KR102323585B1 - Active energy ray-curable adhesive composition, cured product and adhesive sheet - Google Patents

Abstract

An object of the present invention is to provide an active energy ray-curable pressure-sensitive adhesive composition, a cured product, and an adhesive sheet.
The present invention is
(A) (a1) polyol, (a2) aliphatic polyisocyanate, (a3) hydroxyl group-containing mono(meth)acrylate, and (a4) hydroxyl group-containing polyurethane, which is a reaction product of a photopolymerization initiator;
(B) (b1) Alkyl mono(meth)acrylate in which the straight-chain alkyl group not containing an alicyclic structure has 4 or more and 18 or less carbon atoms, and the branched alkyl group not containing an alicyclic structure has 4 or more and 18 or less carbon atoms. ) acrylate and (b2) at least one alkyl mono (meth) acrylate selected from alkyl mono (meth) acrylates having 6 to 15 carbon atoms in the alkyl group containing an alicyclic structure;
(C) containing mono (meth) acrylate containing a primary hydroxyl group,
(A) component is 10 mol% or more and 90 mol% or less of (a3) component is introduced with respect to the isocyanate group at the terminal of the urethane prepolymer composed of (a1) component and (a2) component, and (a4) component is 10 mol% Introduced more than 90 mol%
It relates to an active energy ray-curable adhesive composition.

Description

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

The present invention relates to an active energy ray-curable pressure-sensitive adhesive composition, a cured product, and an adhesive sheet.

Recently, a display device such as a touch panel is used in digital information devices such as a mobile phone, a portable game machine, and a car navigation system. In addition, in such a display device, an optical member such as a liquid crystal element, a light emitting diode element, and an organic electroluminescence element is often used.

In manufacturing a display device, a transparent double-sided adhesive sheet is used for bonding the display device and the optical member or between the optical members. Such double-sided pressure-sensitive adhesive sheets are required to have properties such as transparency, weather resistance, and metal corrosion prevention properties.

In addition, in the touch panel, in order to improve design (designability), cosmetic printing on the frame portion (printing performed on the back side of the periphery of the display (white part of the glass cover on the surface, etc.)) Some are implemented. Since cosmetic printing generates a step difference between the printed part and the non-printed part, the adhesive layer of the double-sided adhesive sheet has traceability (hereinafter also referred to as "step followability") to fill the printing step. is required If the level difference followability is insufficient, the adhesive layer may float in the vicinity of the level difference, and thus there is a risk of light reflection loss.

On the other hand, there is a process of cutting when processing the adhesive sheet, and it is required that the adhesive layer of the cut part does not adhere to the blade after cutting. In addition, it is also necessary that cross-sectional roughness does not occur in the adhesive layer of the cut part. When the elastic modulus at room temperature is low in the adhesive layer, the adhesive layer of the cut part adheres to the punching blade after the punching process, and there is a risk that the cross-sectional roughness of the cut part of the adhesive layer may occur. this gets worse

As a pressure-sensitive adhesive layer with improved step followability and flexibility, a thermosetting UV-curable pressure-sensitive adhesive composition comprising a base polymer containing a methacrylic acid ester monomer and a plasticizer has been proposed (see Patent Document 1). In addition, as the pressure-sensitive adhesive sheet with improved step followability and punching processability, as an adhesive layer, a polymerizable urethane polymer having ethylenically unsaturated groups at both ends of the molecule (A), and one hydroxyl group at one terminal of the molecule, Moreover, the ultraviolet curable adhesive composition containing the polymerizable urethane polymer (B) which has one ethylenically unsaturated group at the other terminal, and a monofunctional acrylate 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 a plasticizer having a low softening point is used, there is concern about a decrease in the holding force at a high temperature. In addition, since a plasticizer having a low softening point is used, the elastic modulus at room temperature is lowered, and after the punching process, there is a fear that the cut part is attached to the punching blade and the cut part of the adhesive layer is roughened. Moreover, since the said ultraviolet curable adhesive composition contains a lot of solvent, when producing an adhesive sheet, the process of removing a solvent is required.

Only the combination of the polyfunctional urethane acrylate and the monofunctional urethane acrylate of Patent Document 2 is insufficient in the adhesion to the substrate and the followability to the step. In addition, although no endurance test (heat resistance, moist heat resistance test, etc.) is performed in Patent Document 2, even if the durability test is performed, there is a fear that peeling off or a decrease in step followability after the test occurs.

In the present invention, it is an object of the present invention to provide an active energy ray-curable pressure-sensitive adhesive composition, a cured product, and an adhesive sheet that can be used without a solvent and is compatible with high step followability and workability even in a single layer, and also excellent in adhesive strength.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination in order to solve the said subject, the present inventors find that the said subject can be solved by using a predetermined active energy ray-curable adhesive composition, its hardened|cured material, and the adhesive sheet provided with its hardened|cured material, and this invention has completed

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

(Item 1)

(A) (a1) polyol, (a2) aliphatic polyisocyanate, (a3) hydroxyl group-containing mono(meth)acrylate, and (a4) hydroxyl group-containing polyurethane, which is a reaction product of a photopolymerization initiator;

(B) (b1) Alkyl mono(meth)acrylate in which the straight-chain alkyl group not containing an alicyclic structure has 4 or more and 18 or less carbon atoms, and the branched alkyl group not containing an alicyclic structure has 4 or more and 18 or less carbon atoms. ) acrylate and (b2) at least one alkyl mono (meth) acrylate selected from alkyl mono (meth) acrylates having 6 to 15 carbon atoms in the alkyl group containing an alicyclic structure;

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

(A) component is 10 mol% or more and 90 mol% or less of (a3) component is introduced with respect to the isocyanate group at the terminal of the urethane prepolymer composed of (a1) component and (a2) component, and (a4) component is 10 mol% Introduced more than 90 mol%

An active energy ray-curable pressure-sensitive adhesive composition.

(Item 2)

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

(Item 3)

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

(Item 4)

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

(Item 5)

(A) The active energy ray-curable adhesive composition in any one of items 1-4 whose weight average molecular weights of component are 10,000 or more and 90,000 or less.

(Item 6)

A cured product of the active energy ray-curable pressure-sensitive adhesive composition according to any one of items 1 to 5.

(Item 7)

The cured product according to item 6, wherein the storage modulus G' at 25°C and 1 Hz is 8×10 ⁴ pa or more, and the loss coefficient T a δ at 50°C and 1 Hz is 0.4 or more.

(Item 8)

A pressure-sensitive adhesive sheet comprising the cured product according to item 6 or 7 on at least one surface of a substrate surface.

