CN113474428A - Adhesive and adhesive sheet and method of using the same - Google Patents

Adhesive and adhesive sheet and method of using the same Download PDF

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Publication number
CN113474428A
CN113474428A CN202080015700.1A CN202080015700A CN113474428A CN 113474428 A CN113474428 A CN 113474428A CN 202080015700 A CN202080015700 A CN 202080015700A CN 113474428 A CN113474428 A CN 113474428A
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China
Prior art keywords
adhesive
sheet
adherend
irradiation
meth
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CN202080015700.1A
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Chinese (zh)
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CN113474428B (en
Inventor
田边慎吾
松帆志幸
石崎慎治
中村尚稔
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Toyochem Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention provides an adhesive capable of forming an adhesive layer, wherein the adhesive layer has good wettability expansibility to an adherend before irradiation of active energy rays, has removability capable of being attached to the adherend again, can be attached with adhesive force which is not easy to be peeled from the adherend, and can be easily peeled from the adherend after irradiation of the active energy rays, and the adhesive force is effectively reduced. The adhesive of the present invention comprises: a (meth) acryloyl group-free hydroxyl-terminated Urethane Prepolymer (UPH) which is a reaction product of 1 or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and 1 or more polyisocyanates (N); a polyfunctional isocyanate compound (I); and a radically polymerizable Monomer (MX) having 3 or more (meth) acryloyl groups in one molecule. The adhesive layer (12) composed of a cured product of the adhesive of the present invention has a reduced adhesive force due to irradiation with an active energy ray.

Description

Adhesive and adhesive sheet and method of using the same
Technical Field
The invention relates to an adhesive and an adhesive sheet and a method of using the same.
Background
Conventionally, pressure-sensitive adhesive sheets having an adhesive layer formed on a substrate sheet have been widely used as surface protective sheets for various members. As the adhesive, there are an acrylic adhesive, a silicone adhesive, a urethane adhesive, and the like. Since the acrylic pressure-sensitive adhesive has excellent adhesive strength and high adhesive force, the removability after the pressure-sensitive adhesive is bonded to an adherend is not good. Silicone adhesives are likely to cause contamination of adherends, and further, silicone resins having low molecular weights may volatilize and adsorb on the surfaces of devices such as electronic devices, causing troubles. In contrast, the urethane adhesive has good adhesion to an adherend, is relatively excellent in removability, and is difficult to volatilize.
In this specification, unless otherwise specified, "adhesive agent" is an adhesive agent having removability (removable adhesive agent), and "adhesive sheet" is an adhesive sheet having removability (removable adhesive sheet).
As a method for producing a urethane-based adhesive, there are a method of using a hydroxyl-terminated urethane prepolymer and a polyfunctional isocyanate compound, which are reaction products of a compound having an active hydrogen group such as a polyol and a polyisocyanate, and a method of reacting a polyol and a polyfunctional isocyanate compound at once without using a hydroxyl-terminated urethane prepolymer (one-shot method).
A general method for producing an adhesive sheet includes: a coating step of coating an adhesive on a substrate sheet; a heating step of forming a bonding layer including a cured adhesive material by subjecting the formed coating layer to a heat drying treatment; a winding step of winding the obtained adhesive sheet around a winding core to form an adhesive sheet roll; and a curing step of curing the adhesive sheet roll.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2011/121303.
Patent document 2: international publication No. 2016/092971.
Patent document 3: japanese patent laid-open No. 2014-196383.
Disclosure of Invention
Problems to be solved by the invention
Flat panel displays such as Liquid Crystal Displays (LCDs) and organic electroluminescent displays (OELDs), and touch panel displays in which the flat panel displays and the touch panel are combined are widely used in electronic devices such as Televisions (TVs), Personal Computers (PCs), mobile phones, and portable information terminals.
The urethane-based adhesive sheet is preferably used as a surface protective sheet for flat panel displays, touch panel displays, and substrates produced or used in these production steps (glass substrates, ITO/glass substrates having an ITO (indium tin oxide) film formed on a glass substrate, and the like), optical members, and the like.
In the production process of flat panel displays, touch panel displays, and the like, since productivity is improved, it is preferable that the adherend with an adhesive sheet can be conveyed at high speed to a processing section where necessary processes are performed. For example, automatic high-speed conveyance has been studied in which an adherend with an adhesive sheet is sucked from the adhesive sheet side using a vacuum suction member and lifted and conveyed to a desired location. In the automatic high-speed conveyance, it is preferable that the adherend with the adhesive sheet has a high adhesive force with which the adhesive sheet does not peel off from the adherend when being adsorbed on the vacuum adsorbing member. On the other hand, in the adherend with a pressure-sensitive adhesive sheet after completion of the required steps, the pressure-sensitive adhesive sheet preferably has a low adhesive strength so that the pressure-sensitive adhesive sheet can be peeled off at a high speed.
Patent document 1 discloses a switchable pressure-sensitive adhesive composition comprising a base adhesive polymer, a curable molecule curable by radical polymerization, a photoinitiator, and an internal crosslinking agent curable by a mechanism other than radical polymerization (claim 1).
The light irradiation causes polymerization of the curable molecules, thereby decreasing the peel strength. The rate of decrease in peel strength after light irradiation is, for example, 30 to 98%, preferably 50 to 95% (claims 15 and 16).
The composition described in patent document 1 is preferably a composition for a medical adhesive dressing (claim 25).
The base binder polymer is preferably a polyacrylate (claim 8). In [ example ], only an acrylic adhesive containing polyacrylate as a base adhesive polymer was produced. Since the acrylic pressure-sensitive adhesive has high adhesive force, the adhesive has poor wet spreadability on an adherend, and it is difficult to attach the adhesive in order without introducing air bubbles. Further, since the acrylic pressure-sensitive adhesive has a high adhesive force, the removability after the pressure-sensitive adhesive is bonded to an adherend is not good, and the remounting is difficult.
For example, in the acrylic pressure-sensitive adhesive sheet produced in example 8 of patent document 1, the adhesive force before light irradiation is about 1200 to 100gf/25mm, and the adhesive force after light irradiation is about 100 to 30gf/25mm (in terms of data in table 11). Since the acrylic pressure-sensitive adhesive sheet has a very high adhesive strength before light irradiation, the adhesive sheet is inferior in wet extensibility and removability. Although the adhesive strength of the acrylic adhesive sheet is reduced by light irradiation, the adhesive strength after light irradiation is still high, and high-speed peeling is difficult.
Patent document 2 discloses an ultraviolet-curable adhesive composition containing a urethane resin (a) having a hydroxyl group and a (meth) acryloyl group, a polyisocyanate crosslinking agent (B), a (meth) acrylic compound (C) having 2 or more (meth) acryloyl groups, an organic solvent (D), and a photopolymerization initiator (E) (claim 1).
Patent document 2 discloses a method for producing an ultraviolet-curable pressure-sensitive adhesive sheet in which the ultraviolet-curable pressure-sensitive adhesive composition is applied to a substrate and then the organic solvent (D) is dried (claim 9). Further, a method for producing a laminate by bonding 2 or more adherends using the above ultraviolet-curable pressure-sensitive adhesive sheet and then irradiating with ultraviolet rays is disclosed (claim 10).
The Adhesive described in patent document 2 is intended for use as an Optically Clear Adhesive (OCA) (paragraph 0002), and is not intended for use as a removable Adhesive. The pressure-sensitive adhesive sheet for optical clear adhesive is required to have high level difference traceability when it is adhered to an adherend, and is required to have no peeling after 2 or more adherends are adhered. In patent document 2, before ultraviolet irradiation, the crosslinking density is designed to be low while paying attention to the level difference trackability, and the removability is lowered by increasing the crosslinking density by ultraviolet irradiation.
In [ example ] of patent document 2, in order to suppress the crosslinking density before irradiation with ultraviolet rays, only a bifunctional polyol is used as a raw material polyol of the urethane resin (a).
In patent document 2, both the urethane resin (a) and the (meth) acrylic compound (C) as the photopolymerizable monomer have a (meth) acryloyl group, and the crosslinking density of the adhesive layer after irradiation with ultraviolet rays can be effectively increased (paragraph 0014). However, when both the urethane resin (a) and the (meth) acrylic compound (C) as the photopolymerizable monomer have a (meth) acryloyl group, the reactivity is too high, and the reaction is likely to start and proceed by irradiation with a small amount of ultraviolet light contained in the light of a fluorescent lamp or in the ambient light such as sunlight, and the adhesive force may be lowered. Irradiation with a small amount of ultraviolet light contained in ambient light during vacuum suction conveyance of an adherend is not preferable because the adhesive force of the adhesive layer is reduced.
Patent document 3 discloses an adhesive containing 30 to 80 parts by weight of a photopolymerizable monomer (B) having 1 (meth) acryloyl group, 0.05 to 3 parts by weight of a photopolymerization initiator (C), and 0.1 to 5 parts by weight of a silane coupling agent (D) per 100 parts by weight of a urethane resin (a) (claim 1).
In [ example ] of patent document 3, the number of functional groups of the photopolymerizable monomer (B) used is 1 to 2. In this case, crosslinking of the adhesive layer by light irradiation may be insufficient, and the decrease in adhesive strength after light irradiation may be insufficient for high-speed peeling.
The symbols of the components described in patent documents 1 to 3 are those described in these documents, and do not have any relationship with the symbols used for the components of the present invention.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive agent capable of forming an adhesive layer which has good wettability expandability with respect to an adherend before irradiation with active energy rays such as ultraviolet rays, has removability capable of being reattached to the adherend, can be attached with an adhesive force which is less likely to peel off from the adherend, and is capable of easily peeling off from the adherend by effectively reducing the adhesive force after irradiation with the active energy rays.
Another object of the present invention is to provide a pressure-sensitive adhesive sheet which has good wettability to an adherend before irradiation with an active energy ray such as an ultraviolet ray, has removability to the adherend to enable reattachment, can be attached with an adhesive strength which is less likely to peel off from the adherend, and has an adhesive strength which is effectively reduced after irradiation with the active energy ray to enable easy peeling from the adherend.
