atoms, more preferably hydroxy. Ethyl (meth) acrylate.

The component (a3) may be a commercially available product. As the said product, 2-hydroxyethyl acrylate (product name "HEA", the product made by Osaka Organic Chemical Industry Ltd.), 2-hydroxyethyl methacrylate (product name "2-HEA") , Mitsubishi Gas Chemical Co., Ltd. (product of MITSUBISHI GAS CHEMICAL COMPANY, INC.), 2-hydroxypropyl methacrylate ((product name "light ester HOP (N)", Kyoeisha Chemical Co., Ltd.) ., Ltd.) Product), (product name "2-hydroxypropyl methacrylate", Nippon Catalyst Co., Ltd. product)), 4-hydroxybutyl acrylate (product name "4 -HBA ", Osaka Organic Chemical Industry Co., Ltd.), 2-hydroxybutyl methacrylate (Product name" Light ester HOH (N) ", Kyoeisha Chemical Co., Ltd.), 2-Acryloyloxyethyl 2-hydroxyethyl phthalic acid (product name "HO-MPE (N)", Kyoeisha Chemical Co., Ltd.), 2-hydroxy-3- phenoxy This and the like (Ischia Chemical Co., product name to "epoxy ester M-600A", Bridge) acrylate.

Since mol% of (a3) component introduce | transduced into the isocyanate group in the terminal of the urethane prepolymer which consists of (a1) component and (a2) component is excellent in sclerosis | hardenability in an adhesive composition, and excellent in workability in an adhesion layer, When the sum total of (a3) component and (a4) component is 100 mol%, they are 10 mol% or more and 90 mol% or less, Preferably they are 20 mol% or more and 80 mol% or less.

<(a4) component>

(a4) A component is a hydroxyl-containing photoinitiator. By using the component (a4), the step tracking ability is excellent in the adhesive layer. The component (a4) is not particularly limited, and various known ones may be used. (a4) A component may be used independently and may use 2 or more types together.

Examples of the component (a4) include a primary monohydric hydroxyl group-containing photopolymerization initiator, a secondary monohydric hydroxyl group-containing photopolymerization initiator, a tertiary monohydric hydroxyl group-containing photopolymerization initiator, a divalent hydroxyl group-containing photopolymerization initiator, and the like.

In the present specification, the monovalent hydroxyl group refers to one having one hydroxyl group. In the present specification, the divalent hydroxyl group refers to two hydroxyl groups. In the present specification, the primary hydroxyl group refers to a substance in which one carbon atom is bonded to a carbon atom to which the hydroxyl group is bonded. In the present specification, the secondary hydroxyl group refers to a substance in which two carbon atoms are bonded to a carbon atom to which the hydroxyl group is bonded. In the present specification, the tertiary hydroxyl group refers to a substance in which three carbon atoms are bonded to a carbon atom to which the hydroxyl group is bonded.

As a secondary monovalent hydroxyl group containing photoinitiator, 2-hydroxy-2- phenylacetophenone etc. are illustrated.

As a tertiary monohydric hydroxyl group containing photoinitiator, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, etc. are illustrated.

As a divalent hydroxyl group containing photoinitiator, 2-hydroxy-4 '-(2-hydroxyethoxy) -2-methylpropiophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2 -Hydroxy-2-methyl-1-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one and the like are exemplified.

The component (a4) is preferably a tertiary monohydric hydroxyl group-containing photoinitiator, because it is excellent in step tracking in the adhesive layer, and more preferably 1-hydroxycyclohexylphenyl ketone and / or 2-hydroxy Oxy-2-methyl-1-phenyl-propan-1-one.

The component (a4) may be a commercially available product. Examples of the product include 2-hydroxy-2-phenylacetophenone (product code "B0079", manufactured by Tokyo Chemical Industry Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone ((product name "OMNIRAD184", IVM JRESIS) Product), (product name "Lu-Na200", DBSH Japan Co., Ltd.), 2-hydroxy-2-methyl- 1-phenyl-propane- 1-one ((product name "OMMIRD1173", IRM R) , (Product name "LuNa100", DHS Japan Co., Ltd.), 2-hydroxy-4 '-(2-hydroxyethoxy) -2-methylpropiophenone (product code "H1361", Tokyo hardening industry) Co., Ltd.), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (product name "OMNIRR2929", the product of IRM RH Co., Ltd.) , 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl))-benzyl] phenyl} -2-methyl-propane-1-one (product name "OMNIRAD127", IV Ｒｅｓ Such as ns, Inc.) is exemplified.

The mol% of the component (a4) introduced into the isocyanate group at the terminal of the urethane prepolymer composed of the component (a1) and the component (a2) is excellent in step followability in the pressure-sensitive adhesive layer, so that the component (a3) and (a4) When the sum total of components is 100 mol%, they are 10 mol% or more and 90 mol% or less, More preferably, they are 20 mol% or more and 80 mol% or less.

The molar ratio of the component (a3) and the component (a4) introduced into the isocyanate group at the terminal of the urethane prepolymer composed of the component (a1) and the component (a2) ([(a3) component mol] / [(a4) component mol] ) Is excellent in step followability in the pressure-sensitive adhesive layer, and excellent in processability in the pressure-sensitive adhesive layer, preferably 1/9 to 9/1, and more preferably 1/5 to 3/1.

Moreover, "mol ratio of (a3) component and (a4) component introduced into the isocyanate group in the terminal of the urethane prepolymer which consists of a component (a1) and (a2)" is reacting with the isocyanate group in the terminal of a urethane prepolymer. It is a ratio of (a3) component and (a4) component. In order to obtain (A) component which made (a3) component and (a4) component into the desired mol ratio, (a3) component and (a4) component of the quantity which react with all these with respect to the quantity of isocyanate groups which exist in a urethane prepolymer What is necessary is to mix and react in the desired mol ratio.