Since the active energy ray-curable pressure-sensitive adhesive composition of the present invention can be used without a solvent, the solvent removal step can be omitted when producing the pressure-sensitive adhesive sheet. In addition, the pressure-sensitive adhesive layer (hereinafter, also referred to as "cured product") of the active energy ray-curable pressure-sensitive adhesive composition of the present invention has high step followability (ie, flexibility during heating) and workability (ie, toughness at room temperature) even if it is a single layer. )) is compatible and exhibits excellent adhesive force. In addition, the adhesive layer is colorless and transparent, and has excellent durability in a high-temperature, high-humidity environment.

The present invention is

(A) (a1) polyol (hereinafter also referred to as “(a1) component”), (a2) aliphatic polyisocyanate (hereinafter also referred to as “(a2) component”), (a3) hydroxyl-containing mono (meth) acrylate (hereinafter also referred to as “component (a3)”) and (a4) a hydroxyl group-containing photopolymerization initiator (hereinafter also referred to as “component (a4)”) of polyurethane (hereinafter also referred to as “component (A)”) and ,

(B) (b1) Alkyl mono(meth)acrylate in which the straight-chain alkyl group not containing an alicyclic structure has 4 to 18 carbon atoms, and the branched alkyl group not containing an alicyclic structure has 4 to 18 carbon atoms The following alkyl mono(meth)acrylates (hereinafter also referred to as “(b1) component”) and (b2) alkyl mono(meth)acrylates having 6 to 15 carbon atoms in the alkyl group containing the alicyclic structure (hereinafter referred to as “(b2) ) one or more alkyl mono (meth) acrylates (hereinafter also referred to as "(B) component") selected from)

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

(A) component is 10 mol% or more and 90 mol% or less of (a3) component is introduced with respect to the isocyanate group at the terminal of the urethane prepolymer composed of (a1) component and (a2) component, and (a4) component is 10 mol% Introduced more than 90 mol%

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

Hereinafter, each component will be described in detail. In addition, in this specification, (meth)acrylate is an acrylate and/or a methacrylate.

<(A) component>

(A) Component is the polyurethane which is a reaction material of (a1) component, (a2) component, (a3) component, and (a4) component.

<(a1) component>

(a1) A component is a polyol. (a1) By using a polyol as a component, the adhesive layer of this invention is excellent in transparency and flexibility. A polyol as used herein 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. (a1) The component may be a crystalline polyol or an amorphous polyol may be sufficient as it.

In the present specification, the crystalline polyol preferably refers to a substance in which the polyol has a crystal structure at 20°C or more and 60°C or less, more preferably 20°C or more and 40°C or less, and most preferably 25°C. .

(a1) As a component, a polyether polyol, a polyester polyol, a polymer polyol, a poly(meth)acryl polyol, a polycarbonate polyol, a castor oil-type polyol, and a polyolefin polyol are illustrated. In addition, in this specification, (meth)acryl refers to acryl and/or methacryl.

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

The polyether polyol may be a commercially available product. Examples of the product include polyetherdiol (product name "Adeca Polyether P Series", manufactured by AA Co., Ltd.), polyether triol (product name "Adeca Polyether G Series", manufactured by AA Co., Ltd.), polyether tetra All (product name “Adeca Polyether EDP Series”, manufactured by ADA Co., Ltd.), polyether polyol (product name “Adeca Polyether P1000”, “Adeca Polyether P2000”, ADECA Polyether P2000, ADECA Co., Ltd. product), polyethylene glycol ( Product name 「Polyethylene glycol #1,540」, product of NACALAI TESQUE, INC.), dipropylene glycol (product name 「Dipropylene glycol」, product of JUNSEI CHEMICAL CO., LTD.) ), polypropylene glycol (product name: “Polypropylene glycol 400”, manufactured by Pure Chemical Co., Ltd.), polytetramethylene ether glycol (product name “PMTG650”, “PMTG1000”, “PTMG 2000”, Mitsubishi Chemical Co., Ltd.) (Mitsubishi Chemical Corporation) etc. are illustrated.

The polyester polyol may be a commercially available product. As the product, high refractive index grade polyester polyol (product name "Polylite RX-4800", manufactured by DIC Co., Ltd.), high crystallinity grade polyester polyol (product name "Polylite O-X-2523", "Polylite") OD-X-2547”, manufactured by DAC Co., Ltd.), transparent grade polyester polyol (product name: “Polylite OD-X-2420”, “Polylite OD-X-2692”, manufactured by DK Co., Ltd.), high Adhesive grade polyester polyol (product name: “Polylite ODP-X-2108”, manufactured by DLC Co., Ltd.), polyester polyol (product name “ELCOPY Series”, manufactured by Ubekosan Co., Ltd.) , polycaprolactone polyol (product name "Polylite O-X-2155", manufactured by DRC Co., Ltd.), polycaprolactonediol (product name "Placcel 200", manufactured by Daicel Corporation) , polycaprolactone triol (product name "Flaxel 300", manufactured by Daicel Co., Ltd.), polycaprolactone tetraol (product name "Flaxel 400", manufactured by Daicel Co., Ltd.) and the like.

The polymer polyol may be a commercially available product. Examples of the product include polymer polyols (product names "RTFlow series", "Sharpflow series", manufactured by Sanyo Chemical Industries, Ltd.), polymer polyols (product names "Exenol series", AGC Co., Ltd.) product) and the like.

The poly(meth)acryl polyol may be a commercially available product. As the product, acrylic polyol (product name: “Acrylic Polyol #6000”, manufactured by Taisei Fine Chemical Co., Ltd.), acrylic polyol (product name “ERTERAC7315-XS-60”, Jangheung Materials Industry Co., Ltd.) Responsible company (product of Eternal Materials Corporation.), acrylic polyol (product name "Acrylic Polyol P#5984", manufactured by Donghwa Sung Co., Ltd. (TOEI KASEI CO., LTD.)) and the like are exemplified.

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

The castor oil-based polyol may be a commercially available product. As the product, a castor oil-based polyol (product name “URC H series”, manufactured by Itoh Oil Chemicals Co., Ltd.), a castor oil-based polyol (product name “castor oil-based polyol HSMC-025P”, “ Castor oil-based polyol HSMC-075P", Hokoku Corporation (product of Hokoku Corporation), etc. are illustrated.

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 product, polybutadienediol ((product name: “PＰｏｌｙｂｄ R-45ＨＴ”) -1000", "NISOSO-PB-2000", "NISOS-POG-1000", "Nihon Soda" (Nippon Soda) (Nippon Soda) (Nippon Soda), Ltd. Addition polybutadienediol (product names "NISOSO-PA-1000", "NISOS-PAG-2000", manufactured by Nippon Soda Co., Ltd.) and the like are exemplified.