Means for solving the problems
The pressure-sensitive adhesive of the present invention is a removable pressure-sensitive adhesive comprising a hydroxyl-terminated Urethane Prepolymer (UPH) which is a reaction product of 1 or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and 1 or more polyisocyanates (N) and does not contain a (meth) acryloyl group, and a polyfunctional isocyanate compound (I), and further comprising a radical polymerizable Monomer (MX) containing 3 or more (meth) acryloyl groups in one molecule, wherein the pressure-sensitive adhesive layer composed of a cured product of the pressure-sensitive adhesive has a reduced adhesive force due to irradiation of an active energy ray.
The adhesive sheet of the present invention comprises a base sheet and an adhesive layer comprising a cured product of the adhesive of the present invention.
The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet suitable for a surface protective sheet.
The method for using the adhesive sheet of the present invention comprises: a step of bonding the adhesive sheet to the surface of an adherend; irradiating the adhesive sheet bonded to the surface of the adherend with active energy rays to reduce the adhesive strength of the adhesive sheet; and a step of peeling the pressure-sensitive adhesive sheet having a reduced adhesive force from the adherend.
In the present specification, unless otherwise specified, "adhesive force" is determined by the method described in [ example ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an adhesive agent capable of forming an adhesive layer which has good wettability and spreadability on an adherend before irradiation with active energy rays such as ultraviolet rays and has removability capable of being reattached to the adherend and which can be attached with an adhesive force that is less likely to peel off from the adherend, and which has an adhesive force effectively reduced after irradiation with active energy rays and can be easily peeled off from the adherend.
Further, according to the present invention, there can be provided a pressure-sensitive adhesive sheet which has good wettability to an adherend before irradiation with an active energy ray such as ultraviolet ray, has removability to the adherend to enable reattachment, can be attached with an adhesive strength which is less likely to peel off from the adherend, and can be easily peeled off from the adherend by effectively reducing the adhesive strength after irradiation with the active energy ray.
Drawings
Fig. 1 is a schematic cross-sectional view of an adhesive sheet according to embodiment 1 of the present invention.
Fig. 2 is a schematic cross-sectional view of the adhesive sheet according to embodiment 2 of the present invention.
Detailed Description
[ Binders ]
The adhesive of the present invention is a removable urethane adhesive comprising a hydroxyl-terminated Urethane Prepolymer (UPH) which is a reaction product of 1 or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and 1 or more polyisocyanates (N) and does not contain a (meth) acryloyl group, a polyfunctional isocyanate compound (I), and a radical polymerizable Monomer (MX) having 3 or more (meth) acryloyl groups in one molecule.
The adhesive sheet of the present invention is a urethane-based adhesive sheet comprising a base sheet and an adhesive layer composed of a cured product of the adhesive of the present invention.
The adhesive strength of the adhesive layer composed of the cured product of the adhesive of the present invention can be reduced before irradiation with active energy rays and after irradiation.
(hydroxyl-terminated Urethane Prepolymer (UPH))
The hydroxyl-terminated Urethane Prepolymer (UPH) is a reaction product obtained by copolymerizing 1 or more kinds of active hydrogen group-containing compounds (HX) and 1 or more kinds of polyisocyanates (N). If necessary, the copolymerization reaction can be carried out in the presence of 1 or more catalysts. If necessary, 1 or more solvents can be used in the copolymerization reaction. The hydroxyl terminated Urethane Prepolymer (UPH) is free of (meth) acryloyl groups.
< Compound containing active Hydrogen group (HX) >)
The active hydrogen group-containing compound (HX) is a compound having a plurality of active hydrogen groups in one molecule.
As the active hydrogen group, a Hydroxyl group (Hydroxyl group), a mercapto group, an amino group (in the present specification, unless otherwise specified, an amino group includes an imino group), and the like can be given. Examples of the active hydrogen group-containing compound (HX) include polyols having a plurality of hydroxyl groups in one molecule, polyamines having a plurality of amino groups in one molecule, aminoalcohols having amino groups and hydroxyl groups in one molecule, and polythiols having a plurality of mercapto groups in one molecule. These active hydrogen group-containing compounds (HX) may be non-polymeric or polymeric. These can be used in 1 or 2 or more.
Among them, polyhydric alcohols are preferable. Polyamines and polythiols are highly reactive with polyisocyanates and have a short pot life, and therefore, when they are used, they are preferably used in combination with polyols.
Examples of the polyol that can be used as the active hydrogen group-containing compound (HX) include polyester polyols, polyether polyols, polyacrylic polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil polyols. Among them, polyester polyols, polyether polyols, and combinations thereof are preferred. Preferably, the 1 or more active hydrogen group-containing compounds (HX) include polyether polyols.
As the polyester polyol that can be used as the active hydrogen group-containing compound (HX), a known polyester polyol can be used. Examples of the polyester polyol include compounds (esterified products) obtained by an esterification reaction of 1 or more polyol components and 1 or more acid components.
Examples of the polyhydric alcohol component as the raw material include Ethylene Glycol (EG), Propylene Glycol (PG), diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, and the like.
Examples of the acid component of the raw material include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1, 4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 4' -biphenyldicarboxylic acid, and acid anhydrides thereof.
As the polyether polyol that can be used as the active hydrogen group-containing compound (HX), a known polyether polyol can be used. Examples of the polyether polyol include compounds (addition polymers) obtained by addition polymerization of 1 or more kinds of ethylene oxide compounds using, as an initiator, an active hydrogen group-containing compound having a plurality of active hydrogen groups in one molecule.
Examples of the initiator include hydroxyl group-containing compounds and amines. Specific examples thereof include bifunctional initiators such as Ethylene Glycol (EG), Propylene Glycol (PG), 1, 4-butanediol, neopentyl glycol, butylethylpentanediol, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine; trifunctional initiators such as glycerol, trimethylolpropane and triethanolamine; tetrafunctional initiators such as pentaerythritol, ethylenediamine and aromatic diamines.
Examples of the oxirane compound include Alkylene Oxides (AO) such as Ethylene Oxide (EO), Propylene Oxide (PO), and Butylene Oxide (BO); tetrahydrofuran (THF), and the like.
The polyether polyol is preferably an alkylene oxide adduct of an active hydrogen-containing compound (also referred to as polyoxyalkylene polyol). Among these, bifunctional polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), PPG having Ethylene Oxide (EO) added to the end (PPG-EO), and polyalkylene glycol such as polytetramethylene glycol are preferable; trifunctional polyether polyols such as alkylene oxide adducts of glycerin, and the like.
Examples of polyamines that can be used as the active hydrogen group-containing compound (HX) include ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine, 1, 9-nonylenediamine, 1, 10-decylenediamine, 1, 12-dodecylenediamine, 1, 14-tetradecylenediamine, 1, 16-hexadecylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 1, 5-diamino-2-methylpentane, isophoronediamine, 1, 3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3, aliphatic polyamines such as 3, 5-trimethyl-cyclohexylamine, dimethylene amine having a norbornane skeleton, m-xylylenediamine (MXDA), hexamethylenediamine carbamate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; and aromatic polyamines such as 3, 3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), 4 '-diaminodiphenylmethane, 2, 4' -diaminodiphenylmethane, 3 '-diaminodiphenylmethane, 3, 4' -diaminodiphenylmethane, 2 '-diaminobiphenyl, 3' -diaminobiphenyl, 2, 4-diaminophenol, 2, 5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2, 3-tolylenediamine, 2, 4-tolylenediamine, 2, 5-tolylenediamine, 2, 6-tolylenediamine, 3, 4-tolylenediamine, and diethyltolylenediamine.
Examples of aminoalcohols that can be used as the active hydrogen group-containing compound (HX) include hydroxyl group-containing monoamines such as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tris (hydroxymethyl) aminomethane, and 2-amino-2-ethyl-1, 3-propanediol; diamines having a hydroxyl group such as N- (2-hydroxypropyl) ethanolamine, and the like.
Examples of polythiols which can be used as the active hydrogen group-containing compound (HX) include methanedithiol, 1, 3-butanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 2-benzenedithiol, 1, 3-benzenedithiol, 1, 4-benzenedithiol, 1, 10-decanedithiol, 1, 2-ethanedithiol, 1, 6-hexanedithiol, 1, 9-nonanedithiol, 1, 8-octanedithiol, 1, 5-pentanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, toluene-3, 4-dithiol, 3, 6-dichloro-1, 2-benzenedithiol, 1, 5-naphthalenedithiol, 1, 2-benzenedithiol, benzene-dithiol, 1, 3-benzenedimethylthiol, 1, 4-benzenedimethylthiol, 4' -thiobisbenzenethiol, 2, 5-dimercapto-1, 3, 4-thiadiazole, 1, 8-dimercapto-3, 6-dioxaoctane, 1, 5-dimercapto-3-thiopentane, 2-di-n-butylamino-4, 6-dimercapto-s-triazine, and a mercapto terminal polymer (such as polysulfide polymer).
The 1 or more active hydrogen group-containing compounds (HX) may include a bifunctional active hydrogen group-containing compound and/or a trifunctional or more active hydrogen group-containing compound. In general, a bifunctional active hydrogen group-containing compound has two-dimensional crosslinkability and can impart appropriate flexibility to an adhesive layer. The active hydrogen group-containing compound having a trifunctional group or more has three-dimensional crosslinkability, and can impart appropriate hardness to the adhesive layer. The properties of the urethane adhesive such as adhesive strength, cohesive strength, and removability can be adjusted by selecting the number of functional groups (the number of active hydrogen groups) of each active hydrogen group-containing compound (HX). The number of functional groups of each material can be selected so that the properties such as adhesive force, cohesive force, and removability fall within preferable ranges according to the application and the like.
From the viewpoint of easy compatibility between the adhesive strength and the removability, the 1 or more active hydrogen group-containing compounds (HX) preferably contain a bifunctional active hydrogen group-containing compound and a trifunctional or more active hydrogen group-containing compound.
The number average molecular weight (Mn) of the active hydrogen group-containing compound (HX) is not particularly limited. In view of preferable adhesion and wettability of the adhesive layer, the Mn of the active hydrogen group-containing compound (HX) is preferably 50 to 20000, more preferably 100 to 7000, and particularly preferably 400 to 5000.