<Additive which can be mix | blended with other (A) component>

(A) component may also contain various additives as needed. The additive may be various known ones. An additive may be used independently and may use 2 or more types together.

As an additive, a catalyst, a nucleating agent, a crystallization promoter, a chain transfer agent, etc. are illustrated.

Although the manufacturing method of (A) component is not specifically limited, The manufacturing method of various well-known polyurethane can be employ | adopted. Component (A) reacts component (a1) with component (a2) to produce a urethane prepolymer (hereinafter referred to as component (A ')) having one or more isocyanate groups at its ends, and then (A') component and (a3). The reaction temperature and reaction time are not particularly limited, but are usually 70 ° C. or more and 85 ° C. or less, 1 hour or more and 5 hours or less. It is possible to use (b1) component, (b2) component, etc. of this invention as a diluent, and (b1) component is preferable, and you may use a polymerization inhibitor so that a component (a3) may not superpose | polymerize.

The weight average molecular weight of the component (A) is preferably 10,000 or more and 90,000 or less, more preferably 20,000 or more and 70,000 or less, because of excellent adhesive force and step-followability in the adhesive layer. When the weight average molecular weight of (A) component is less than the said minimum, it exists in the tendency for the adhesive force of an adhesion layer to become weak, and when it exceeds the said upper limit, the viscosity of an adhesive composition will become high and manufacture will become difficult. In this specification, a weight average molecular weight is the polystyrene conversion value by the gel permeation chromatography method.

Since content of (A) component is excellent in sclerosis | hardenability in an adhesive composition, and excellent in adhesive force and step | following traceability in an adhesion layer, the total of (A) component, (B) component, and (C) component is 100 mass% When it is set as the solid content, Preferably it is 20 mass% or more and 70 mass% or less, More preferably, they are 20 mass% or more and 60 mass% or less, More preferably, they are 25 mass% or more and 50 mass% or less.

<(B) component>

(B) component is 1 or more types chosen from the following (b1) component and (b2) component.

<(b1) component>

The component (b1) is an alkyl mono (meth) acrylate having 4 to 18 carbon atoms of a linear alkyl group containing no alicyclic structure and an alkyl mono (meth) having 4 to 18 carbon atoms of a branched alkyl group containing no alicyclic structure. ) At least one alkyl mono (meth) acrylate selected from. By using the component (b1), the step tracking ability is excellent in the adhesive layer. Various well-known things may be sufficient as (b1) component. (b1) A component may be used independently and may use 2 or more types together. When the carbon number of the alkyl group in the alkyl mono (meth) acrylate of (b1) component is 19 or more, compatibility is bad and it is difficult to acquire the effect of this invention. Moreover, when the carbon number of the alkyl group in the alkyl mono (meth) acrylate of (b1) component is 3 or less, since boiling point is low, the storage stability of a product is inferior.

Alkyl mono (meth) acrylates having 4 to 18 carbon atoms of a linear alkyl group containing no alicyclic structure, such as n-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl ( Meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hexadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylic Rate and the like are exemplified.

Alkyl mono (meth) acrylates having 4 to 18 carbon atoms of a branched alkyl group containing no alicyclic structure, isoamyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and iso Decyl (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. are illustrated.

The component (b1) may be a commercially available product. As the said product, butyl acrylate (a brand name "butyl acrylate", the product made by TOAGOSEI CO., LTD.), Nonyl acrylate (a product name "Viscoat # 197", Osaka organic chemical industry ( Product), lauryl acrylate (product name "light acrylate LA", Kyoeisha Chemical Co., Ltd.), stearyl acrylate (product name "light acrylate SA", Kyoeisha Chemical Co., Ltd. product) , Isostearyl acrylate (product name "ISTA", Osaka Organic Chemical Co., Ltd.), isoamyl acrylate (product name "light acrylate IAA", Kyoeisha Chemical Co., Ltd.), isononyl acrylate (product name) "Iononyl acrylate", product made by Osaka Organic Chemical Industry Co., Ltd., isodecyl acrylate (Product name "IDAA", product made by Osaka Organic Chemical Industry Co., Ltd.), 2-ethylhexyl acrylate (Product name "Acrylic acid-2- Ethylhexyl ”, US Such as Mitsubishi Chemical Co., Ltd.) are exemplified.

The content of the component (b1) is preferably in terms of solid content when the total of the component (A), the component (B) and the component (C) is 100% by mass because of excellent step tracking in the adhesive layer. Is 15 mass% or more and 65 mass% or less, More preferably, they are 15 mass% or more and 60 mass% or less, More preferably, they are 20 mass% or more and 50 mass% or less.

<(b2) component>

The component (b2) is an alkyl mono (meth) acrylate having 6 to 15 carbon atoms in the alkyl group containing an alicyclic structure. By using (b2) component, it is excellent in workability in an adhesion layer. Various well-known things may be sufficient as (b2) component. (b2) A component may be used independently and may use 2 or more types together.

As the component (b2), cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc. are illustrated.

(b2) A component is excellent in workability in an adhesion layer, Preferably cyclohexyl (meth) acrylate, 3,3, 5- trimethyl cyclohexyl (meth) acrylate, 4-t-butyl cyclohexyl ( It is 1 or more types chosen from the group which consists of a meta) acrylate, an isobonyl (meth) acrylate, and a dicyclopentanyl (meth) acrylate, More preferably, isobonyl (meth) acrylate and / or dicyclopentanyl ( Meta) acrylate.