Since component (a1) is excellent in the toughness and adhesive force at room temperature of an adhesive layer, Preferably it is a polyol provided with crystallinity at 20 degreeC or more and 60 degrees C or less, More preferably, it is a crystalline polyether polyol. The component (a1) is preferably at least one selected from the group consisting of polyether polyols, polycaprolactone polyols and polyolefin polyols, more preferably polyether polyols and polyolefins, from the viewpoint of being relatively excellent in heat and moisture resistance. It is at least 1 type selected from the group which consists of polyols.

(a1) Since the number average molecular weight of a component is excellent in adhesive force and step|step difference followability|trackability of an adhesive layer, Preferably they are 700 or more and 10,000 or less. If the number average molecular weight of the component (a1) is less than the above lower limit, the adhesive layer tends to become hard, and when the above upper limit is exceeded, the adhesive layer tends to become soft. tends to In the present specification, the number average molecular weight can be obtained by the method described in JIS K7252-1:2016.

(a1) Since an adhesive layer is excellent in step|step difference followability|trackability and workability, as for the number of hydroxyl groups of component, Preferably they are 1.5 or more and 3 or less, More preferably, they are 1.8 or more and 2.5 or less. In this specification, the number of hydroxyl groups can be calculated|required by the method described in JISK1557-1:2007. Specifically, in the present invention, the number of hydroxyl groups can be obtained by an acetylation method.

<(a2) component>

(a2) A component is an 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.

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

(a2) As a component, linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic aliphatic polyisocyanate, etc. are illustrated.

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

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

As alicyclic aliphatic diisocyanate, dicyclohexylmethane 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.

As linear aliphatic triisocyanate, lysine triisocyanate etc. are illustrated.

Since component (a2) is excellent in durability after a heat-and-moisture test in an adhesive layer and is excellent in step|step difference followability, Preferably it is an aliphatic diisocyanate, More preferably, it is linear aliphatic diisocyanate and/or an alicyclic aliphatic diisocyanate. am.

(a2) The component may be a commercially available product. As the product, 1,5-pentamethylene diisocyanate (product name "STABiO PDP", manufactured by Mitsui Chemicals, Inc.), hexamethylene diisocyanate (product name "HDD", Toso ( Co., Ltd.), 2,6-diisocyanatomethyl hexanoate (product name 「LDI」, manufactured by Chuo KASEIHIN CO., INC), trimethylhexamethylene diisocyanate (product code 「T1176」, Tokyo Hwasung Industrial Co., Ltd. (product of Tokyo Chemical Industry Co., Ltd.), dicyclohexylmethane 4,4'-diisocyanate (product name 「H12MDA」, manufactured by JoongAng Chemical Co., Ltd.) (Product name: Mitsupa Nato-IP), methyl cyclohexate 600 (Bisocyanato Chemical Co., Ltd.), Central Chemicals Co., Ltd. product), lysine triisocyanate (product name "LIT", manufactured by JoongAng Chemical Co., Ltd.), etc. are illustrated.

(a1) is usually 1.01~2 mol number (NCO _(a2)) between the ratio (NCO _(a2) / OH _(a1)) of the isocyanate group of the mol number of (OH _(a1)) and (a2) components of the hydroxyl component it is about

<(a3) component>

(a3) A component is a hydroxyl-containing mono(meth)acrylate. (a3) By using a component, it is excellent in sclerosis|hardenability in an adhesive composition, and is excellent in workability in an adhesion layer. (a3) When an adhesive composition is manufactured without containing a component, hardening will fail and an adhesive layer will become soft too much in room temperature. Since the adhesive layer tends to adhere to the surface of the blade of a cutting machine when cutting the base material etc. containing such an adhesive layer, the adhesive composition which does not contain the (a3) component is unpreferable. Moreover, (a3) component is not specifically limited, Various well-known things may be sufficient. (a3) A component may be used independently and may use 2 or more types together.

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

(a3) component is excellent in sclerosis|hardenability in an adhesive composition, and is excellent in processability in an adhesive layer, Preferably it is a C5-C10 hydroxyl-containing mono(meth)acrylate, More preferably, it is hydroxy It is ethyl (meth)acrylate.

(a3) The component may be a commercially available product. As the product, 2-hydroxyethyl acrylate (product name "HEA", manufactured by Osaka Organic Chemical Industry Ltd.), 2-hydroxyethyl methacrylate (product name "2-EMA") , Mitsubishi Gas Chemical Co., Ltd. (MITSUBISHI GAS CHEMICAL COMPANY, INC.), 2-hydroxypropyl methacrylate ((Product name 「Light Ester HPO(N)」, Kyoeisha Chemical Co., Ltd.) ., Ltd.), (product name 「2-hydroxypropyl methacrylate」, manufactured by NIPPON SHOKUBAI CO., LTD.)), 4-hydroxybutyl acrylate (product name 「4 -HBA", Osaka Organic Chemical Co., Ltd. product), 2-hydroxybutyl methacrylate (product name "Light Ester HOB(N)", manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl -2-hydroxyethyl phthalic acid (product name “HOP-MA-MP(N)”, manufactured by Kyoeisha Chemical Co., Ltd.), 2-hydroxy-3-phenoxypropyl acrylate (product name “epoxy ester M-600A”, Kyoeisha Chemical Co., Ltd. product) etc. are illustrated.

The mol% of the component (a3) introduced into the isocyanate group at the terminal of the urethane prepolymer composed of the component (a1) and the component (a2) is excellent in curability in the pressure-sensitive adhesive composition and excellent in workability in the pressure-sensitive adhesive layer, (a3) When the sum total of a 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 (a4) component, it is excellent in step|step difference followability|trackability in an adhesive layer. (a4) A component is not specifically limited, Various well-known things may be sufficient. (a4) A component may be used independently and may use 2 or more types together.

Examples of the component (a4) include a first-class monovalent hydroxyl group-containing photopolymerization initiator, a second-class monovalent hydroxyl group-containing photoinitiator, a tertiary monovalent hydroxyl group-containing photopolymerization initiator, and a divalent hydroxyl group-containing photopolymerization initiator.

In this specification, a monovalent|monohydric hydroxyl group means that the number of hydroxyl groups is one. In this specification, a divalent hydroxyl group means that the number of hydroxyl groups is two. In the present specification, the primary hydroxyl group refers to a substance in which one carbon atom is bonded to the 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 the carbon atom to which the hydroxyl group is bonded. The tertiary hydroxyl group as used herein refers to a substance in which three carbon atoms are bonded to the carbon atom to which the hydroxyl group is bonded.

Examples of the secondary monovalent hydroxyl group-containing photopolymerization initiator include 2-hydroxy-2-phenylacetophenone.

Examples of the tertiary monovalent hydroxyl group-containing photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

As a photoinitiator containing a divalent hydroxyl group, 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-propan-1-one and the like are exemplified.