< polyisocyanate (N) >
As the polyisocyanate (N), known polyisocyanates can be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
Examples of the aromatic polyisocyanate include 1, 3-phenylene diisocyanate, 4 ' -diphenyl diisocyanate, 1, 4-phenylene diisocyanate, 4 ' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4 ' -toluidine diisocyanate, 2, 4, 6-triisocyanate toluene, 1, 3, 5-triisocyanate benzene, dimethoxyaniline diisocyanate, 4 ' -diphenyl ether diisocyanate, and 4, 4 ' -triphenylmethane triisocyanate, omega ' -diisocyanate-1, 3-dimethylbenzene, omega ' -diisocyanate-1, 4-dimethylbenzene, omega, omega' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, and 1, 3-tetramethylxylylene diisocyanate.
Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene Diisocyanate (HDI), pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, and 2, 4, 4-trimethylhexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), and 1, 4-bis (isocyanotomethyl) cyclohexane.
In addition, examples of the polyisocyanate include trimethylolpropane adducts, biurets, allophanates, trimers (the trimers contain isocyanurate rings), and the like of the above polyisocyanates.
The preferred raw material mixing ratio of the hydroxyl-terminated Urethane Prepolymer (UPH) is as follows.
The raw material mixing ratio is preferably determined so that the ratio (NCO/H ratio) of the number of moles of isocyanate groups (NCO) in the polyisocyanate (N) to the total number of moles of active hydrogen groups (H) in the plurality of active hydrogen group-containing compounds (HX) is 0.20 to 0.95, more preferably 0.40 to 0.80. The closer the NCO/H ratio is to 1, the more likely it is that the hydroxyl-terminated Urethane Prepolymer (UPH) is likely to gel during synthesis. When the NCO/H ratio is 0.95 or less, gelation at the time of synthesizing a hydroxyl-terminated Urethane Prepolymer (UPH) can be effectively suppressed.
< catalyst >
In the polymerization of the hydroxyl-terminated Urethane Prepolymer (UPH), 1 or more kinds of catalysts can be used as necessary. As the catalyst, a known catalyst can be used, and examples thereof include a tertiary amine compound and an organic metal compound.
Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1, 8-diazabicyclo (5, 4, 0) undec-7-ene (DBU).
Examples of the organic metal compound include tin compounds and non-tin compounds.
Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dioctyltin dilaurate, dibutyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
Examples of the non-tin compound include titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate and butoxytitanium trichloride; lead systems such as lead oleate, lead 2-ethylhexoate, lead benzoate, and lead naphthenate; iron systems such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt systems such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc systems such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate.
The kind and amount of the catalyst can be appropriately designed within a range in which the reaction proceeds well.
When a plurality of active hydrogen group-containing compounds (HX) having different reactivity are used in combination, there is a possibility that polymerization stability in a single catalyst system is not good or a reaction solution is likely to be cloudy due to the difference in reactivity between these compounds. In this case, the use of 2 or more catalysts makes it easy to control the reaction (for example, reaction rate) and can solve the above-mentioned problems. In a system using a plurality of active hydrogen group-containing compounds (HX) having different reactivities in combination, it is preferable to use 2 or more catalysts. The combination of 2 or more catalysts is not particularly limited, and examples thereof include tertiary amine/organic metal type, tin type/non-tin type, and tin type/tin type. Tin-based/tin-based is preferred, and dioctyltin dilaurate and tin 2-ethylhexanoate are more preferred.
The mass ratio of tin 2-ethylhexanoate to dioctyltin dilaurate (tin 2-ethylhexanoate/dioctyltin dilaurate) is not particularly limited, but is preferably greater than 0 and less than 1, and more preferably 0.2 to 0.8. If the mass ratio is less than 1, the balance of the catalyst activity is good, gelation and white turbidity of the reaction solution are effectively suppressed, and the polymerization stability is further improved.
The amount of the 1 or more catalysts used is not particularly limited, but is preferably 0.01 to 1.0% by mass based on the total amount of the 1 or more active hydrogen group-containing compounds (HX) and the 1 or more polyisocyanates (N).
< solvent >
In the polymerization of the hydroxyl-terminated Urethane Prepolymer (UPH), 1 or more kinds of solvents can be used as necessary. As the solvent, known solvents can be used, and methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, and the like can be mentioned. Ethyl acetate, toluene and the like are particularly preferable from the viewpoints of solubility of the hydroxyl-terminated Urethane Prepolymer (UPH), boiling point of the solvent and the like.
< polymerization method of hydroxyl-terminated Urethane Prepolymer (UPH) >
The polymerization method of the hydroxyl-terminated Urethane Prepolymer (UPH) is not particularly limited, and known polymerization methods such as bulk polymerization and solution polymerization can be used.
Examples of the polymerization step of the hydroxyl-terminated Urethane Prepolymer (UPH) include: step 1) a step of putting 1 or more kinds of active hydrogen group-containing compounds (HX), 1 or more kinds of polyisocyanates (N), 1 or more kinds of catalysts as necessary, and 1 or more kinds of solvents as necessary into a flask together; step 2) a step of adding 1 or more kinds of active hydrogen group-containing compounds (HX), 1 or more kinds of catalysts as needed, and 1 or more kinds of solvents as needed to a flask, and dropping 1 or more kinds of polyisocyanate (N) thereto.
When a plurality of active hydrogen group-containing compounds (HX) and/or polyisocyanates (N) are used, the reaction may be carried out in a plurality of stages.
The reaction temperature when the catalyst is used is preferably less than 100 ℃, more preferably 50 to 95 ℃, and particularly preferably 60 to 85 ℃. When the reaction temperature is 100 ℃ or higher, the reaction rate, polymerization stability, and the like are difficult to control, and a hydroxyl-terminated Urethane Prepolymer (UPH) having a desired molecular weight may be difficult to form. The reaction temperature when no catalyst is used is preferably 100 ℃ or higher, more preferably 110 ℃ or higher.
(polyfunctional isocyanate Compound (I))
As the polyfunctional isocyanate compound (I), known compounds can be used, and compounds exemplified by polyisocyanate (N) which is a raw material of hydroxyl-terminated Urethane Prepolymer (UPH) (specifically, aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, and trimethylolpropane adducts/biuret/allophanate/trimers of these compounds) can be used.
(radically polymerizable Monomer (MX))
The adhesive of the present invention contains a radical polymerizable Monomer (MX) containing 3 or more (meth) acryloyl groups in one molecule. In the present specification, "(meth) acryloyl" refers to acryloyl and methacryloyl.
The radical polymerizable Monomer (MX) is a material which is polymerized and cured by irradiation with an active energy ray such as ultraviolet ray or electron beam in the presence of a radical polymerization initiator (R) as necessary. The radical polymerizable Monomer (MX) is preferably ultraviolet-curable by ultraviolet irradiation.
When the pressure-sensitive adhesive sheet of the pressure-sensitive adhesive of the present invention containing the radical polymerizable Monomer (MX) is used, the pressure-sensitive adhesive layer is cured by polymerization of the radical polymerizable Monomer (MX) caused by irradiation with an active energy ray after the pressure-sensitive adhesive sheet is applied to an adherend, and the pressure-sensitive adhesive sheet can be easily peeled from the adherend.
In the present invention, since the trifunctional or more radical polymerizable Monomer (MX) containing 3 or more (meth) acryloyl groups is used, a crosslinking reaction proceeds during polymerization of the radical polymerizable Monomer (MX), and curing of the adhesive layer and a decrease in adhesive force due to the curing can be effectively caused. Since curing of the adhesive layer and a decrease in adhesive force caused thereby can be caused more efficiently, the number of (meth) acryloyl groups contained in the radical polymerizable Monomer (MX) is preferably 4 or more, more preferably 5 or more. Since curing of the adhesive layer and a decrease in adhesive force caused thereby can be caused more effectively, the amount of the radical polymerizable Monomer (MX) containing 5 or more (meth) acryloyl groups is preferably 20% by mass or more, more preferably 40% by mass or more, particularly preferably 60% by mass or more, and most preferably 80% by mass or more, relative to the total amount of the radical polymerizable Monomer (MX).
The radical polymerizable Monomer (MX) having 3 or more (meth) acryloyl groups in one molecule is not particularly limited, and a known monomer can be used. Specific examples thereof include trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (acryloyloxyethyl) isocyanurate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (2-hydroxyethyl) acrylate, and pentaerythritol tetra (meth) acrylate, Ester compounds of a polyhydric alcohol such as alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and 1, 2, 3-cyclohexane tetra (meth) acrylate, and (meth) acrylic acid; and polyfunctional poly (meth) acrylate compounds such as polyurethane poly (meth) acrylate, polyester poly (meth) acrylate, polyether poly (meth) acrylate, polyacrylic poly (meth) acrylate, polyalcohol poly (meth) acrylate, polyepoxy poly (meth) acrylate, polyspiroacetal poly (meth) acrylate, polybutadiene poly (meth) acrylate, polythiolpolyene poly (meth) acrylate, and polysilicpoly (meth) acrylate. These compounds can be used in 1 or 2 or more.
The radical polymerizable Monomer (MX) preferably contains an active hydrogen group such as a hydroxyl group and an amino group. In this case, when the radical polymerizable Monomer (MX) is polymerized, a part of the radical polymerizable Monomer (MX) can be bonded to the urethane resin via the polyfunctional isocyanate compound (I), and curing of the adhesive layer and a decrease in adhesive force caused thereby can be more effectively caused.
It is particularly preferable that the radically polymerizable Monomer (MX) contains a hydroxyl group. Examples of the radical polymerizable Monomer (MX) having 3 or more (meth) acryloyl groups and hydroxyl groups include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. These monomers can be used in 1 or 2 or more.
In patent document 2 exemplified in [ background art ], (meth) acryloyl groups are present in both the urethane resin (a) and the (meth) acrylic compound (C) as a photopolymerizable monomer, thereby effectively increasing the crosslinking density of the adhesive layer after irradiation with ultraviolet rays (paragraph 0014). However, when both the urethane resin (a) and the (meth) acrylic compound (C) as the photopolymerizable monomer have a (meth) acryloyl group, the reactivity is too high, and the reaction is easily started and progressed by irradiation with a small amount of ultraviolet light contained in light of a fluorescent lamp or ambient light such as sunlight, and the adhesive force may be lowered. When the adherend is transported by vacuum adsorption, etc., the adhesive force of the adhesive layer is undesirably reduced by irradiation with a small amount of ultraviolet light contained in ambient light.