The component (b2) may be a commercially available product. As the said product, cyclohexyl methacrylate (product name "light ester CH", Kyoeisha Chemical Co., Ltd. product), cyclohexyl acrylate (product name "Biscote # 155", Osaka Organic Chemical Industry Co., Ltd. product), 4-t-butylcyclohexyl methacrylate (product name "4-t-butylcyclohexyl methacrylate", the product made by MC Unitec Co., Ltd.), 4-t-butylcyclohexyl Acrylate (Product name "BLEMMER" TBCCA) Nichiyu Co., Ltd. (NOF CORPORATION), Isobonyl acrylate (Product name "IAWA", Osaka Organic Chemical Industry Co., Ltd.), Dicyclopentanyl acrylate ( The product name "FA-513AS", the Hitachi Chemicals Co., Ltd. product, dicyclopentenyl acrylate (product name "FA-511AS", Hitachi Chemical Co., Ltd. product), etc. are illustrated.

Carbon number of the ring-containing alkyl group of (b2) component is 6 or more and 15 or less, Preferably it is 6 or more and 10 or less.

When content of (b2) component is excellent in workability in an adhesion layer, and the sum total of (A) component, (B) component, and (C) component is 100 mass%, it is preferable in terms of solid content 10 It is mass% or more and 60 mass% or less, More preferably, they are 15 mass% or more and 60 mass% or less, More preferably, they are 15 mass% or more and 50 mass% or less.

It is particularly preferable that the component (B) contains both the component (b1) and the component (b2), because both of the step tracking and workability of the adhesive layer are excellent.

When content of (B) component makes the sum total of (A) component, (B) component, and (C) component 100 mass%, Preferably it is 25 mass% or more and 75 mass% or less in conversion of solid content, More preferably, they are 30 mass% or more and 70 mass% or less, More preferably, they are 30 mass% or more and 65 mass% or less.

<(C) component>

(C) component is a primary hydroxyl group containing mono (meth) acrylate. By using (C) component, it is excellent in sclerosis | hardenability in an adhesive composition and excellent in durability after a heat-and-moisture test in an adhesion layer. (C) component is not specifically limited, Various well-known things may be sufficient. (C) component may be used independently and may use 2 or more types together. When the mono (meth) acrylate which does not have a hydroxyl group is used as a substitute of (C) component, the durability after a heat-and-moisture test and the haze value after a heat-and-moisture test are inferior. Moreover, when the secondary hydroxyl group containing mono (meth) acrylate is used as a substitute of (C) component, the haze value after a moisture-resistant heat test is inferior.

As (C) component, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate, etc. This is illustrated.

(C) The component is excellent in sclerosis | hardenability in an adhesive composition, and excellent in durability after a heat-and-moisture test in an adhesion layer, Preferably 2-hydroxyethyl (meth) acrylate and / or 4-hydroxybutyl (Meth) acrylate.

The component (C) may be a commercially available product. As the product, 2-hydroxyethyl acrylate (product name "HEA", product of Osaka Organic Chemical Industry Co., Ltd.), 2-hydroxyethyl methacrylate (product name "2-HEMA", product of Mitsubishi Gas Chemical Co., Ltd.) ), 4-hydroxybutyl acrylate (product name "4-HWA", product of Osaka Organic Chemical Industry Co., Ltd.), 1, 4- cyclohexane dimethanol monoacrylate (product name "CHDMMA", product of Mitsubishi Chemical Co., Ltd.) ) And the like are exemplified.

Content of (C) component is 100 mass% of the sum total of (A) component, (B) component, and (C) component because it is excellent in sclerosis | hardenability in an adhesive composition and excellent in durability after a heat-and-moisture test in an adhesion layer. In terms of solid content, it is preferably 5% by mass or more and 55% by mass or less, more preferably 5% by mass or more and 50% by mass or less, still more preferably 10% by mass or more and 40% by mass or less. .

<(D) component>

It is preferable to make the adhesive composition of this invention contain a radical type photoinitiator (henceforth "(D) component") because an adhesive layer is excellent in sclerosis | hardenability. (D) component is not specifically limited, Various well-known things may be sufficient. (D) component may be used independently and may use 2 or more types together.

As (D) component, an alkyl phenone type photoinitiator, an acyl phosphine oxide type photoinitiator, a hydrogen drawing type photoinitiator, an oxime ester type photoinitiator, etc. are illustrated.

As an alkylphenone type photoinitiator, benzyl dimethyl ketal, such as 2, 2- dimethoxy- 1, 2- diphenyl ethanol-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2- Α-hydrides such as hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Alpha)-aminoalkyl phenone, such as oxyalkyl phenone and 2-methyl-1- (4-methylthio phenyl) -2-morpholino propane- 1-one, etc. are illustrated.

Examples of the acylphosphine oxide type photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.

Phenylglyoxylic acid methyl ester etc. are illustrated as a hydrogen extraction type photoinitiator.

As oxime ester type photoinitiator, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

(D) Component is excellent in sclerosis | hardenability in an adhesive composition, Preferably it is an (alpha)-hydroxyalkyl phenone type photoinitiator and / or an acylphosphine oxide type photoinitiator.

The component (D) may be a commercially available product. As the said product, 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one (product name "OMNIRAD 651", the product made by IRM Corporation), 2-hydroxy-2-methyl-1-phenyl-propane- 1-On ((Product Code `` H0991 '', manufactured by Tokyo Chemical Industry Co., Ltd.), (Product Name `` OMNIRAD1173 '', IVM イ ル サ イ ニ ス Co., Ltd.), (Product Name `` LuNa100 '', DFSH Japan Co., Ltd.)), 1- Hydroxy-cyclohexyl-phenyl-ketone ((product name "OMMIRD184", IRM RH Co., Ltd. product), (product name "LuN200", DBS Japan Co., Ltd. product)), 1- [4- (2-hydroxyethoxy ) -Phenyl] -2-hydroxy-2-methyl-1-propane-1-one (product name "OMNIRAD 2959", IRM Corporation), 2-methyl-1- (4-methylthiophenyl) -2- Morpholino propane-1-one (product name "OMNIRAD 907", IPM RISS Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (made Name "OMNIRAD TPO", IBM RJ's product, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (product name "'OMMIRD 819', IBM's product's product), phenylglyoxylic acid methyl ester (product name) "OMNIRAD MWF", manufactured by IJM RESIS, Inc., 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] ), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (product name "OMNIRAD OZ02", IRM R 4) etc. are illustrated.