Since component (a4) is excellent in step|step difference followability|trackability in an adhesive layer, Preferably it is a tertiary monovalent hydroxyl-containing photoinitiator, More preferably, 1-hydroxycyclohexylphenyl ketone and/or 2-hydroxy hydroxy-2-methyl-1-phenyl-propan-1-one.

(a4) The component may be a commercially available product. As the product, 2-hydroxy-2-phenylacetophenone (product code "B0079", manufactured by Toh Kyung-Kyung Industrial Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone ((product name: "OMGIMR", IRA), product), (product name “Lｕｎａ200”, manufactured by DPS Japan Co., Ltd.)), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ((product name: “OMP” (product name “OMP”), manufactured by RN) , (Product name “Lｕｎａ100”, manufactured by DHS Japan Co., Ltd.)), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (product code “H1361”, Tokyo Kyung Hee Industry Co., Ltd.) Co., Ltd. product), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name 「OMR2959」, manufactured by IGMT , 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl))-benzyl]phenyl}-2-methyl-propan-1-one (product name "OMNIMRAD127", IMG The product of R&amp;C, Inc.) etc. are illustrated.

The mol% of the (a4) component introduced into the isocyanate group at the terminal of the urethane prepolymer composed of the (a1) component and the (a2) component is excellent in the level difference followability in the adhesive layer, and the (a3) component and (a4) When the 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.

Molar ratio of (a3) component and (a4) component introduced into the isocyanate group at the terminal of the urethane prepolymer composed of (a1) component and (a2) component ([(a3) component mol]/ [(a4) component mol] ) is excellent in step difference followability in an adhesive layer and excellent in workability in an adhesive layer, Preferably it is 1/9-9/1, More preferably, it is 1/5-3/1.

In addition, "the mol ratio of (a3) component and (a4) component introduced into the isocyanate group at the terminal of the urethane prepolymer composed of (a1) component and (a2) component" is the isocyanate group at the terminal of the urethane prepolymer reacting (a3) It is a ratio of a component and (a4) component. In order to obtain component (A) in which the component (a3) and component (a4) are in a desired mol ratio, the component (a3) and component (a4) in an amount reacting with all of them relative to the amount of isocyanate groups present in the urethane prepolymer Mix and react in the desired mol ratio.

<Additives that can be blended with other components (A)>

(A) You may contain various additives in component as needed. Various well-known things may be sufficient as an additive. An additive may be used independently and may use 2 or more types together.

As the additive, a catalyst, a crystal nucleating agent, a crystallization accelerator, a chain transfer agent, and the like are exemplified.

(A) Although the manufacturing method of a component is not specifically limited, The manufacturing method of various well-known polyurethane is employable. The component (A) reacts the component (a1) and the component (a2) to produce a urethane prepolymer having one or more isocyanate groups at the terminal (hereinafter, component (A′)), and then the component (A′) and (a3) ) and (a4) component are reacted.Reaction temperature and reaction time are not particularly limited, but usually 70 ℃ or more and 85 ℃ or less, 1 hour or more and 5 hours or less. In the present invention, it is possible to use component (b1), component (b2), etc. as a diluent, preferably component (b1), and a polymerization inhibitor may be used so that component (a3) does not polymerize in the reaction system.

(A) Since the weight average molecular weight of component is excellent in adhesive force and step|step difference followability|trackability in an adhesion layer, Preferably it is 10,000 or more and 90,000 or less, More preferably, they are 20,000 or more and 70,000 or less. (A) When the weight average molecular weight of component is less than the said lower limit, the adhesive force of an adhesive layer tends to become weak, and when the said upper limit is exceeded, there exists a tendency for the viscosity of an adhesive composition to become high and manufacture becomes difficult. In this specification, the weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography method.

Content of (A) component is excellent in sclerosis|hardenability in an adhesive composition, and since it is excellent in adhesive force and step|step difference followability in an adhesion layer, the sum total of (A) component, (B) component, and (C)component is 100 mass % In terms of solid content, preferably 20 mass % or more and 70 mass % or less, more preferably 20 mass % or more and 60 mass % or less, and still more preferably 25 mass % or more and 50 mass % or less.

<(B) component>

(B) A 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 in which the linear alkyl group not containing an alicyclic structure has 4 or more and 18 or less carbon atoms, and an alkyl mono (meth) acrylate having 4 or more and 18 or less carbon atoms in the branched alkyl group not containing an alicyclic structure. ) at least one alkyl mono (meth) acrylate selected from acrylates. (b1) By using component, it is excellent in step|step difference followability|trackability in an adhesion layer. (b1) Various well-known things may be sufficient as a component. (b1) A component may be used independently and may use 2 or more types together. (b1) When carbon number of the alkyl group in the alkyl mono(meth)acrylate of a component is 19 or more, compatibility is bad and it is difficult to acquire the effect of this invention. Moreover, when carbon number of the alkyl group in the alkyl mono(meth)acrylate of (b1) component is 3 or less, since a boiling point is low, the storage stability of a product is inferior.

As an alkyl mono (meth) acrylate having 4 or more and 18 or less carbon atoms of a linear alkyl group containing no alicyclic structure, 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.

As an alkyl mono (meth) acrylate having 4 or more and 18 or less carbon atoms of the branched alkyl group not containing an alicyclic structure, isoamyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, iso Decyl (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. are illustrated.

(b1) A commercially available product may be sufficient as a component. As the product, butyl acrylate (product name “butyl acrylate”, manufactured by TOAGOSEI CO., LTD.), nonyl acrylate (product name “Viscoat #197”, Osaka Organic Chemical Co., Ltd.) product), lauryl acrylate (product name “Light Acrylate LA”, manufactured by Kyoeisha Chemical Co., Ltd.), stearyl acrylate (product name “Light Acrylate SA”, manufactured by Kyoeisha Chemical Co., Ltd.) , isostearyl acrylate (product name “ITSA”, manufactured by Osaka Organic Chemical Co., Ltd.), isoamyl acrylate (product name “Light Acrylate IAA”, manufactured by Kyoeisha Chemical Co., Ltd.), isononyl acrylate (product name) 「Isononyl acrylate」, manufactured by Osaka Organic Chemical Industry Co., Ltd.), isodecyl acrylate (product name 「IDAA」, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2-ethylhexyl acrylate (product name 「Acrylic acid-2- ethylhexyl", Mitsubishi Chemical Co., Ltd. product) etc. are illustrated.

The content of the component (b1) is preferable in terms of solid content when the total of the component (A), the component (B) and the component (C) is 100% by mass from the fact that the content of the component is excellent in the level difference followability 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>

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

(b2) As a component, 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) component is excellent in workability in an adhesion layer, Preferably cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 4-t- butylcyclohexyl ( At least one selected from the group consisting of meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate, more preferably isobornyl (meth) acrylate and/or dicyclopentanyl ( meth) acrylate.