In the present invention, since the hydroxyl-terminated Urethane Prepolymer (UPH) does not contain a (meth) acryloyl group, it is possible to suppress a crosslinking reaction caused by irradiation with a small amount of ultraviolet rays contained in ambient light, and to suppress peeling of an adherend from the pressure-sensitive adhesive sheet when the adherend is transported by vacuum adsorption.
(radical polymerization initiator (R))
The adhesive of the present invention may optionally contain a radical polymerization initiator (R) for initiating the polymerization of the radical polymerizable Monomer (MX) upon irradiation with an active energy ray. When the radical polymerizable Monomer (MX) is ultraviolet-curable, the adhesive of the present invention preferably contains a radical polymerization initiator (R) (the radical polymerization initiator (R) in this case is also referred to as a photopolymerization initiator (RL)).
The radical polymerization initiator (R) is not particularly limited, and a known radical polymerization initiator can be used. Examples thereof include acetophenone polymerization initiators such as 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one; benzoin-based polymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; benzophenone-based polymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone and 4-benzoyl-4' -methyldiphenyl sulfide; thioxanthone-based polymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2, 4-diisopropylthioxanthone; 2, 4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthoyl-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphthoyl-1-yl) -4, triazine-based polymerization initiators such as 6-bis (trichloromethyl) -s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine and 2, 4-trichloromethyl (4' -methoxystyryl) -6-triazine; an acylphosphine oxide-based polymerization initiator; a borate-based polymerization initiator; a carbazole-based polymerization initiator; imidazole-based polymerization initiators, and the like. These polymerization initiators can be used in 1 kind or 2 or more kinds.
(plasticizer (P))
From the viewpoint of reducing the adhesive force of the adhesive layer and improving the wettability, the adhesive of the present invention may further contain 1 or more kinds of plasticizers (P) as necessary. The plasticizer (P) is not particularly limited, and an organic acid ester is preferable from the viewpoint of compatibility with other components.
Examples of the ester of a monobasic or polybasic acid and an alcohol include isostearyl laurate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, isostearyl palmitate, isocetyl stearate, octyldodecyl oleate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, diisodecyl adipate, diisostearyl adipate, dibutyl sebacate, diisocetyl sebacate, tributyl acetylcitrate, tributyl trimellitate, trioctyl trimellitate, trihexyl trimellitate, trioleate, and triisocetyl trimellitate.
Examples of the ester of another acid with an alcohol include esters of an unsaturated or branched fatty acid such as myristoleic acid, oleic acid, linoleic acid, linolenic acid, isopalmitic acid, and isostearic acid with an alcohol such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, and sorbitan.
As the ester of a mono-or polybasic acid with a polyalkylene glycol, for example, polyethylene glycol dihexanoate, polyethylene glycol di-2-ethylhexanoate, polyethylene glycol dilaurate, polyethylene glycol dioleate, and diethylene glycol monomethyl adipate, etc. are mentioned.
The molecular weight (formula weight or Mn) of the organic acid ester is preferably 250 to 1000, more preferably 400 to 900, and particularly preferably 500 to 850, from the viewpoint of improving wettability. When the molecular weight is 250 or more, the heat resistance of the adhesive layer is good, and when the molecular weight is 1000 or less, the wettability of the adhesive becomes good.
(solvent)
The adhesive of the present invention can contain 1 or more solvents as necessary. As the solvent, known solvents can be used, and methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, and the like can be mentioned. From the viewpoints of solubility of the hydroxyl-terminated Urethane Prepolymer (UPH), boiling point of the solvent, and the like, ethyl acetate, toluene, and the like are particularly preferable.
(deterioration inhibitor)
The adhesive of the present invention can contain 1 or more kinds of deterioration inhibitors as necessary. This can suppress deterioration of various properties due to long-term use of the adhesive layer. Examples of the deterioration inhibitor include hydrolysis resistance agents, antioxidants, ultraviolet absorbers, and light stabilizers.
< hydrolysis resistance agent >
When the adhesive layer undergoes a hydrolysis reaction under (wet) thermal conditions or the like to generate a carboxyl group, a hydrolysis resistant agent can be used to block the carboxyl group. Examples of the hydrolysis resistance agent include carbodiimide-based, oxazoline-based, and epoxy-based agents. Among them, from the viewpoint of the effect of suppressing hydrolysis, a carbodiimide type is preferable.
The carbodiimide-based hydrolysis inhibitor is a compound having 1 or more carbodiimide groups in one molecule.
Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, and naphthylcarbodiimide.
The polycarbodiimide compound can be produced by decarbonylating and condensing a diisocyanate in the presence of a carbodiimidization catalyst. Examples of the diisocyanate include 4, 4 ' -diphenylmethane diisocyanate, 3 ' -dimethoxy-4, 4 ' -diphenylmethane diisocyanate, 3 ' -dimethyl-4, 4 ' -diphenylmethane diisocyanate, 4 ' -diphenyl ether diisocyanate, 3 ' -dimethyl-4, 4 ' -diphenyl ether diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 1-methoxyphenyl-2, 4-diisocyanate, isophorone diisocyanate, 4 ' -dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and phospholene oxides (phospholene oxides) such as 3-phospholene isomers of the above compounds.
Examples of the oxazoline-based hydrolysis inhibitor include 2, 2 '-o-phenylenebis (2-oxazoline), 2' -m-phenylenebis (2-oxazoline), 2 '-p-phenylenebis (4-methyl-2-oxazoline), 2' -m-phenylenebis (4-methyl-2-oxazoline), 2 '-p-phenylenebis (4, 4' -dimethyl-2-oxazoline), 2 '-m-phenylenebis (4, 4' -dimethyl-2-oxazoline), 2 '-ethylenebis (2-oxazoline), 2' -tetramethylenebis (2-oxazoline), 2, 2 '-hexamethylenebis (2-oxazoline), 2' -octamethylenebis (2-oxazoline), 2 '-ethylenebis (4-methyl-2-oxazoline), 2' -diphenylenebis (2-oxazoline), and the like.
Examples of the epoxy-based hydrolysis agent include diglycidyl ethers of aliphatic diols such as 1, 6-hexanediol, neopentyl glycol, and polyalkylene glycol; polyglycidyl ethers of aliphatic polyhydric alcohols such as sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, and trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol; diglycidyl esters or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, and sebacic acid; diglycidyl ethers or polyglycidyl ethers of polyhydric phenols such as resorcinol, bis (p-hydroxyphenyl) methane, 2, 2-bis (p-hydroxyphenyl) propane, tris (p-hydroxyphenyl) methane and 1, 1, 2, 2-tetrakis (p-hydroxyphenyl) ethane; n-glycidyl derivatives of amines such as N, N-diglycidylaniline, N-diglycidyltoluidine, and N, N' -tetraglycidyl-bis (p-aminophenyl) methane; triglycidyl derivatives of aminophenols; triglycidyl tris (2-hydroxyethyl) isocyanurate, triglycidyl isocyanurate; epoxy resins such as o-cresol type epoxy resins and phenol novolac type epoxy resins.
The amount of the hydrolysis resistant agent added is not particularly limited, but is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4.5 parts by mass, and particularly preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
< antioxidant >
Examples of the antioxidant include a radical trapping agent and a peroxide decomposer. Examples of the radical trapping agent include phenol compounds and amine compounds. Examples of the peroxide decomposer include sulfur compounds and phosphorus compounds.
Examples of the phenolic compound include 2, 6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2, 6-di-t-butyl-4-ethylphenol, stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), 4 '-thiobis (3-methyl-6-t-butylphenol), 4' -butylidenebis (3-methyl-6-t-butylphenol), 3, 9-bis [1, 1-dimethyl-2- [ β - (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2, 4, 8, 10-tetraoxaspiro [5.5] undecane, phenylpropanoic acid, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-, C7-C9 side chain alkyl ester, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [ methylene-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxyphenyl) propionate ] methane, ethylene glycol bis [3, 3 ' -bis (4 ' -hydroxy-3 ' -t-butylphenyl) butyrate ] and 1, 3, 5-tris (3 ', 5 ' -di-t-butyl-4 ' -hydroxybenzyl) -S-triazine- 2, 4, 6- (1H, 3H, 5H) trione, tocopherol, and the like.
Examples of the sulfur-based antioxidant include dilauryl 3, 3 ' -thiodipropionate, dimyristyl 3, 3 ' -thiodipropionate, and distearyl 3, 3 ' -thiodipropionate.
Examples of the phosphorus-based compound include triphenyl phosphite, diphenylisodecyl phosphite, 4' -butylidenebis (3-methyl-6-tert-butylphenyl ditridecyl) phosphite, cycloneopentanetetraylbis (octadecyl phosphite), tris (nonylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3, 5-di-tert-butyl-4-hydroxybenzyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene, tris (2, 4-di-t-butylphenyl) phosphite, cycloneopentanetetraylbis (2, 6-di-t-butyl-4-methylphenyl) phosphite, and 2, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, and the like.
By using the antioxidant, thermal deterioration of the hydroxyl-terminated Urethane Prepolymer (UPH) can be prevented.
The amount of the antioxidant to be added is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and particularly preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
As the antioxidant, from the viewpoint of stability and effect of preventing oxidation, it is preferable to use one or more phenol compounds as the radical trapping agent, and it is more preferable to use 1 or more phenol compounds as the radical trapping agent in combination with 1 or more phosphorus compounds as the peroxide decomposer. Further, as the antioxidant, a phenol-based compound as a radical trapping agent and a phosphorus-based compound as a peroxide decomposer are used in combination, and it is particularly preferable to use these antioxidants in combination with the hydrolysis resistance agent.
< ultraviolet absorber >
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalamide compounds, cyanoacrylate compounds, and triazine compounds.