Content of (D) component is preferable when the sum total of (A) component, (B) component, and (C) component is 100 mass% from the thing excellent in curability and durability after a heat-and-moisture test in an adhesion layer. Preferably it is 0.1 mass% or more and 3 mass% or less in conversion of solid content, More preferably, they are 0.2 mass% or more and 2 mass% or less, More preferably, they are 0.2 mass% or more and 1.5 mass% or less.

<Other compoundable additives>

The adhesive composition of this invention may also contain various additives as needed.

The additive is not particularly limited and may be various known ones. An additive may be used independently and may use 2 or more types together.

Examples of the additive include surface conditioners, surfactants, ultraviolet absorbers, antioxidants, light stabilizers, tackifiers, inorganic fillers, silane coupling agents, colloidal silica, antifoaming agents, wetting agents, rust inhibitors, plasticizers, chain transfer agents, and photosensitizers. do.

The adhesive composition of this invention may contain a solvent. It does not specifically limit as a solvent, Various well-known things may be sufficient. A solvent may be used independently and may use 2 or more types together.

Examples of the solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, amide solvents, and the like.

As a ketone solvent, methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone, cyclohexanone, etc. are illustrated.

Toluene, xylene, etc. are illustrated as an aromatic solvent.

As an alcohol solvent, methanol, ethanol, n-propanol, isopropanol, butanol, etc. are illustrated.

Examples of the glycol ether solvent include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate.

As an ester solvent, ethyl acetate, butyl acetate, methyl cellosolve acetate, a cellosolve acetate, etc. are illustrated.

Examples of the petroleum solvent include Solvesso 100 (manufactured by Exxon Mobil Corporation), Solvetso 150 (manufactured by Exxon Mobil Corporation), and the like.

As the haloalkane solvent, chloroform and the like are exemplified.

Dimethylformamide etc. are illustrated as an amide solvent.

The adhesive composition of this invention can be used even if it does not contain a solvent. Therefore, the adhesive composition of this invention does not contain a solvent preferably from a viewpoint that cost and an influence on an environment can be suppressed.

Since the viscosity (mPas / 25 degreeC) of the adhesive composition of this invention is excellent in handling property in an adhesive composition, Preferably it is 100 or more and 10,000 or less, More preferably, it is 300 or more and 8,000 or less, More preferably It is more than 500 and less than 7,000. In the present invention, the viscosity is a measured value (5 minutes) by an E-type viscometer (product name "TV-10", manufactured by Toki Sangyo Co., Ltd.).

The adhesive composition of this invention is obtained by mixing (A) component, (B) component and (C) component, and (D) component and other compoundable additives as needed. Although the mixing order is not specifically limited, You may mix sequentially or you may mix all at once.

<Hardened product>

It is one of this invention also hardened | cured by irradiating an active energy ray, such as an ultraviolet-ray, to an adhesive composition.

When a solvent is contained in an adhesive composition, it can dry-process before ultraviolet irradiation.

As an ultraviolet light source, the ultraviolet irradiation apparatus provided with a xenon lamp, a high pressure mercury lamp, and a metal halide lamp is illustrated. Conditions such as irradiation intensity and the accumulated light quantity also the conveying speed of the ultraviolet light in the apparatus is not particularly limited, but usually the irradiation intensity is 80mW / cm ² than 160mW / cm ² or less, the conveying speed is 3m / min or more 50m / min. hereinafter, the cumulative dose over 100mJ / cm ² is 3,000mJ / cm ² or less.

After apply | coating an adhesive composition to various plastic film base materials, and forming a layer of an adhesive composition, you may obtain hardened | cured material by irradiating an ultraviolet-ray to the said layer.

Examples of the method for applying the pressure-sensitive adhesive composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like.

The application amount is a range in which the mass after drying is usually 1 g / m ² or more and 1,000 g / m ² or less, preferably 3 g / m ² or more and 500 g / m ² or less.

Although the thickness of the hardened | cured material of this invention is not specifically limited, Since the adhesion layer exhibits the step traceability suitably and it is hard to generate | occur | produce a bubble, Preferably, the coating film after drying is 10 micrometers or more and 1,000 micrometers or less, More preferably, It is 25 micrometers or more and 500 micrometers or less.

As for the hardened | cured material of this invention, storage elastic modulus G '(henceforth "G'" in 25 degreeC and 1 Hz) becomes like this. Preferably it is 8 * 10 <^4> PA or more, More preferably, it is 8 * 10 <^4> PA. It is more than 1x10 ⁷ Pa. The loss factor TAδ (hereinafter also referred to as "TAnδ") at 50 ° C and 1 Hz is preferably 0.4 or more, and more preferably 0.4 or more and 2 or less. Since such a characteristic is provided, it is considered that the cured product is compatible with workability (G 'at room temperature) and step tracking (Tann at heating), and exhibits excellent adhesive strength and excellent durability after a heat-and-moisture resistance test. Is more preferably 1 × 10 ⁵ Pa or more and 1 × 10 ⁷ Pa or less, and TAδ is still more preferably 0.5 or more and 1.5 or less. The coefficient can be obtained by the method described in JIS K7244-1: 1998.

Specifically, the storage elastic modulus and the loss coefficient are measured by a commercially available measuring instrument (product name "MCR302", manufactured by Anton Paar) under the following conditions. From the measurement results, the storage modulus G 'at 25 ° C and the loss coefficient at 50 ° C are obtained.