(b2) A commercially available product may be sufficient as a component. As the product, cyclohexyl methacrylate (product name "Light Ester CH", manufactured by Kyoeisha Chemical Co., Ltd.), cyclohexyl acrylate (product name "Viscoat #155", manufactured by Osaka Organic Chemical Industry Co., Ltd.), 4-t-butylcyclohexyl methacrylate (product name “4-t-butylcyclohexyl methacrylate”, manufactured by MCC Unitec Co., Ltd.), 4-t-butylcyclohexyl Acrylates (product name “BLEMMER TBR” manufactured by NOF CORPORATION), isobornyl acrylate (product name “IBA”, manufactured by Osaka Organic Chemical Co., Ltd.), dicyclopentanyl acrylate ( The product name "FAA-513AS", Hitachi Chemical Company, Ltd. product), dicyclopentenyl acrylate (product name "FAA-511AS", Hitachi Chemical Company, Ltd. product) etc. are illustrated.

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

Since content of (b2) component is excellent in workability in an adhesion layer, when the sum total of (A) component, (B) component, and (C)component is 100 mass %, Preferably it is 10 in conversion of solid content. They are 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.

Since component (B) is excellent in both the step|step difference followable|trackability of an adhesion layer, and workability, it is especially preferable that both (b1) component and (b2) component are included.

(B) When content of component makes the sum total of (A) component, (B) component, and (C)component 100 mass %, Preferably they are 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) A component is a primary hydroxyl group containing mono(meth)acrylate. (C) By using component, it is excellent in sclerosis|hardenability in an adhesive composition, and it is excellent in durability after a moist-and-heat-resistance test in an adhesion layer. (C) A component is not specifically limited, Various well-known things may be sufficient. (C) A component may be used independently and may use 2 or more types together. (C) When mono(meth)acrylate which does not have a hydroxyl group is used as a substitute for component, the durability after a heat-and-moisture test and the haze value after a heat-and-moisture test are inferior. Moreover, when the mono(meth)acrylate containing a secondary hydroxyl group is used as a substitute for (C)component, the haze value after a heat-and-moisture resistance test is inferior.

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

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

(C) A commercially available product may be sufficient as a component. As said product, 2-hydroxyethyl acrylate (product name "HEA", manufactured by Osaka Organic Chemical Co., Ltd.), 2-hydroxyethyl methacrylate (product name "2-HEMMA", manufactured by Mitsubishi Gas Chemical Co., Ltd.) ; ) and the like are exemplified.

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

<(D)component>

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

(D) As a component, an alkylphenone type photoinitiator, an acylphosphine oxide type photoinitiator, a hydrogen extraction 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-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2- α-hydroxyl such as hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one and α-aminoalkylphenones such as hydroxyalkylphenone and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

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

As a hydrogen extraction type photoinitiator, phenylglyoxylic acid methyl ester etc. are illustrated.

As an 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 are exemplified.

(D) Since component is excellent in sclerosis|hardenability in an adhesive composition, Preferably they are (alpha)-hydroxyalkylphenone type|mold photoinitiator and/or an acylphosphine oxide type|mold photoinitiator.

(D) A commercially available product may be sufficient as a component. Examples of the product include 2,2-dimethoxy-1,2-diphenylethan-1-one (product name “OMR 651”, manufactured by IMG RHEV), 2-hydroxy-2-methyl-1-phenyl-propane- 1-ON ((Product code 「H0991」, manufactured by Dongkyung Sung Industrial Co., Ltd.), (Product name 「OMGIM」, RXNｓｉ)ｎｓ), (Product name 「L·LFAN100」, Hydroxy-cyclohexyl-phenyl-ketone ((Product name 「OMDN 184」, IMG M/D), (Product name 「LTOX(Note) 1-hydroxyl-D200」 )-Phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name “OMD 2959”, manufactured by IGM Corporation), 2-methyl-1-(4-methylthiophenyl)-2- Reno Dimorpholino-1-one (product name "OMNIRAD 907", IGM Resins Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name "OMNIRAD TPO", IGM Resins Co., Ltd.), bis ( 2,4,6-trimethylbenzoyl) -phenyl phosphine oxide (trade name "OMNIRAD 819", IGM Resins Co., Ltd.), phenyl rigs glyoxylic acid methyl ester (product name "OMNIRAD MBF", IGM Resins Co., Ltd.), 1,2 -Octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (product name "OMD OD 01", IMG M RD 1-[9-Ethyl oxime, Ethanone, manufactured by Ethanone-6) (2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (product names "OMD OD 02", IMG RM products) and the like are exemplified.

Since content of (D)component is excellent in sclerosis|hardenability and durability after a heat-and-moisture test in an adhesion layer, when the sum total of (A)component, (B)component, and (C)component makes 100 mass %, it is preferable Preferably, they are 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 mixable additives>

The pressure-sensitive adhesive composition of the present invention may contain various additives as needed.

An additive is not specifically limited, Various well-known things may be sufficient. An additive may be used independently and may use 2 or more types together.

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

The pressure-sensitive adhesive composition of the present 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.

Examples of the ketone solvent include methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone, and cyclohexanone.

As an aromatic solvent, toluene, xylene, etc. are illustrated.

As the alcohol solvent, methanol, ethanol, n-propanol, isopropanol, butanol and the like are exemplified.

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.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate or cellosolve acetate.

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

As a haloalkane solvent, chloroform etc. are illustrated.

As an amide solvent, dimethylformamide etc. are illustrated.

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

Viscosity (mPA·g/25°C) of the pressure-sensitive adhesive composition of the present invention is excellent in handling properties in the pressure-sensitive adhesive composition, preferably 100 or more and 10,000 or less, more preferably 300 or more and 8,000 or less, and still more preferably Usually 500 or more and 7,000 or less. In the present invention, the viscosity is a value (5 minutes) measured by an E-type viscometer (product name "TVE-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 mixable additives as needed. Although the order of mixing is not specifically limited, You may mix sequentially, and you may mix all at once.

<Cured material>

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

When a solvent is included in the pressure-sensitive adhesive composition, drying treatment may be performed before UV irradiation.

As the ultraviolet light source, an ultraviolet irradiation device including a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp is exemplified. 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 the pressure-sensitive adhesive composition is applied to various plastic film substrates to form a layer of the pressure-sensitive adhesive composition, the layer may be irradiated with ultraviolet rays to obtain a cured product.

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

The application amount is usually 1 g/m ² or more and 1,000 g/m ² or less, and preferably 3 g/m ² or more and 500 g/m ² or less.

The thickness of the cured product of the present invention is not particularly limited, but since the adhesive layer exhibits adequate step-difference tracking properties and is unlikely to generate bubbles, the coating film after drying is preferably 10 μm or more and 1,000 μm or less, more preferably 25 μm or more and 500 μm or less.