The amount of the ultraviolet absorber added can be appropriately designed within a range in which the initiation and progress of polymerization of the radical polymerizable Monomer (MX) by irradiation with active energy rays are not suppressed and the reaction of the radical polymerizable Monomer (MX) is not easily initiated by the light of a fluorescent lamp or the ambient light such as sunlight. When the radical polymerizable Monomer (MX) is uv-curable, the amount of the uv absorber to be added is designed according to the type of the uv absorber, the wavelength range of uv light to be irradiated to the adhesive layer, and the cumulative amount of light. The amount of the ultraviolet absorber added is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2.5 parts by mass, and particularly preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
< light stabilizer >
Examples of the light stabilizer include hindered amine compounds and hindered piperidine compounds. The amount of the light stabilizer to be added is not particularly limited, but is preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1.5 parts by mass, and particularly preferably 0.2 to 1 part by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
(antistatic Agent (AS))
The adhesive of the present invention can contain 1 or more antistatic Agents (AS) AS needed. Examples of the antistatic Agent (AS) include inorganic salts, ionic liquids, ionic solids, and surfactants, and among them, ionic liquids and ionic solids are preferable. The "ionic liquid" is also referred to as an ambient temperature molten salt, and is a salt having fluidity at 25 ℃.
Examples of the inorganic salt include sodium chloride, potassium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium carbonate, and sodium thiocyanate.
Examples of the imidazolium ion-containing ionic liquid include 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1, 3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide, and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
As the ionic liquid containing a pyridinium ion, for example, examples thereof include 1-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butylpyridinium bis (trifluoromethylsulfonyl) imide, 1-hexylpyridinium bis (trifluoromethylsulfonyl) imide, 1-octylpyridinium bis (trifluoromethylsulfonyl) imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methylpyridinium bis (perfluoroethylsulfonyl) imide and 1-methylpyridinium bis (perfluorobutylsulfonyl) imide.
Examples of the ammonium ion-containing ionic liquid include 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, and tri-N-butylmethylammonium bis (trifluoromethanesulfonyl) imide.
In addition, commercially available ionic liquids such as pyrrolidinium salts, phosphonium salts, and sulfonium salts can be suitably used.
The ionic solid is a salt of a cation and an anion, as in the case of the ionic liquid, and shows a solid state at 25 ℃ under normal pressure. As the cation, for example, an alkali metal ion, a phosphonium ion, a pyridinium ion, an ammonium ion, and the like are preferable.
Examples of the ionic solid containing an alkali metal ion include lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium bis (heptafluoropropylsulfonyl) imide, lithium bis (nonafluorobutylsulfonyl) imide, sodium bis (fluorosulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, sodium bis (pentafluoroethylsulfonyl) imide, sodium bis (heptafluoropropylsulfonyl) imide, sodium bis (nonafluorobutylsulfonyl) imide, potassium bis (fluorosulfonyl) imide, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (pentafluoroethylsulfonyl) imide, potassium bis (heptafluoropropylsulfonyl) imide, and potassium bis (nonafluorobutylsulfonyl) imide.
Examples of the ionic solid containing a phosphonium ion include tetrabutylphosphonium bis (fluorosulfonyl imide), tetrabutylphosphonium bis (trifluoromethanesulfonyl imide), tetrabutylphosphonium bis (pentafluoroethyl sulfonyl imide), tetrabutylphosphonium bis (heptafluoropropyl sulfonyl imide), tetrabutylphosphonium bis (nonafluorobutyl sulfonyl imide), tributylhexadecylphosphonium bis (fluorosulfonyl imide), tributylhexadecylphosphonium bis (trifluoromethylsulfonyl imide), tributylhexadecylphosphonium bis (pentafluoroethyl sulfonyl imide), tributylhexadecylphosphonium bis (heptafluoropropyl sulfonyl imide), tributylhexadecylphosphonium bis (nonafluorobutyl sulfonyl imide), tetraoctylphosphonium bis (fluorosulfonyl imide), tetraoctylphosphonium bis (trifluoromethylsulfonyl imide), tetraoctylphosphonium bis (pentafluoroethyl sulfonyl imide, tetraoctylphosphonium bis (heptafluoropropyl sulfonyl imide), and tetraoctylphosphonium bis (nonafluorobutyl sulfonyl imide).
Examples of the ionic solid containing a pyridinium ion include 1-hexadecyl-4-methylpyridinium difluorosulfonimide, 1-hexadecyl-4-methylpyridinium bistrifluoromethylsulfonimide, 1-hexadecyl-4-methylpyridinium dipentafluoroethylsulfonyl imide, 1-hexadecyl-4-methylpyridinium bistetrafluoropropylsulfonimide, and 1-hexadecyl-4-methylpyridinium bisnonafluorobutylsulfonimide.
Examples of the ionic solid containing an ammonium ion include lauryl trimethyl ammonium chloride, tributylmethyl bis (trifluoromethyl) sulfonyl imide, tributylmethyl bis (pentafluoroethyl) sulfonyl imide, tributylmethyl bis (heptafluoropropyl) sulfonyl imide, tributylmethyl bis (nonafluorobutyl) sulfonyl imide, octyl tributyl bis (trifluoromethyl) sulfonyl imide, octyl tributyl bis (pentafluoroethyl) sulfonyl imide, octyl tributyl bis (heptafluoropropyl) sulfonyl imide, octyl tributyl bis (nonafluorobutyl) sulfonyl imide, tetrabutyl bis (fluoro) sulfonyl imide, tetrabutyl bis (trifluoromethyl) sulfonyl imide, tetrabutyl bis (pentafluoroethyl) sulfonyl imide, tetrabutyl bis (heptafluoropropyl) sulfonyl imide, tetrabutyl bis (nonafluorobutyl) sulfonyl imide, and the like.
In addition, known ionic solids having cations such as pyrrolidinium ion, imidazolium ion, and sulfonium ion can be suitably used.
Examples of the surfactant include nonionic surfactants and anionic surfactants, and any type of surfactant is classified into a low-molecular surfactant and a high-molecular surfactant.
Examples of the nonionic low-molecular-weight surfactant include glycerin fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, and fatty acid diethanolamides.
Examples of the anionic low-molecular-weight surfactant include alkylsulfonates, alkylbenzenesulfonates, and alkylphosphates.
Examples of the amphoteric low-molecular surfactant include alkylbetaines and alkylimidazolium betaines.
Examples of the nonionic polymer surfactant include polyether ester amide type, ethylene oxide-epichlorohydrin type, and polyether ester type.
Examples of the anionic polymer surfactant include polystyrene sulfonic acid type surfactants.
Examples of the amphoteric polymer surfactant include amino acid type amphoteric surfactants such as higher alkyl aminopropionates, and betaine type amphoteric surfactants such as higher alkyl dimethyl betaines and higher alkyl dihydroxyethyl betaines.
The amount of the antistatic Agent (AS) added is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, per 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
(leveling agent)
The adhesive of the present invention can contain a leveling agent, as necessary. By adding the leveling agent, the leveling property of the bonding layer can be improved. Examples of the leveling agent include an acrylic leveling agent, a fluorine leveling agent, and a silicon leveling agent. From the viewpoint of suppressing contamination of an adherend after re-peeling of the pressure-sensitive adhesive sheet, an acrylic leveling agent or the like is preferred.
The amount of the leveling agent to be added is not particularly limited, and is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, and particularly preferably 0.1 to 1 part by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH), from the viewpoints of suppressing contamination with an adhesive after re-peeling of the adhesive sheet and improving the leveling property of the adhesive layer.
(other optional ingredients)
The adhesive of the present invention can contain other arbitrary components as necessary within a range not impairing the effects of the present invention. Examples of the other optional components include a catalyst, a resin other than the urethane resin, a filler (talc, calcium carbonate, titanium oxide, or the like), a metal powder, a colorant (pigment, or the like), a foil, a softening agent, a conductive agent, a silane coupling agent, a lubricant, an anticorrosive agent, a heat-resistant stabilizer, a weather-resistant stabilizer, a polymerization inhibitor, and an antifoaming agent.
When the binder of the present invention contains a catalyst, it is preferable to add a known catalyst inhibitor such as acetylacetone for the purpose of increasing the pot life of the binder.
(mixing ratio)
The adhesive of the present invention contains 1 or more kinds of hydroxyl-terminated Urethane Prepolymers (UPH), 1 or more kinds of polyfunctional isocyanate compounds (I), and 1 or more kinds of radically polymerizable Monomers (MX) containing 3 or more (meth) acryloyl groups in one molecule as essential components, and further contains 1 or more kinds of optional components as necessary. The mixing ratio is not particularly limited, but the mixing ratio is preferably as follows.
The amount of the 1 or more polyfunctional isocyanate compounds (I) is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and particularly preferably 5 to 15 parts by mass, based on 100 parts by mass of the 1 or more hydroxyl-terminated Urethane Prepolymers (UPH). When the amount of 1 or more polyfunctional isocyanate compounds (I) is 1 part by mass or more, the cohesive force of the adhesive layer is good, and when it is 30 parts by mass or less, the pot life is good.
From the viewpoint of the effect of reducing the adhesive force by irradiation with an active energy ray, the amount of the 1 or more radical polymerizable Monomers (MX) is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, particularly preferably 5 to 50 parts by mass, and most preferably 10 to 50 parts by mass, based on 100 parts by mass of the 1 or more hydroxyl-terminated Urethane Prepolymers (UPH).
(method for producing adhesive)
The method for producing the adhesive of the present invention is not particularly limited.
The adhesive of the present invention can be produced by adding and mixing 1 or more kinds of polyfunctional isocyanate compounds (I), 1 or more kinds of radically polymerizable Monomers (MX) containing 3 or more (meth) acryloyl groups in one molecule, and optionally 1 or more kinds of other optional components to 1 or more kinds of hydroxyl-terminated Urethane Prepolymers (UPH) synthesized by the above method (which may be in the form of a solution including a solvent).
[ adhesive sheet ]
The adhesive sheet of the present invention comprises a base sheet and an adhesive layer comprising a cured product of the adhesive of the present invention. The adhesive layer can be formed on one side or both sides of the substrate sheet. The exposed surface of the adhesive layer may be covered with a release sheet as necessary. The release sheet is peeled off before the pressure-sensitive adhesive sheet is attached to the adherend.