Transform mode: Twist

Measuring frequency: 1Hz

Deformation: 0.01 ~ 1% ATV setting

Temperature rise rate: 3 ℃ / min

Temperature: 25 ~ 50 ℃

Shape: Parallel Plate 8.0mmφ

In this specification, storage elastic modulus (G ') is a value proportional to the maximum energy accumulate | stored through a load cycle, and shows rigidity of an adhesion layer, and rigidity is a difficulty of deformation with respect to external force, such as a curvature and a twist. The larger the numerical value of the storage modulus at 25 ° C. and 1 Hz, the higher the rigidity of the adhesive layer at 25 ° C., and the smaller the numerical value, the lower the rigidity of the adhesive layer at 25 ° C. At 25 ° C. and 1 Hz of the cured product of the present invention Since the preferable storage modulus G 'of is 8 * 10 <^4> Pa or more, the hardened | cured material of this invention is excellent in workability at room temperature.

In this specification, the loss coefficient TAδ indicates the ratio of the loss modulus to the storage modulus G ', which indicates how much energy the material absorbs (changes in heat) when the material is deformed. And as the numerical value of the loss coefficient TAδ at 1 Hz is smaller, the energy is not absorbed at 50 ° C., while the larger the numerical value is, the energy is absorbed at 50 ° C. (that is, it is easy to deform) 50 ° C. and 1 Hz of the cured product of the present invention. Since the preferable loss factor TAδ in is 0.4 or more, the cured product of the present invention is excellent in step followability at 50 ° C.

<Molding thing>

As an application example of an adhesive composition, application | coating to the base material of various well-known articles is illustrated. These articles are not particularly limited, and various known ones may be used.

Examples of the article include a main body of a home appliance such as a refrigerator, a television or an air conditioner, a frame and a display of an information terminal such as a remote controller, a mobile phone, a smartphone, a tablet or a PC, and a plastic molded article such as an automobile part or an automobile interior material. do.

The active energy ray-curable pressure-sensitive adhesive composition of the present invention is suitable for optical use. For example, the present invention can be applied to a display panel of a multilayer structure in a digital display device. In addition, as described above, since the adhesive force is excellent and the step tracking ability is also good, when applied to a double-sided adhesive sheet for a touch panel, for example, a decorative plate or an icon sheet is bonded onto the panel, or a capacitive type When bonding the transparent substrate which formed the transparent electrode in a touch panel, and transparent plates, such as glass and a plastic, a bubble does not generate | occur | produce easily. In addition, the adhesive layer is strong at room temperature, the problem that the cut portion adheres to the punching blade and cannot be separated during the punching process, or the problem that the adhesive layer adheres to the punching blade does not occur. have. Since the adhesive layer of this invention is excellent in transparency, it is suitable to use it for displays, such as a television, a smartphone, or a tablet.

<Applicable mention>

The adhesive composition of this invention can be applied to various base materials, such as a metal, plastic, a film, and glass. The various substrates may be various known ones. Various base materials may be used independently and may use 2 or more types together.

As various base materials, various well-known metal, plastic, a film, glass, other resin, etc. are illustrated.

Examples of the metal include iron, aluminum, aluminum plated steel sheets, tin-free steel sheets (TFS), stainless steel sheets, zinc-phosphate treated steel sheets, or zinc-zinc alloy plated steel sheets (bonded steel sheets).

As the plastic, polyester such as ABS, polyimide (PI), polybutene (PB), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET) ( PE), acrylics, such as polymethyl methacrylate (PMMA), FRP, etc. are illustrated.

As the film, PET film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, Ethylene vinyl acetate film, ionomer resin film, ethylene (meth) acrylic acid copolymer film, ethylene (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. are illustrated.

As another base material, an epoxy resin, a melamine resin, a triacetyl cellulose resin, ABS resin, AS resin, norbornene-type resin, etc. are illustrated.

Since the adhesive layer of this invention is excellent in transparency, it is especially preferable to use it for optical use. That is, the adhesive layer of this invention is suitable for especially bonding an optical base material. The adhesive layer of the present invention is suitable for use as an optical transparent adhesive (hereinafter also referred to as "OCA").

The base for optics of this invention is not specifically limited, Various well-known things may be sufficient. An optical base material may be used independently and may use 2 or more types together.

As the substrate for optics, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl Cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film , Plastic films such as polyester sulfone film, polyetherimide film, polyimide film, fluororesin film, polyamide film, acrylic resin film, norbornene-based resin film, cycloolefin resin film, glass, tin dope indium oxide film, ITO Film, transparent conductive peel The like can be given.

Specifically, as a combination of the adhesion layer of this invention and an optical base material,

(1) Glass, adhesive layer of this invention, transparent conductive film (henceforth "ITO")

(2) support film, adhesive layer of the present invention, ITO

(3) support film, pressure-sensitive adhesive layer of the present invention, liquid crystal display

(4) glass, adhesion layer of this invention, liquid crystal display

Etc. can be mentioned.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Comparative Production Examples, Examples, Comparative Examples, Evaluation Examples, and Comparative Evaluation Examples, but the present invention is not limited to these Examples. In the following description, parts and percentages are based on mass.

In this Example, the weight average molecular weight (MV) was measured by the gel permeation chromatography (PCC) of the following conditions.

(PCC measurement condition)

Type: Product name "HLC-8220GPC" (Tosoh Corporation)

Column: Product Name "ＴＳＫｇｅｌ Ｇ1000Ｈ", "ＴＳＫｇｅｌ Ｇ2000Ｈ" (product of Toso Corporation)

Developing Solvent: Tetrahydrofuran

Flow rate: 0.6 ml / min

Measuring temperature: 40 ℃

Detector: Differential Refractive Index Detector

Standard: Monodisperse Polystyrene

Sample: A 20 μL solution obtained by preparing a tetrahydrofuran solution having a concentration of 0.2% from a resin in terms of solid content and filtering the solution with a micro filter.