The storage modulus of the cured product of the present invention according to the 25 ℃ and 1Hz G '(hereinafter, also referred to as "G'") is preferably from 8 × 10 ⁴ is more than Pa, more preferably from 8 × 10 ⁴ Pa More than 1×10 ⁷ P a or less. Further, the loss coefficient T aq delta (hereinafter also referred to as "t a c delta") at 50°C and 1 Hz is preferably 0.4 or more, and more preferably 0.4 or more and 2 or less. Because of these characteristics, it is considered that the cured product exhibits both workability (G' at room temperature) and step followability (Ttδ at heating), and exhibits excellent adhesion and excellent durability after the heat-and-moisture test. In , G' is more preferably 1×10 ⁵ pa or more and 1×10 ⁷ pa or less, and Ta δ is even more preferably 0.5 or more and 1.5 or less. In the present specification, storage modulus and loss of cured product A coefficient can be calculated|required by the method described in JISK7244-1:1998.

Specifically, the storage modulus and the loss coefficient measure the dynamic viscoelasticity of the dynamic viscoelasticity with a commercially available measuring instrument (product name "MCRC302", manufactured by Anton Paar) under the following conditions. And from the measurement result, the storage modulus G' in 25 degreeC and the loss factor in 50 degreeC are calculated|required.

Transform Mode: Twist

Measurement frequency: 1Hz

Deformation: 0.01~1% ATF setting

Temperature increase rate: 3℃/min

Measuring temperature : 25~50℃

Shape: Parallel plate 8.0mmφ

In this specification, the storage modulus (G') is a value proportional to the maximum energy accumulated through the load cycle, and represents the stiffness of the adhesive layer, and the stiffness is the difficulty of deformation with respect to external forces such as bending or twisting. The higher the numerical value of the storage modulus at 25° C. and 1 Hz, the higher the stiffness of the adhesive layer at 25° C., and the smaller the number, the lower the stiffness 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 cured product of the present invention has excellent workability at room temperature.

In this specification, the loss coefficient (Taqδ) refers to the ratio of the loss modulus to the storage modulus (G'). This indicates how much energy the material will absorb (convert to heat) when the material is deformed. And the smaller the numerical value of the loss factor T a δ at 1 Hz, the less energy is absorbed at 50° C., and the larger the value, the more energy is absorbed at 50° C. (that is, it is easily deformed). Since the preferable loss factor T a δ in the ?

<Molded article>

As an application example of the pressure-sensitive adhesive composition, application of various known articles between substrates is exemplified. Those articles are not particularly limited, and various known articles may be used.

Examples of the article include the main body of home appliances such as refrigerators, televisions or air conditioners, their remote controls, frames and displays of information terminals such as mobile phones, smartphones, tablets or PCs, and plastic molded articles such as automobile parts or automobile interior materials. do.

The active energy ray-curable pressure-sensitive adhesive composition of the present invention is suitable for optical use. For example, it is applicable to the display panel of the multilayer structure in a digital display apparatus. In addition, as described above, since the adhesive strength is excellent and the level difference followability is also good, for example, when applied to a double-sided adhesive sheet for a touch panel, a decorative plate or an icon sheet is bonded to the panel, or a capacitive method is used. When the transparent substrate on which the transparent electrode in the touch panel is formed and the transparent plate such as glass or plastic are bonded together, bubbles are less likely to be generated. In addition, since the adhesive layer is strong at room temperature, the problem that the cut part adheres to the punching blade and cannot be separated during punching processing or the problem that the adhesive layer adheres to the punching blade does not occur easily, so it can be processed into various shapes have. Since the adhesive layer of the present invention has excellent transparency, it is suitable for use in displays such as televisions, smartphones, or tablets.

<Applicable equipment>

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

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

Examples of the metal include iron, aluminum, aluminized steel sheet, tin-free steel sheet (TFS), stainless steel sheet, phosphate galvanized steel sheet, or zinc/zinc alloy coated steel sheet (bonderizing steel sheet).

As plastics, polyesters 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, and the like are exemplified.

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, An ethylene vinyl acetate film, an ionomer resin film, an ethylene/(meth)acrylic acid copolymer film, an ethylene/(meth)acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, etc. are illustrated.

Examples of other substrates include epoxy resins, melamine resins, triacetyl cellulose resins, ABS resins, AS resins, norbornene-based resins.

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

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

As an optical substrate, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN), polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, 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, polyetheretherketone film , Polyester sulfone film, polyetherimide film, polyimide film, fluororesin film, polyamide film, acrylic resin film, norbornene-based resin film, cycloolefin resin film, plastic film, glass, tin-doped indium oxide film, ITO A film, a transparent conductive film, etc. are illustrated.

Specifically, as a combination of the adhesive layer of the present invention and the substrate for optics,

(1) Glass, the adhesive layer of the present invention, and a transparent conductive film (hereinafter also referred to as “ITO”)

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

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

(4) Glass, the adhesive layer of the present invention, liquid crystal display

and the like.

[Example]

Hereinafter, the present invention will be described more specifically 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 addition, in the following description, parts and % are based on mass.

In the present Example, the weight average molecular weight (Ml) was measured by gel permeation chromatography (GPC) under the following conditions.

(GPD measurement conditions)

Model: Product name 「HLC-8220GPD」 (manufactured by Tosoh Corporation)

Column: Product name 「TVNＫｇｅｌ G1000H」, 「TSKｅｌ G2000H」 (manufactured by Tosoh Corporation)

Developing solvent: tetrahydrofuran

Flow rate: 0.6mL/min

Measuring temperature: 40℃

Detector: Differential Refractive Index Detector (Refractive Index Detector)

Standard: monodisperse polystyrene

Sample: 20 µL of a solution obtained by preparing a 0.2% concentration of tetrahydrofuran solution in terms of solid content from the resin and filtering the solution through a microfilter

Among the production examples, the NCO measurement method of the urethane prepolymer is as follows.

Measuring device body: potential difference automatic titration device (product name 「ATV-400」, manufactured by Kyoto Electronics Manufacturing Co., Ltd.)

Measurement sequence:

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

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

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

4: Check that the sample is completely dissolved, and leave it for 15 minutes (direct sunlight, out of heat).

5: After 15 minutes, add 100 mL of isopropyl alcohol to the weighing bottle. Place the stirrer piece into the weighing bottle.

6: Titrate using a 0.1 mol/L hydrochloric acid solution (f=1.00) to determine the NCO value.

Measure the amount of sample to be measured after putting it into the automatic titrator. If the measurement difference is within 0.30, it is evaluated as good. If it is more than 0.30, measure one more and check within 0.30.