Fig. 1 shows a schematic cross-sectional view of an adhesive sheet according to embodiment 1 of the present invention. In fig. 1, reference numeral 10 is an adhesive sheet, reference numeral 11 is a base sheet, reference numeral 12 is an adhesive layer, and reference numeral 13 is a release sheet. The adhesive sheet 10 is a single-sided adhesive sheet having an adhesive layer formed on one side of a substrate sheet.
Fig. 2 shows a schematic cross-sectional view of an adhesive sheet according to embodiment 2 of the present invention. In fig. 2, reference numeral 20 denotes a pressure-sensitive adhesive sheet, reference numeral 21 denotes a base sheet, reference numerals 22A and 22B denote adhesive layers, and reference numerals 23A and 23B denote release sheets. The pressure-sensitive adhesive sheet 20 is a double-sided pressure-sensitive adhesive sheet in which pressure-sensitive adhesive layers are formed on both sides of a base sheet.
The substrate sheet is not particularly limited, and examples thereof include a resin sheet, paper, and a metal foil. The substrate sheet may be a laminate sheet in which arbitrary 1 or more layers are laminated on at least one surface of the substrate sheets. If necessary, the surface of the substrate sheet on the side where the adhesive layer is formed may be subjected to an easy adhesion treatment such as corona discharge treatment and anchor coating agent application.
The resin constituting the resin sheet is not particularly limited, and examples thereof include ester-based resins such as polyethylene terephthalate (PET); olefin resins such as Polyethylene (PE) and polypropylene (PP); vinyl resins such as polyvinyl chloride; amide resins such as nylon 66; urethane resin (including foam); combinations thereof and the like.
The thickness of the resin sheet from which the polyurethane sheet is removed is not particularly limited, but is preferably 15 to 300 μm. The thickness of the polyurethane sheet (including the foam) is not particularly limited, and is preferably 20 to 50000. mu.m.
The paper is not particularly limited, and may be plain paper, coated paper, art paper, or the like.
The constituent metal of the metal foil is not particularly limited, and examples thereof include aluminum, copper, and a combination thereof.
The release sheet is not particularly limited, and a known release sheet can be used, which is obtained by applying a known release treatment such as coating of a release agent to the surface of a substrate sheet such as a resin sheet or paper.
[ method for producing adhesive sheet ]
The adhesive sheet can be produced by a known method.
First, the adhesive of the present invention is coated on the surface of a substrate sheet, thereby forming a coating layer composed of the adhesive of the present invention. As the coating method, a known method can be used, and examples thereof include a roll coating method, a comma coating method, a die gap coating method, a reverse coating method, a screen printing method, and a gravure coating method.
Then, the coating layer is dried and cured to form a pressure-sensitive adhesive layer composed of a cured product of the pressure-sensitive adhesive of the present invention. The temperature for heating and drying is not particularly limited, but is preferably about 60 to 150 ℃. The thickness of the adhesive layer (thickness after drying) varies depending on the application, and is preferably 0.1 to 200 μm.
Next, a release sheet is attached to the exposed surface of the adhesive layer by a known method as needed.
As described above, a single-sided adhesive sheet can be produced.
By performing the above operation on both sides, a double-sided adhesive sheet can be manufactured.
In contrast to the above method, the adhesive of the present invention may be applied to the surface of a release sheet to form a coating layer composed of the adhesive of the present invention, and then the coating layer may be dried and cured to form an adhesive layer composed of a cured product of the adhesive of the present invention, and a substrate sheet may be laminated on the exposed surface of the adhesive layer.
Preferably, the method for producing the adhesive sheet comprises a coating step of coating an adhesive on a substrate sheet, a heating step of heat-drying the formed coating layer to form an adhesive layer containing a cured product of the adhesive, a winding step of winding the obtained adhesive sheet around a core to form an adhesive sheet roll, and a curing step of curing the adhesive sheet roll.
[ method of Using adhesive sheet ]
The method for using the adhesive sheet of the present invention comprises: a step of bonding the adhesive sheet of the present invention to the surface of an adherend; irradiating the adhesive sheet bonded to the surface of the adherend with active energy rays such as ultraviolet rays and electron beams to reduce the adhesive strength of the adhesive sheet; and a step of peeling the pressure-sensitive adhesive sheet having a reduced adhesive strength from the adherend.
The adhesive of the present invention contains a radical polymerizable Monomer (MX) and, if necessary, a radical polymerization initiator (R). Therefore, the adhesive layer formed of a cured product of the adhesive of the present invention can be polymerized and cured by irradiation with an active energy ray such as ultraviolet ray, and the adhesive strength after irradiation can be effectively reduced before irradiation with the active energy ray.
The pressure-sensitive adhesive layer composed of a cured product of the pressure-sensitive adhesive of the present invention has an appropriate adhesive force before irradiation with an active energy ray such as ultraviolet rays, has good wettability expansibility to an adherend, has removability to the adherend to enable re-attachment, and can be attached with an adhesive force that is not easily peeled off from the adherend, for example, when the adherend is transported by vacuum suction. When an active energy ray is irradiated to the pressure-sensitive adhesive layer formed of a cured product of the pressure-sensitive adhesive of the present invention, the adhesive force is effectively reduced by polymerization of the radical polymerizable Monomer (MX), and the pressure-sensitive adhesive layer is easily peeled from the adherend.
In the production process of flat panel displays, touch panel displays, and the like, it is preferable that the adherend with an adhesive sheet can be conveyed at high speed to a processing section where necessary processes are performed, in order to improve productivity. For example, automatic high-speed conveyance is studied in which an adherend with an adhesive sheet is sucked from the adhesive sheet side using a vacuum suction member and lifted up and conveyed to a desired location. In the automatic high-speed conveyance, it is preferable that the adherend with the adhesive sheet has a high adhesive force with which the adhesive sheet does not peel off from the adherend when being adsorbed on the vacuum adsorbing member. On the other hand, in the adherend with a pressure-sensitive adhesive sheet which has finished the required steps, the pressure-sensitive adhesive sheet preferably has a low adhesive strength so that the pressure-sensitive adhesive sheet can be peeled off at a high speed.
The "adherend with an adhesive sheet" refers to a laminate in which an adhesive sheet is bonded to the surface of a glass substrate, an ITO/glass substrate in which an ITO (indium tin oxide) film is formed on a glass substrate, or an adherend such as an optical component.
In such applications, after the adhesive sheet is bonded to the surface of an adherend and the required steps are completed, the adhesive sheet bonded to the surface of the adherend is irradiated with active energy rays such as ultraviolet rays to reduce the adhesive strength of the adhesive sheet, and the adhesive sheet with reduced adhesive strength can be easily peeled from the adherend.
The adhesive force of the adhesive layer before and after irradiation with the active energy ray and the rate of decrease in the adhesive force of the adhesive layer after irradiation with the active energy ray relative to the adhesive force before irradiation with the active energy ray can be appropriately designed depending on the application and the use conditions. In the application of the adherend using the vacuum suction member to convey the adhesive sheet at a high speed as described above, the following design is preferable.
The rate of decrease in adhesive force after irradiation with active energy rays of the adhesive layer relative to the adhesive force before irradiation with active energy rays is not particularly limited, but is preferably 2/3 or less, more preferably 1/2 or less, and particularly preferably 1/3 or less.
The adhesive force of the adhesive layer before irradiation with an active energy ray is preferably 100gf/25mm or less, more preferably 50gf/25mm or less, particularly preferably 26gf/25mm or less, and most preferably 20gf/25mm or less.
The adhesive force of the adhesive layer before irradiation with an active energy ray is preferably 8gf/25mm or more, more preferably 10gf/25mm or more, and particularly preferably 15gf/25mm or more.
The adhesive force of the adhesive layer after irradiation with an active energy ray is preferably 10gf/25mm or less, more preferably less than 8gf/25mm, still more preferably 6gf/25mm or less, particularly preferably 5gf/25mm or less, and most preferably less than 5gf/25 mm.
As described above, according to the present invention, it is possible to provide an adhesive agent capable of forming an adhesive layer which has good wettability expandability with respect to an adherend before irradiation with active energy rays such as ultraviolet rays, has removability capable of being reattached to the adherend, can be attached with an adhesive force which is less likely to peel off from the adherend, and effectively reduces the adhesive force after irradiation with the active energy rays, and can be easily peeled off from the adherend.
Further, according to the present invention, there can be provided a pressure-sensitive adhesive sheet which has good wettability to an adherend before irradiation with an active energy ray such as ultraviolet ray, has removability to the adherend to enable reattachment, can be attached with an adhesive strength which is less likely to peel off from the adherend, and can be easily peeled off from the adherend by effectively reducing the adhesive strength after irradiation with the active energy ray.
[ use ]
The pressure-sensitive adhesive sheet of the present invention can be used in the form of a tape, a label, a seal, a double-sided tape, or the like. The pressure-sensitive adhesive sheet of the present invention is suitably used as a surface protective sheet, a cosmetic sheet, an anti-slip sheet, and the like.
It is to be noted that, in this specification, unless otherwise specified, "sheet" includes "film" as well as "tape".
Flat panel displays such as Liquid Crystal Displays (LCDs) and organic electroluminescent displays (OELDs), and touch panel displays in which the flat panel displays and the touch panel are combined are widely used in electronic devices such as Televisions (TVs), Personal Computers (PCs), mobile phones, and portable information terminals.
The adhesive sheet of the present invention is suitable for use as a surface protective sheet for flat panel displays, touch panel displays (these are also collectively referred to as "displays"), substrates produced or used in these production steps (glass substrates, ITO/glass substrates having an ITO (indium tin oxide) film formed on a glass substrate, and the like), optical members, and the like.
Examples
Next, synthesis examples, examples of the present invention, and comparative examples will be described. In the following description, "part" means part by mass, "%" means% by mass, and "RH" means relative humidity unless otherwise specified. The unit of the compounding amount in the table is "part by mass" unless otherwise specified. Unless otherwise stated, the amounts of components other than the solvent are calculated as nonvolatile components.
[ measurement of molecular weight ]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by a Gel Permeation Chromatography (GPC) method. The measurement conditions were as follows. Both Mw and Mn are polystyrene equivalent values.