In each manufacture example, the NC measurement method of a urethane prepolymer is as follows.

Measuring device main body: Potentiometer automatic titrator (product name "AT-400", Kyoto Electronics Co., Ltd. ( Kyoto Electronics Manufacturing Co., Ltd.)

Order of measurement:

1: Weigh 0.500 g or more and 1.000 g or less of samples with a weighing bottle.

2: 10 mL of a toluene solution of 0.15 mol / L of dibutylamine is injected.

3: Place the weighing bottle containing the sample into the ultrasonic cleaner to dissolve the sample completely.

4: After confirming that the sample is completely dissolved, it is left to stand for 15 minutes (no direct sunlight or heat).

5: After 15 minutes, 100 mL of isopropyl alcohol was added to the weighing bottle. Put a stirrer piece into the weighing bottle.

6: It titrates using 0.1 mol / L hydrochloric acid solution (f = 1.00), and calculate | requires the NO value.

The sample amount to be measured is put into an automatic titrator and then measured. If the difference is less than 0.30, it is evaluated as good. If 0.30 or more, measure one again and check within 0.30.

Preparation Example 1 Preparation of (A) -1 Component

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air inlet, polytetramethylene ether glycol having a number average molecular weight of 2,000 (A1) as a component (product name: PTM2000, manufactured by Mitsubishi Chemical Co., Ltd.) 863 parts of hexamethylene diisocyanate (product name "HDD", product of Toso Corporation, hereinafter also called "HDDI") as 863 parts of 2-ethylhexyl acrylate as below (it also calls "PTM2000") (a2) component (Product name "Ethyl acrylate 2-ethylhexyl", Mitsubishi Chemical Co., Ltd., hereinafter also referred to as "2-EHA".) 333 parts and 0.5 parts of octylic acid tin were added and reacted at 70 ° C for 2 hours to give an isocyanate group as an intermediate. A 2-EHA solution of the terminal urethane prepolymer was obtained. 17 parts of 2-hydroxyethyl acrylate (product name "HEA", product made from Osaka Organic Chemical Industry Co., Ltd., hereinafter, also referred to as "HEA") as a component, (a4) to the obtained reaction product, and 2-hydroxy as a component 23 parts of -2-methyl-1-phenyl-propan-1-one (product name "Lu-Na100", the product of DHS Japan Co., Ltd., hereafter "L100") are mixed, it is made to react by keeping it at 70 degreeC for 2 hours, By confirming the reaction completion by the measurement of NCO, a 2-EHA solution of the reactant (hereinafter referred to as "(A) -1 component") was obtained.

<Production Examples 2 to 5 and Comparative Production Examples 1 to 4: Preparation of (A) -2 Components to (A) -5 Components and (A) -C1 to (A) -C4 Components>

It carried out similarly to manufacture example 1 except having changed the component as described in Table 1. Table 2 shows mol% of component (a3) and mol% of component (a4) introduced to the isocyanate group at the terminal of the urethane prepolymer composed of the component (a1) and (a2).

Preparation Example 6 Preparation of (A) -6 Components>

Instead of the 2-EHA solution, 333 parts of isobornyl acrylate (hereinafter also referred to as "IABA") solution were used, except that (a1) to (a4) components were changed to those described in Table 1, and It carried out similarly.

Comparative Preparation Example 5 Preparation of (A) -C5 Component>

To the same reactor as in Production Example 1, 683 parts of PETM2000 as the component (a1), 77 parts of HDI as the component (a2), 333 parts of 2-EHA and 0.5 parts of tin octylate were added and reacted at 70 ° C for 2 hours. The 2-EHA solution of the isocyanate group terminal urethane prepolymer which is an intermediate was obtained. 227 parts of PETM2000 as a component (a1) and 13 parts of HEA as a component (a3) were mixed with the obtained reaction product, the reaction product was kept at 70 ° C for 2 hours for reaction, and the reaction was confirmed by NCO measurement. -C5 component ") to obtain a 2-EHA solution. The mol% of the component (a3) in the component (A) -C5 was 50 mol%, and the mol% of the component (a4) was 0 mol%.

The number of Table 1 has shown the mass part of (a1) component, (a2) component, (a3) component, and (a4) component in (A) component. In addition, the meaning of the term in Table 1 is as follows.

PETM2000: Polytetramethylene ether glycol (Product name: PETM2000, manufactured by Mitsubishi Chemical Co., Ltd.)

L220AL: Polycaprolactone polyol (Product name "Placel L220AL", Daicel Co., Ltd.)

HDI: Hexamethylene diisocyanate (product name "HDI", product of Toso Corporation)

IPDI: Isophorone diisocyanate (product name "JESTANNAT IPIDI", product of Evonik Japan Co., Ltd.)

HEA: 2-hydroxyethyl acrylate (product name "HEA", product of Osaka Organic Chemical Industry Co., Ltd.)

L100: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name "LuNa100", DHS Japan Co., Ltd. product)

L200: 1-hydroxycyclohexyl phenyl ketone (product name "LuNa200", DHS Japan Co., Ltd. product)

Example 1: Preparation of pressure-sensitive adhesive composition (1)

As component (A), 2-EHA as component (A) -1 of Production Example 1, component (b1) and isobornyl acrylate as product component (b2) (product name "IAA", manufactured by Osaka Organic Chemical Industry Co., Ltd., hereinafter. , IAA) and (C) component were mixed so that L200 might be HEA and (D) component so that it may become mass% shown in Table 3, and the adhesive composition (1) was obtained.

<Examples 2-12 and Comparative Examples 1-7: Adhesive composition (2)-(12) and adhesive composition (C1)-(C7)>

It carried out similarly to Example 1 except having changed the component as described in Tables 3 and 4.