<Preparation Example 1: Preparation of (A)-1 component>

In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and air inlet, as component (a1), polytetramethylene ether glycol having a number average molecular weight of 2,000 (product name “PMTG2000”, manufactured by Mitsubishi Chemical Co., Ltd.) , hereinafter also referred to as “PMTG2000”) 863 parts, (a2) hexamethylene diisocyanate (product name “HDD”, manufactured by Tosoh Corporation, hereinafter also referred to as “HDD”) 97 parts, 2-ethylhexyl acrylate (Product name "-2-ethylhexyl acrylate", manufactured by Mitsubishi Chemical Co., Ltd., hereinafter also referred to as "2-E-A".) 333 parts and 0.5 parts of tin octylate were added, reacted at 70°C for 2 hours, and an intermediate isocyanate group A 2-EA solution of the terminal urethane prepolymer was obtained. To the obtained reaction product, 17 parts of 2-hydroxyethyl acrylate (product name "HEA", manufactured by Osaka Organic Chemical Co., Ltd., hereinafter also referred to as "HEA") as component (a3), 2-hydroxyethyl acrylate as component (a4) 23 parts of -2-methyl-1-phenyl-propan-1-one (product name “Lｕｎａ100”, manufactured by DPS Japan Co., Ltd., hereinafter also referred to as “L100”) is mixed, and the mixture is heated at 70°C for 2 hours to react. By confirming the completion of the reaction by NCO measurement, a 2-EA solution of the reactant (hereinafter, “(A)-1 component”) was obtained.

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

As described in Table 1, except that the components were changed, it was carried out in the same manner as in Production Example 1. In addition, Table 2 shows the mol% of the component (a3) and the mol% of the component (a4) introduced with respect to the isocyanate group at the terminal of the urethane prepolymer composed of the component (a1) and the component (a2).

<Preparation Example 6: Preparation of (A)-6 component>

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

<Comparative Preparation Example 5: Preparation of (A)-C5 component>

In the same reaction apparatus as in Production Example 1, 683 parts of PTM2000 as a component (a1), 77 parts of HDS as a component (a2), 333 parts of 2-EA, and 0.5 parts of tin octylate were added, and reacted at 70° C. for 2 hours. A 2-EA solution of isocyanate group-terminated urethane prepolymer as an intermediate was obtained. 227 parts of PTMG2000 as component (a1) and 13 parts of HEA as component (a3) were mixed with the obtained reaction product, kept warm at 70° C. for 2 hours, reacted, and reaction completion was confirmed by NMC measurement, and the reaction product (hereinafter, “(A) -C5 component") of 2-EH solution was obtained. (A)-C5 mol% of component (a3) was 50 mol%, and mol% of (a4) component was 0 mol%.

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

PTMG2000: polytetramethylene ether glycol (product name 「PTMG2000」, manufactured by Mitsubishi Chemical Co., Ltd.)

L220A L: Polycaprolactone polyol (product name 「Flaxel L220A L」, manufactured by Daicel Co., Ltd.)

DHID: Hexamethylene diisocyanate (product name 「DHID」, manufactured by Tosoh Co., Ltd.)

IPA: Isophorone diisocyanate (product name 「VESTSA」, Evonik Japan Co., Ltd. product)

HEA: 2-hydroxyethyl acrylate (product name 「HEA」, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

L100: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name “Lｕｎａ100”, manufactured by DHS Japan Co., Ltd.)

L200: 1-Hydroxycyclohexylphenyl ketone (product name “Lｕｎａ200”, manufactured by DHS Japan Co., Ltd.)

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

(A) As component (A)-1 component of Production Example 1, as component (b1), 2-EHA, as component (b2) isobornyl acrylate (product name "IBA", Osaka Organic Chemical Industry Co., Ltd. product, the following The pressure-sensitive adhesive composition (1) was obtained by mixing L200 as mass % shown in Table 3 as HEA and (D)component as HEA and (D)component (C).

<Examples 2-12 and Comparative Examples 1-7: Adhesive compositions (2) to (12) and pressure-sensitive adhesive compositions (C1) to (C7)>

It carried out in the same manner as in Example 1 except that the components were changed as shown in Tables 3 and 4.

<Performance evaluation (1): Viscosity (mＰa ｓ)>

The viscosities of the pressure-sensitive adhesive compositions (1) to (12) and the pressure-sensitive adhesive compositions (C1) to (C7) were measured at 25° C. using a commercially available measuring instrument (product name “TVE-10 viscometer”, manufactured by Dongdong Industries Co., Ltd.) did.

<Performance evaluation (2): Storage modulus (G’) and loss coefficient Tａｎδ>

Any one of the pressure-sensitive adhesive compositions (1) to (12) and (C1) to (C7) is coated with a 75 μm thick heavy peeling-treated polyester film (product name “SP-PET-03-75BU”, Panak Co., Ltd.) (product of PANAC CO., LTD.), applied so that the film thickness of the adhesive layer after curing becomes 200 μm, and a light peeling-treated polyester film (product name “SP-PET”) with a thickness of 38 μm on the pressure-sensitive adhesive composition application layer -01-38BU", manufactured by Panak Co., Ltd.), is attached to the peeled surface. Subsequently, on the obtained coating film, a high-pressure mercury lamp in the atmosphere (excluding adhesive compositions (9) and (C4): 100 mW/cm ² , 900 mJ/cm ² , pressure-sensitive adhesive compositions (9) and (C4): 100 mW/cm ² , 3,000 mJ) /cm ² By irradiating ultraviolet rays with an ultraviolet ray, a laminated film (light peeling polyester film/adhesive layer/heavy peeling polyester film) including an adhesive layer was produced. Next, a 1 cm x 1 cm test piece was cut out from the laminated film. Next, the light peeling polyester film and the heavy peeling polyester film are peeled off from the test piece, and a sheet (adhesive sheets (1) to (12) and (C1) comprising 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 hung on a commercially available measuring instrument (product name "MCRC302", manufactured by Antonpar Corporation), and the dynamic viscoelasticity was measured under the following conditions. And from the measurement result, the storage modulus G' in 25 degreeC and 1 Hz, and the loss coefficient Ttδ in 50 degreeC and 1 Hz were calculated|required.

(Measuring conditions)

Transform Mode: Twist

Measurement frequency: 1Hz

Deformation: 0.01~1% ATF setting

Temperature increase rate: 3℃/min

Measuring 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 performance evaluation (2) was irradiated with light with a wavelength of 500 nm, and its transmittance (%) ) was measured, and compatibility was evaluated based on the following criteria.