The device comprises the following steps: shimadzu promience (Shimadzu corporation).
A chromatographic column: three SHODEX LF-804 (available from Showa Denko K.K.) were connected in series.
A detector: a differential refractive index detector.
Solvent: tetrahydrofuran (THF).
Flow rate: 1 mL/min.
Temperature of the solvent: at 40 ℃.
Sample concentration: 0.2 percent.
Sample injection amount: 200 μ L.
[ Material ]
The materials used are as follows.
< Compound containing active Hydrogen group (HX) >)
(HX-1): kuraray polyol P-2010, polyester polyol, number average molecular weight Mn2000, hydroxyl number 2, product of Coly corporation (クラレ Co.).
(HX-2): sannix GP-3000, polyether polyol, Mn3000, hydroxyl number 3, produced by Sanyo chemical industries.
(HX-3): sannix GL-3000, polyether polyol, Mn3000, hydroxyl number 3, Sanyo chemical industry company.
(HX-4): excenol 851, polyether polyol, number average molecular weight Mn6700, hydroxyl number 3, manufactured by AGC Co.
(HX-5): sannix PP-1000, polyether polyol, Mn1000, hydroxyl number 2, Sanyo chemical industries.
(HX-6): 1, 4-Hexane Dimethanol (CHDM).
< Compound containing an active Hydrogen group (HY) >)
(HY-1): 2-hydroxyethyl acrylate (HEA).
< polyisocyanate (N) >
(N-1): desmodur H, Hexamethylene Diisocyanate (HDI), manufactured by Kabushi Kochu urethane corporation (Kabushi コベストロウレタン Co.).
(N-2): desmodur I, isophorone diisocyanate (IPDI), product of Kabushi Kochu urethane (Kabushi コベストロウレタン Co.).
(N-3): desmodur T-80, Toluene Diisocyanate (TDI), product of Kabushi Kaisha urethane (Kabushi コベストロウレタン Co.).
< polyfunctional isocyanate Compound (I) >)
(I-1): sumidur HT, trimethylolpropane adduct of hexamethylene diisocyanate, nonvolatile fraction of 75%, product of Kabushi urethane corporation (Kabushiki コベストロウレタン).
(I-2): takenate D-110N, trimethylolpropane adduct of xylylene diisocyanate, nonvolatile matter 75%, manufactured by Mitsui chemical Co.
< free radical polymerizable Monomer (MX) >)
(MX-1): miramer M500, dipentaerythritol pentaacrylate, 5 acryloyl groups, 1 hydroxyl group, manufactured by Meiyuan corporation (MIWON).
(MX-2): miramer M600, dipentaerythritol hexaacrylate, 6 acryloyl groups, 0 hydroxyl group, manufactured by Meiyuan corporation (MIWON).
(MX-3): miramer M300, trimethylolpropane triacrylate, 3 acryloyl groups, 0 hydroxyl groups, product of Meiyuan corporation (MIWON Co.).
(MX-4): miramer M340, pentaerythritol triacrylate, 3 acryloyl groups, 1 hydroxyl group, product of Meiyuan corporation (MIWON).
(MX-5): sartomer CN925, aliphatic urethane tetraacrylate, 4 acryloyl groups, 0 hydroxyl groups, available from Arkema, France (アルケマ Co.).
< photopolymerization initiator (RL) >
(RL-1): irgacure TPO, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, product of BASF corporation.
(RL-2): SB-PI 712, 4-methylbenzophenone, manufactured by Sanyo trade company.
< plasticizer (P) >)
(P-1): acetyl tributyl citrate (ATBC), manufactured by Mitsubishi chemical corporation (Mitsubishi ケミカル).
(P-2): monosizer W262, ether ester plasticizers, available from DIC.
< antioxidant (O) >
(O-1): irganox 1010, hindered phenol antioxidant, product of BASF corporation.
< antistatic Agent (AS) >
(AS-1): IL-P14, Ionic liquid, Kyoho chemical industries.
[ Synthesis example of a solution of a hydroxyl-terminated Urethane Prepolymer (UPH) ]
(Synthesis example 1)
400 parts of an active hydrogen group-containing compound (HX-1), 600 parts of an active hydrogen group-containing compound (HX-2) and 57 parts of a polyisocyanate (N-1) were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer and a dropping funnel. To this solution, 705 parts of toluene, 0.1 part of dibutyltin dilaurate as a catalyst, and 0.04 part of tin 2-ethylhexanoate were added and mixed. The internal liquid was gradually warmed to 90 ℃ and reacted at 90 ℃ for 2 hours.
Sampling was performed as needed, and after confirming the elimination of the residual isocyanate group by infrared absorption (IR) spectroscopy, the reaction solution was cooled to 30 ℃. The reaction was carried out as described above to obtain a solution (nonvolatile content: 60%) of a hydroxyl-terminated urethane prepolymer (UPH 1). The weight average molecular weight Mw of the resulting hydroxyl-terminated urethane prepolymer (UPH1) was 83000. The compounding composition and Mw of the obtained hydroxyl-terminated urethane prepolymer are shown in table 1.
(Synthesis examples 2 to 7)
Synthesis examples 2 to 7 were carried out in the same manner as in Synthesis example 1 except that the kind of the active hydrogen group-containing compound (HX), the kind of the polyisocyanate (N) and the mixing ratio were changed to obtain colorless and transparent solutions of hydroxyl-terminated urethane prepolymers (UPH-2) to (UPH-7). In each synthesis example, the compounding composition and Mw of the obtained hydroxyl-terminated urethane prepolymer are shown in table 1.
(Synthesis example 11)
Synthesis example 11 was carried out in the same manner as in Synthesis example 7 except that an active hydrogen group-containing compound (HY) having 1 active hydrogen group and 1 (meth) acryloyl group in one molecule was added to the charged composition to obtain a colorless and transparent solution of hydroxy-terminated urethane prepolymer (UPA-1). The compounding composition and Mw of the obtained hydroxyl-terminated urethane prepolymer are shown in table 1.
TABLE 1
Figure BDA0003221369980000291
[ Synthesis example of Acrylic Resin (AR) ]
(Synthesis example 21)
990 parts of n-butyl acrylate, 10 parts of 4-hydroxybutyl acrylate and 1000 parts of ethyl acetate were put into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel, and mixed. The internal liquid was gradually heated to 90 ℃ and after confirming the reflux of the solvent, 2 parts of azobisisobutyronitrile was added and mixed. After 8 hours, the reaction solution was cooled to terminate the reaction. The procedure was carried out as described above to obtain a solution of the acrylic resin (AR1) (nonvolatile content: 50%). The weight average molecular weight Mw of the resulting acrylic resin was 890000.
[ production of adhesive and pressure-sensitive adhesive sheet ]
(example 1)
With respect to 100 parts of the hydroxyl-terminated urethane prepolymer (UPH1) solution obtained in Synthesis example 1, 1 part of a polyfunctional isocyanate compound (I-1), 5 parts of a radically polymerizable monomer (MX-1), 10 parts of a radically polymerizable monomer (MX-2), 3 parts of a radically polymerizable monomer (MX-3), 1 part of a photopolymerization initiator (RL-1), 1 part of a photopolymerization initiator (RL-2), 30 parts of a plasticizer (P-1), 0.1 part of an antioxidant (O-1), 0.1 part of an antistatic agent (AS-1) and 80 parts of ethyl acetate AS a solvent were mixed and stirred by a disperser to obtain a urethane-based adhesive. The amounts of the respective materials other than the solvent to be blended are shown by the amounts of nonvolatile components (the same applies to other examples and comparative examples). The compounding composition is shown in Table 2.
As a substrate sheet, a polyethylene terephthalate sheet (PET sheet with both surfaces easily bonded, COSMOSHINE A-4300, manufactured by Toyo Boseki Co., Ltd.) having a thickness of 75 μm was prepared. The obtained adhesive was applied to one surface of the substrate sheet so that the thickness after drying became 75 μm, and dried at 100 ℃ for 5 minutes to form an adhesive layer. A release sheet (Super Stik SP-PET38, manufactured by Nihon Denko Co., Ltd. (リンテック)) having a thickness of 38 μm was bonded to the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet. After 1 week of aging in an environment of 23-50% RH, various evaluations were provided.
(examples 2 to 35, comparative examples 1 to 3)
Urethane-based or acrylic-based adhesives and adhesive sheets using the same were produced in the same manner as in example 1, except that the compounding composition of the adhesives was changed as shown in tables 2 to 6 in examples 2 to 35 and comparative examples 1 to 3.
[ evaluation items and evaluation methods ]
The evaluation items and evaluation methods of the adhesive and the pressure-sensitive adhesive sheet are as follows.
(Wet expandability)
A test piece having a width of 100mm and a length of 200mm was cut out from the obtained adhesive sheet, and after leaving in an atmosphere of 23 to 50% RH for 30 minutes, the release sheet was peeled off from the test piece. Both ends of the test piece were held with both hands, and the both hands were separated after the center portion of the exposed adhesive layer was brought into contact with the glass plate. The time taken for the entire adhesive layer to adhere to the glass plate by the weight of the test piece was measured, and the wet spreadability of the adhesive was evaluated. The shorter the time taken until the glass plate is attached to the glass plate, the better the wettability (affinity for the adherend) is. The evaluation criteria are as follows.
Very good: the time taken until the adhesive was applied was less than 6 seconds, which was excellent.
O: the time until the adhesion was 6 seconds or more and less than 8 seconds, which was good.
And (delta): the time until the attachment is 8 seconds or more and less than 10 seconds, and is practical.
X: the time required until the attachment is 10 seconds or more, and therefore, the method is not practical.
(adhesive force before Ultraviolet (UV) irradiation and removability)
A test piece having a width of 25mm and a length of 100mm was cut out from the obtained adhesive sheet, and after leaving in an atmosphere of 23 to 50% RH for 30 minutes, the release sheet was peeled off from the test piece. The exposed adhesive layer side of the test piece was bonded to a stainless steel (SUS) plate under an environment of 23 to 50% RH, and pressure-bonded using a 2kg roller. After leaving for 24 hours, the adhesive strength (adhesive strength before UV irradiation) was measured using a tensile tester (Tensilon: manufactured by Olympic technologies, Inc. (オリエンテック)) at a peel speed of 0.3 m/min and a peel angle of 180 ℃ in accordance with JIS Z0237. Further, the lower the adhesive force before UV irradiation, the higher the removability, and the reattachment was easy. The evaluation criteria are as follows.