<Performance Evaluation (1): Viscosity (MPa · s)>

The viscosity of the pressure-sensitive adhesive compositions (1) to (12) and the pressure-sensitive adhesive compositions (C1) to (C7) was measured at 25 ° C using a commercially available measuring instrument (product name "TV-10 Type Viscometer", manufactured by KKK). did.

<Performance evaluation (2): storage modulus (G ') and loss factor Tａｎδ

One of the pressure-sensitive adhesive compositions (1) to (12) and (C1) to (C7) is a 75 μm-thick heavy-peel-processed polyester film (product name "SP-PET-03-75BU", Panak Co., Ltd.) (PANAC CO., LTD.)), It is apply | coated so that the film thickness of the adhesion layer after hardening may be set to 200 micrometers, and the 38-micrometer-thick hard peeling polyester film (product name "SP-PET) to an adhesive composition application layer -01-38BU ", Panak Co., Ltd. product) are bonded together. Subsequently, the high pressure mercury lamp (other than adhesive composition (9) and (C4): 100 mW / cm ² , 900 mJ / cm ² , pressure-sensitive adhesive composition (9) and (C4): 100 mW / cm ² , 3,000 mJ in air) / cm ² ) to produce a laminated film (light-peeled polyester film / adhesive layer / heavy peeled polyester film) containing an adhesive layer. Next, the test piece of 1 cm x 1 cm was cut out from the said laminated | multilayer film. Next, the light-peeled polyester film and the heavy-peeled polyester film are peeled from the test piece, and the sheet (adhesive sheets (1) to (12) and (C1) composed of only an adhesive layer (hereinafter also referred to as "cured product")). (C7)) was obtained. The pressure-sensitive adhesive sheets (1) to (12) and (C1) to (C7) were placed on a commercially available measuring instrument (product name "MCR302", manufactured by Antonpar), and the dynamic viscoelasticity was measured under the following conditions. From the measurement results, the storage modulus G 'at 25 ° C and 1 Hz and the loss coefficient TAδ at 50 ° C and 1 Hz were determined.

(Measuring conditions)

Transform mode: Twist

Measuring frequency: 1Hz

Deformation: 0.01 ~ 1% ATV setting

Temperature rise rate: 3 ℃ / min

Temperature: 25 ~ 50 ℃

Shape: Parallel Plate 8.0mmφ

<Performance Evaluation (3): Compatibility>

Using a spectrophotometer (product name "U-3210 type magnetic spectrophotometer", manufactured by Hitachi, Ltd.), the adhesive sheet of the performance evaluation (2) was irradiated with light having a wavelength of 500 nm and its transmittance (% ) Was measured and compatibility was evaluated according to the following criteria.

○: 85% or more

×: less than 85%

<Evaluation (4): step followability>

In the performance evaluation (2), a laminated film was produced so that the film thickness of the pressure-sensitive adhesive composition after curing was 100 μm, the light-peeled polyester film was peeled off, and instead, a 50 μm-thick polyester film (product name “COSMOSHINE ) A-4300 ", manufactured by TOYOBO CO., LTD., Were bonded together with a 2 kg roller, and left standing for 2 hours. Subsequently, the test piece of 8 cm x 8 cm was cut out from this, and the heavy peeling polyester film was peeled off, and the single-sided adhesive sheet (Cosmoshine A-4300 / adhesive layer) was produced. A polyester film piece (5 cm x 5 cm x 50 μm) is stacked on a glass plate (10 cm x 10 cm x 2 mm), and a single-sided adhesive sheet (adhesive layer / Cosmoshine A-4300) (5 cm x 5 cm x 150 μm) is further stacked on it. Laminated body (Cosmo shine A-4300 (50μm thickness) / adhesive layer (100μm thickness) / polyester film piece (50μm thickness) / glass plate (2mm thickness) by adhering with a 2kg roller (laminated body (1-1) -(12-1) and (C1-1)-(C7-1)) were produced.

After stacking (1-1)-(12-1) and (C1-1)-(C7-1) by autoclave on 50 degreeC, 0.5 Mpa, and the conditions for 20 minutes, it is 25 degreeC After standing still for 24 hours on 50% of humidity, it evaluated on 85 degreeC, 85% of humidity, and 24 hours in a thermo-hygrostat. Step followability of the adhesive layer in this state was visually evaluated based on the following criteria.

1: Lifting is not confirmed along each edge of a polyester film piece, and an air bubble is not confirmed, either

2: Lifting is not confirmed along each side of the polyester film piece, but five fine bubbles can be confirmed to the limit.

3: A slightly wider lift is observed along each side of the polyester film piece, and 10 fine bubbles can be confirmed to the limit.

4: A wide float is confirmed along each side of the polyester film piece, and a plurality of large bubbles as well as fine bubbles can be confirmed.

<Performance evaluation (5): haze value>

In the performance evaluation (2), a laminated film was produced so that the film thickness of the pressure-sensitive adhesive composition after curing was 100 μm, the light-peeled polyester film was peeled off, and instead, a 50 μm-thick polyester film (product name “Cosmo Shine A- 4300 "and Toyobo Co., Ltd.) were bonded together with a 2 kg roller, and left still for 2 hours. Subsequently, the test piece of 8 cm x 8 cm was cut out from this, and the heavy peeling polyester film was peeled off, and the single-sided adhesive sheet (Cosmoshine A-4300 / adhesive layer) was produced. Laminate (Cosmo shine A-4300 (50μm thick) by stacking one-sided adhesive sheet (adhesive layer / Cosmoshine A-4300) (5cm × 5cm × 150μm) on a glass plate (10cm × 10cm × 2mm) and sticking it with 2kg roller. / Adhesive layer (100 micrometer thickness) / glass plate (2 mm thickness) (laminated body (1-2)-(12-2), and (C1-2)-(C7-2)) were produced.