○ : 85% or more

× : less than 85%

<Performance Evaluation (4): Step Followability>

In the performance evaluation (2), a laminated film was prepared so that the film thickness of the pressure-sensitive adhesive composition after curing was 100 μm, and the light peeling polyester film was peeled off, and instead a 50 μm thick polyester film (product name “COSMOSHINE”) ) A-4300", Toyobo Co., Ltd. product (TOYOBO CO., LTD.) was joined with a 2 kg roller, and it left still for 2 hours. Subsequently, an 8 cm x 8 cm test piece was cut out from this and the heavy peeling-treated polyester film was peeled off to prepare a single-sided adhesive sheet (Cosmoshine A-4300/adhesive layer). A piece of polyester film (5cm×5cm×50μm) is superimposed on a glass plate (10cm×10cm×2mm), and a single-sided adhesive sheet (adhesive layer/Cosmoshine A-4300) (5cm×5cm×150μm) is further superimposed on it, By adhering with a 2 kg roller, a laminate (Cosmoshine A-4300 (50 µm thick)/Adhesive layer (100 µm thick)/Polyester film piece (50 µm thick)/Glass plate (2 mm thick)) (Laminate (1-1) to (12-1) and (C1-1) to (C7-1)) were prepared.

After treating the laminates (1-1) to (12-1) and (C1-1) to (C7-1) in an autoclave under the conditions of 50°C, 0.5Mp, and 20 minutes, 25°C After leaving still for 24 hours under the conditions of , 50% of humidity, it evaluated under the conditions of 85 degreeC, humidity of 85%, and 24 hours in a thermo-hygrostat. The following reference|standards visually evaluated the level|step difference followability|trackability of the adhesive layer of the said state.

1: Floating is not recognized along each side of a polyester film piece, and a bubble is not recognized either.

2: Although floating is not recognized along each side of a polyester film piece, 5 microbubbles can be confirmed as a limit.

3: A slightly wide float is confirmed along each side of the polyester film piece, and 10 fine bubbles can also be confirmed as a limit.

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

<Performance evaluation (5): haze value>

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

The haze values of the laminates (1-2) to (12-2) and (C1-2) to (C7-2) were measured with a commercially available measuring instrument (product name “Haze Transmittance Meter HMD-150”, Murakami Color Co., Ltd.) Measurement was made in accordance with JIS K 7136:2000 using a technical laboratory (manufactured by Murakami Color Research Laboratory). Moreover, the obtained haze value is the value which included the haze value of the base material (Cosmoshine A-4300 and a glass plate).

<Performance evaluation (6): haze value (after moist heat test)>

The haze values of the laminates (1-2) to (12-2) and (C1-2) to (C7-2) after standing still for 500 hours in a thermo-hygrostat at a temperature of 85°C and a humidity of 85% were measured using a commercially available measuring instrument ( It measured based on JISK7136:2000 using the product name "Haze transmittance meter HMD-150", manufactured by Murakami Color Technology Research Institute. Moreover, the obtained haze value is the value which included the haze value of the base material (Cosmoshine A-4300 and a glass plate).

<Performance evaluation (7): Adhesion>

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

<Performance evaluation (8): durability (after moist heat test)>

After the laminates (1-2) to (12-2) and (C1-2) to (C7-2) were left still for 500 hours in a thermo-hygrostat at a temperature of 85°C and a humidity of 85%, the durability of the adhesive layer was evaluated as follows. evaluated on the basis of

○: No peeling of the substrate, displacement of the adhesive layer, bubbles in the adhesive layer, or breakage of the adhesive layer

×: At least one defect such as peeling of the substrate, misalignment of the adhesive layer, bubbles in the adhesive layer, or breakage of the adhesive layer occurs

The meanings of terms in Tables 3 and 4 are as follows.

※1: The usage-amount (mass %) described in a table|surface is a ratio in case the total mass of (A) component, (B) component, and (C) component is 100 mass %. The mass% of component does not contain 2-EA solution or IBA solution.The 2-EA solution and IBA solution of component (A) are included in the mass% of component (B).

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

2-EHP: 2-ethylhexyl acrylate (product name "2-ethylhexyl acrylate", manufactured by Mitsubishi Chemical Co., Ltd.)

ITSA: Isostearyl acrylate (product name 「ISOTS」, manufactured by Osaka Organic Chemical Co., Ltd.)

BA: n-butyl acrylate (product name “butyl acrylate”, manufactured by Mitsubishi Chemical Co., Ltd.)

IBA: Isobornyl acrylate (product name 「IBA」, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

HEA: 2-hydroxyethyl acrylate (product name 「HEA」, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

PHPA : 2-hydroxypropyl (meth)acrylate

4HBR: 4-hydroxybutyl acrylate (product name 「4-HBA」, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

L200: 1-Hydroxycyclohexylphenyl ketone (product name “Lｕｎａ200”, manufactured by DHS Japan Co., Ltd.)

TPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name “SPS”, manufactured by DPS Japan Co., Ltd.)

Claims (8)

(A) (a1) polyol, (a2) aliphatic polyisocyanate, (a3) hydroxyl group-containing mono(meth)acrylate, and (a4) hydroxyl group-containing polyurethane, which is a reaction product of a photopolymerization initiator;
(B) (b1) Alkyl mono(meth)acrylate in which the straight-chain alkyl group not containing an alicyclic structure has 4 or more and 18 or less carbon atoms, and the branched alkyl group not containing an alicyclic structure has 4 or more and 18 or less carbon atoms. ) acrylate and (b2) at least one alkyl mono (meth) acrylate selected from alkyl mono (meth) acrylates having 6 to 15 carbon atoms in the alkyl group containing an alicyclic structure;
(C) containing mono (meth) acrylate containing a primary hydroxyl group,
(A) component is 10 mol% or more and 90 mol% or less of (a3) component is introduced with respect to the isocyanate group at the terminal of the urethane prepolymer composed of (a1) component and (a2) component, and (a4) component is 10 mol% Introduced more than 90 mol%
An active energy ray-curable pressure-sensitive adhesive composition.
According to claim 1,
(A) 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, (B) component is 25 mass % or more It is 75 mass % or less, and (C)component is 5 mass % or more and 55 mass % or less The active energy ray hardening type adhesive composition.
3. The method of claim 1 or 2,
(a1) An active energy ray-curable pressure-sensitive adhesive composition having a number average molecular weight of 700 or more and 10,000 or less.
3. The method of claim 1 or 2,
(a3) The active energy ray-curable adhesive composition whose component is a C5-C10 hydroxyl-containing mono(meth)acrylate.
3. The method of claim 1 or 2,
(A) The weight average molecular weight of the component is 10,000 or more and 90,000 or less
An active energy ray-curable pressure-sensitive adhesive composition.
A cured product of the active energy ray-curable pressure-sensitive adhesive composition according to claim 1 or 2.
7. The method of claim 6,
A cured product having a storage modulus G' of 8×10 ⁴ pa or more at 25°C and 1 Hz, and a loss coefficient T ab δ at 50°C and 1 Hz of 0.4 or more.
An adhesive sheet comprising the cured product of claim 6 on at least one surface of a substrate surface.