Very good: less than 20gf/25mm, excellent.
O: 20gf/25mm or more and less than 50gf/25mm is preferable.
And (delta): it is practically usable at 50gf/25mm or more and 100gf/25mm or less.
X: more than 100gf/25mm, it is not practical.
(vacuum adsorption holding adaptability)
A test piece having a width of 70mm and a length of 100mm was cut out from the obtained adhesive sheet, and after being left for 3 hours in an environment including a general fluorescent lamp emitting light including ultraviolet rays and adjusted to 23 to 50% RH, a peel-off piece was peeled off from the test piece. The exposed adhesive layer side of the test piece was bonded to a caustic soda glass plate in an atmosphere of 23 to 50% RH, and pressure-bonded using a 2kg roller. Then, the steel sheet was left to stand at 60 to 90% RH for 24 hours and then air-cooled in an atmosphere of 23 to 50% RH for 1 hour. A weight of 0.5kg was attached to the back surface (surface on the side to which the test piece was not attached) of the glass plate. The test piece/glass plate/weight laminate was held by suction with a vacuum suction member from the upper surface (substrate surface, PET surface) side of the test piece, lifted for 1 minute, and it was confirmed whether or not the glass plate having the weight of 0.5kg attached to the back surface thereof peeled off the test piece and fallen. The test was conducted 20 times to examine the number of dropping. The smaller the number of dropping, the higher the vacuum adsorption holding adaptability, and more preferably, the less dropping is performed at all. The evaluation criteria are as follows.
Very good: does not fall off at all and is excellent.
O: the number of dropping was 1, which was good.
And (delta): the number of dropping is 2-3, and the method is practical.
X: the number of dropping times was 4 or more, and this was not practical.
(adhesive force and removability after Ultraviolet (UV) irradiation)
A test piece having a width of 25mm and a length of 100mm was cut out from the obtained adhesive sheet, left to stand in an environment of 23 to 50% RH for 30 minutes, and then the release sheet was peeled off from the test piece, and the exposed adhesive layer side of the test piece was attached to a stainless steel (SUS) plate and pressure-bonded using a 2kg roller. After being left for 24 hours in an atmosphere of 23 to 50% RH, the test piece was subjected to Ultraviolet (UV) irradiation using a high-pressure mercury lamp (peak wavelength: 254nm, 365nm, 405nm, and 435nm, output: 120W) under a cumulative dose of 1000 mJ. After air-cooling for 1 hour in an atmosphere of 23 to 50% RH, the adhesive force (adhesive force after UV irradiation) was measured using a tensile tester (Tensilon: manufactured by Olympic technologies, Inc. (オリエンテック)) under conditions of a peeling speed of 0.3 m/min and a peeling angle of 180 deg. In addition, the reduction rate of the adhesive force before UV irradiation was determined. It is preferable that the lower the adhesive force and the reduction rate of the adhesive force after UV irradiation, the higher the peeling speed. The evaluation criteria are as follows.
Very good: the adhesive strength was less than 5gf/25mm, and the rate of decrease in adhesive strength was 2/3 or less, which was excellent.
O: the adhesive strength was 5gf/25mm or more and less than 8gf/25mm, and the rate of decrease in adhesive strength was 2/3 or less, which was good.
And (delta): the adhesive force is 8gf/25mm or more and 10gf/25mm or less, and the rate of decrease in adhesive force is 2/3 or less, and therefore, the adhesive force is practically applicable.
X: the adhesive force was more than 10gf/25mm, or the rate of decrease of the adhesive force was more than 2/3, and it was not practical.
[ evaluation results ]
The evaluation results are shown in tables 2 to 6.
In examples 1 to 35, a urethane adhesive was produced, which comprises a hydroxyl-terminated Urethane Prepolymer (UPH) that is a reaction product of 1 or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and 1 or more polyisocyanates (N), and a polyfunctional isocyanate compound (I), and a radical polymerizable Monomer (MX) having 3 or more (meth) acryloyl groups in one molecule, wherein the hydroxyl-terminated Urethane Prepolymer (UPH) does not contain a (meth) acryloyl group. In these examples, an adhesive sheet was produced using the obtained adhesive.
In examples 1 to 35, the adhesive layers of the obtained adhesive sheets all had good wet spreadability with respect to the adherend. The pressure-sensitive adhesive sheets obtained in these examples all had an appropriate adhesive force before UV irradiation, had removability to be reattachable to an adherend, and were capable of being attached with an adhesive force that was not readily releasable from an adherend, and had good vacuum suction holding suitability. The pressure-sensitive adhesive sheets obtained in these examples each had an adhesive force effectively reduced after UV irradiation, and could be easily peeled from an adherend, and were suitable for high-speed peeling.
The pressure-sensitive adhesive sheet obtained in comparative example 1 using an Acrylic Resin (AR) in place of the hydroxyl-terminated Urethane Prepolymer (UPH) had very high adhesive strength before UV irradiation, poor wet extensibility to an adherend, and poor removability. The pressure-sensitive adhesive sheet obtained in comparative example 1 was still high in adhesive force after UV irradiation, and was not suitable for high-speed peeling.
In comparative example 2 in which a hydroxyl-terminated Urethane Prepolymer (UPA) which is a reaction product of 1 or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule, 1 or more active hydrogen group-containing compounds (HY) having 1 active hydrogen group and 1 (meth) acryloyl group in one molecule, and 1 or more polyisocyanates (N) was used instead of the hydroxyl-terminated Urethane Prepolymer (UPH), the obtained adhesive sheet had poor vacuum adsorption holding suitability before UV irradiation. The adhesive layer absorbs a small amount of UV emitted from the fluorescent lamp, and the reaction of the radical polymerizable Monomer (MX) starts to proceed, and it is considered that the adhesive force is reduced before UV irradiation, and the vacuum adsorption holding property is not good.
In comparative example 3, a conventional urethane adhesive that was not designed for vacuum adsorption conveyance use was produced. The adhesive force of the obtained adhesive sheet before UV irradiation was low and the vacuum adsorption holding property was poor. In comparative example 3, since the radical polymerizable Monomer (MX) was not used, the decrease in adhesive force after UV irradiation was small, which is not preferable.
TABLE 2
Figure BDA0003221369980000341
TABLE 3
Figure BDA0003221369980000351
TABLE 4
Figure BDA0003221369980000361
TABLE 5
Figure BDA0003221369980000371
TABLE 6
Figure BDA0003221369980000381
The present invention is not limited to the above-described embodiments and examples, and can be modified as appropriate without departing from the spirit and scope of the present invention.
The present application is based on and claims priority from japanese patent application No. 2019-030666, filed on 2019, 2/22, the entire contents of which are incorporated herein by reference.
Description of the reference numerals
10. 20: an adhesive sheet; 11. 21: a substrate sheet; 12. 22A, 22B: an adhesive layer; 13. 23A, 23B: and (4) peeling off the sheet.

Claims (12)

1. An adhesive, wherein,
the adhesive is a removable adhesive comprising a hydroxyl-terminated urethane prepolymer UPH and a polyfunctional isocyanate compound I, wherein the hydroxyl-terminated urethane prepolymer UPH is a reaction product of 1 or more active hydrogen group-containing compounds HX having a plurality of active hydrogen groups in one molecule and 1 or more polyisocyanates N, and contains no (meth) acryloyl group,
the adhesive further contains a radical polymerizable monomer MX containing 3 or more (meth) acryloyl groups in one molecule,
the adhesive layer composed of a cured product of the adhesive is reduced in adhesive strength by irradiation with an active energy ray.
2. The adhesive of claim 1, wherein,
the adhesive layer has a reduction rate of the adhesive force after irradiation with an active energy ray relative to the adhesive force before irradiation with an active energy ray, measured using a tensile tester at a peeling speed of 0.3 m/min and a peeling angle of 180 DEG in accordance with JIS Z0237, of 2/3 or less.
3. The adhesive of claim 1 or 2,
the adhesive force of the adhesive layer before irradiation with an active energy ray, measured using a tensile tester at a peeling speed of 0.3 m/min and a peeling angle of 180 DEG in accordance with JIS Z0237, is 100gf/25mm or less.
4. The adhesive according to any one of claims 1 to 3,
the adhesive force of the adhesive layer after irradiation with an active energy ray, measured using a tensile tester at a peeling speed of 0.3 m/min and a peeling angle of 180 DEG in accordance with JIS Z0237, is 10gf/25mm or less.
5. The adhesive according to any one of claims 1 to 4,
the 1 or more active hydrogen group-containing compounds HX include trifunctional or more polyols having 3 or more hydroxyl groups in one molecule.
6. The adhesive according to any one of claims 1 to 5,
the radical polymerizable monomer MX contains 5 or more (meth) acryloyl groups in one molecule.
7. The adhesive according to any one of claims 1 to 6,
the adhesive also includes a plasticizer.
8. The adhesive according to any one of claims 1 to 7,
the adhesive also contains an antistatic agent.
9. The adhesive according to any one of claims 1 to 8,
the adhesive further comprises 1 or more deterioration inhibitors selected from the group consisting of antioxidants, hydrolysis resistance agents, ultraviolet absorbers, and light stabilizers.
10. An adhesive sheet, wherein,
the adhesive sheet comprises a base sheet and an adhesive layer comprising a cured product of the adhesive according to any one of claims 1 to 9.
11. The adhesive sheet according to claim 10, wherein,
the adhesive sheet is used for a surface protective sheet.
12. A method of using the adhesive sheet according to claim 10 or 11,
the method of using the adhesive sheet includes:
a step of bonding the adhesive sheet to the surface of an adherend;
irradiating the adhesive sheet bonded to the surface of the adherend with active energy rays to reduce the adhesive strength of the adhesive sheet; and
and peeling the pressure-sensitive adhesive sheet having a reduced adhesive strength from the adherend.
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