Haze value of laminated body (1-2)-(12-2) and (C1-2)-(C7-2) the commercially available measuring instrument (product name "haze permeability meter HM-150", Murakami color) It was measured according to JIS K 7136: 2000 using a technical laboratory (manufactured by Murakami Color Research Laboratory). Moreover, the obtained haze value is a value containing the haze value of a base material (Cosmoshine A-4300 and a glass plate).

<Performance Evaluation (6): Haze Value (After Moisture and Heat Test)>

A commercially available measuring instrument for haze values of laminates (1-2) to (12-2) and (C1-2) to (C7-2) after standing for 500 hours in a constant temperature and humidity chamber with a temperature of 85 ° C and a humidity of 85% ( It measured according to JIS K 7136: 2000 using the product name "Haze-transmittance meter HM-150" and the product of Murakami Color Research Institute. Moreover, the obtained haze value is a value containing the haze value of a base material (Cosmoshine A-4300 and a glass plate).

<Performance Evaluation (7): Adhesive Strength>

The laminates (1-2) to (12-2) and (C1-2) to (C7-2) were allowed to stand for 24 hours under conditions of 25 ° C and 50% humidity. Adhesive force (N / 25mm) was measured by peeling the single-sided adhesive sheet (adhesive layer / Cosmoshine A-4300) from the glass plate at a speed of 300 mm / min in the 180 ° direction. For the measurement, a commercially available machine (product name "Tensilon Universal Testing Machine", manufactured by AND Co., Ltd.) was used.

<Performance Evaluation (8): Durability (After Moisture and Heat Test)>

After the laminates (1-2) to (12-2) and (C1-2) to (C7-2) were allowed to stand in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 85% for 500 hours, the durability of the adhesive layer was determined as follows. Evaluated by reference.

(Circle): There is no peeling of a base material, the shift of the adhesion layer position, the bubble in an adhesion layer, and the damage of an adhesion layer.

X: Peeling of a base material, the shift of the adhesion layer position, the bubble in an adhesion layer, and at least 1 defect of breakage of an adhesion layer generate | occur | produce.

The meaning of the term in Table 3 and Table 4 is as follows.

* 1: The usage-amount (mass%) described in the table | surface is a ratio when the total mass of (A) component, (B) component, and (C) component is 100 mass%. The 2-EHA solution and the IAA solution are not contained in the mass% of, The 2-EHA solution and the IAA solution of the component (A) are contained in the mass% of 2-EHA and IAA of the component (B).

* 2: The usage-amount (mass%) of (D) component is a ratio in the case where the total mass of (A) component, (B) component, and (C) component is 100 mass%.

2-EHA: 2-ethylhexyl acrylate (product name "2-ethylhexyl acrylate", the product of Mitsubishi Chemical Corporation)

ISTA: Isostearyl acrylate (product name `` ISSA '', product of Osaka Organic Chemical Co., Ltd.)

BA: n-butyl acrylate (product name "butyl acrylate", Mitsubishi Chemical Co., Ltd. product)

IA: Isobonyl acrylate (product name `` IA '', product of Osaka Organic Chemical Industry Co., Ltd.)

HEA: 2-hydroxyethyl acrylate (product name "HEA", product of Osaka Organic Chemical Industry Co., Ltd.)

HPA: 2-hydroxypropyl (meth) acrylate

4HBA: 4-hydroxybutyl acrylate

L200: 1-hydroxycyclohexyl phenyl ketone (product name "LuNa200", DHS Japan Co., Ltd. product)

TFT: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide

Claims (8)

(A) Polyurethane which is a reaction product of (a1) polyol, (a2) aliphatic polyisocyanate, (a3) hydroxyl-containing mono (meth) acrylate, and (a4) hydroxyl-containing photoinitiator,
(B) (b1) Alkyl mono (meth) acrylate having 4 to 18 carbon atoms of a linear alkyl group containing no alicyclic structure, Alkyl mono (meth) having 4 to 18 carbon atoms of a branched alkyl group containing no alicyclic structure At least one alkyl mono (meth) acrylate selected from alkylmono (meth) acrylates having 6 to 15 carbon atoms in the alkyl group containing a) acrylate and (b2) an alicyclic structure,
(C) containing a primary hydroxyl group containing mono (meth) acrylate,
10 mol% or more and 90 mol% or less of (a3) component are introduce | transduced into the isocyanate group in the terminal of the urethane prepolymer which (A) component consists of (a1) component and (a2) component, and (a4) component is 10 mol% More than 90mol%
Active energy ray-curable pressure-sensitive adhesive composition.
The method of claim 1,
When the sum total of (A) component, (B) component, and (C) component is 100 mass%, (A) component is 20 mass% or more and 70 mass% or less, and (B) component is 25 mass% or more 75 mass% or less and (C) component are 5 mass% or more and 55 mass% or less active energy ray hardening-type adhesive composition.
The method according to claim 1 or 2,
The active energy ray hardening type adhesive composition whose number average molecular weights of (a1) component are 700 or more and 10,000 or less.
The method according to any one of claims 1 to 3,
(a3) The active energy ray-curable pressure-sensitive adhesive composition wherein the component is a hydroxyl group-containing mono (meth) acrylate having 5 to 10 carbon atoms.
The method according to any one of claims 1 to 4,
(A) The weight average molecular weight of component is 10,000 or more and 90,000 or less
Active energy ray curable pressure-sensitive adhesive composition.
Hardened | cured material of the active-energy-ray-curable adhesive composition of any one of Claims 1-5.
The method of claim 6,
Hardened | cured material whose storage elastic modulus G 'in 25 degreeC and 1 Hz is 8 * 10 <^4> Pa or more, and the loss coefficient TAδ in 50 degreeC and 1Hz is 0.4 or more.
The adhesive sheet which comprises the hardened | cured material of Claim 6 or 7 in at least one surface of a base material surface.