TW201927984A - Adhesive, adhesive sheet and laminate forming an adhesive layer that has a good yield and is less likely to have decreased re-peelability after high temperature aging - Google Patents

Abstract

The present invention provides an adhesive, an adhesive sheet and a laminate that can form an adhesive layer that has a good yield and is less likely to have decreased re-peelability after high temperature aging. The adhesive comprises: urethane polyol (A) having a weight average molecular weight of 100,000 to 500,000, which is a reactant of a polyol (a) and a polyisocyanate (b), an isocyanate curing agent (B), an antioxidant (D), an antistatic agent (E) and a polyfunctional polyol (F). The polyfunctional polyol (F) preferably has 3 or more hydroxyl groups in one molecule.

Description

Adhesive, adhesive sheet and laminate

The present invention relates to an antistatic adhesive. Moreover, it is related with the adhesive sheet and laminated body using the said adhesive.

Liquid crystal display (LCD), organic electroluminescence display (organic light emitting diode (OLED)) and other flat panel displays (FPD), FPD and touch panel (touch pannel ) The combined display device such as a touch screen panel (TSP) is widely used in televisions (TVs), personal computers (PCs), and portable information terminals.

Conventionally, in order to protect an optical member used in a display device from scratches and dust adhesion, a surface protection sheet has been widely used.

Adhesives containing urethane resins (hereinafter referred to as urethane adhesives) are used for various types of bonded bodies typified by glass and are excellent in moderate adhesion and re-peelability. In the adhesive layer of the surface protection sheet. With regard to such a surface protection sheet, in order to prevent damage to an electronic device inside the FPD or TSP caused by static electricity generated when peeling from a bonded body, antistatic performance may be required.

Patent Document 1 discloses a urethane-based adhesive composition, which is characterized by containing a hydroxyl group-containing polyurethane resin (A), a polyfunctional isocyanate compound (B), and containing no hydroxyl group and isocyanate group. The compound (C) and the ionic compound (D) having a molecular weight of 250 to 1,000 and containing 0.05 to 5 parts by weight of the component (D) relative to 100 parts by weight of the total of the components (A) to (C).

Patent Document 2 discloses a urethane-based adhesive containing a polyurethane-based resin containing a polyol (A) and a polyfunctional isocyanate compound ( In the polyurethane resin obtained by curing the composition of B), the equivalent ratio of NCO group to OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is NCO group / OH The base exceeds 1.0 and is 5.0 or less, and the urethane-based adhesive contains an ionic liquid containing a fluorine organic anion. [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2017-105866 [Patent Literature 2] Japanese Patent Laid-Open No. 2015-098503

[Problems to be Solved by the Invention] Although conventional adhesives have required antistatic properties by including an antistatic agent, the metal catalyst in the adhesive is coordinated with the antistatic agent and reacts with the isocyanate hardener. The speed decreases, so the hardening speed decreases. In addition, if the surface protection sheet is manufactured roll-to-roll rather than sheet by sheet, the step generated when the front end of the surface protection sheet is attached to the winding roller of the coating device passes The winding pressure is applied to the adhesive layer and the winding is performed, so that the effect of the step difference remains in the form of an indentation on the adhesive layer. Therefore, it is necessary to discard the surface protection sheet until the indentation disappears. Furthermore, the decrease in the hardening speed caused by the preparation of the antistatic agent decreases the cohesive force of the adhesive layer immediately after the application. Therefore, there is a problem that the sheet length until the indentation disappears increases, and the yield of the surface protection sheet is increased. decline. In addition, the decrease in the hardening speed has a problem in that the crosslinking density of the adhesive layer is lowered, the adhesive force is increased after lapse of time at a high temperature, and re-peelability is lowered. Furthermore, since the adhesive of Patent Document 2 is produced by a so-called one-shot method in which a urethane polyol is not used, the cohesive force of the adhesive layer immediately after coating is low and the yield is poor.

An object of the present invention is to provide an adhesive, an adhesive sheet, and a laminated body that can form an adhesive layer having a good yield and a releasability that does not easily decrease with time and temperature. [Technical means to solve the problem]

The inventors of the present invention have repeatedly conducted diligent studies in order to solve the problems, and as a result, have found that the problems can be solved by the following embodiments, and the present invention has been completed. [1] An adhesive comprising a urethane polyol (A) having a weight average molecular weight of 100,000 to 500,000 as a reactant of the polyol (a) and the polyisocyanate (b), and an isocyanate hardener (B), antioxidant (D), antistatic agent (E), and polyfunctional polyol (F). [2] The adhesive according to [1], wherein the number of hydroxyl groups in one molecule of the polyfunctional polyol (F) is 3 or more. [3] The adhesive according to [1] or [2], further comprising a plasticizer (C). [4] The adhesive according to [3], wherein the plasticizer (C) is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the urethane polyol (A). [5] The adhesive according to any one of [1] to [4], which contains 2 to 50 parts by mass of the compound relative to 100 parts by mass of the urethane polyol (A). The polyfunctional polyol (F) is described. [6] The adhesive according to any one of [1] to [5], wherein the polyfunctional polyol (F) has a primary hydroxyl group at a terminal. [7] An adhesive sheet comprising a base material and an adhesive layer as a cured product of the adhesive according to any one of [1] to [6]. [8] A laminated body comprising: a member selected from the group consisting of a transparent conductive film, glass, an acrylic plate, a polycarbonate plate, an olefin plate, and an inorganic barrier layer; and according to [7] Followed by the film. [Effect of the invention]

According to the present invention described above, it is possible to provide an adhesive, an adhesive sheet, and a laminated body that can form an adhesive layer having a good yield, and whose releasability does not easily decrease after a high temperature over time.

Terms are defined before the description of the present invention. In this specification, a to-be-joined body means the object to which an adhesive tape is attached. The adhesive sheet includes a base material and an adhesive layer containing a cured product of the adhesive of the present specification. In addition, "tape", "film", and "sheet" have the same meaning. Furthermore, the main component refers to a component having the largest amount of preparation among a plurality of types of components.

In this specification, unless otherwise specified, "molecular weight" is an exponential average molecular weight (Mn). In addition, "Mn" is a polystyrene-equivalent number average molecular weight measured by the gel permeation chromatography (GPC) measurement.

The adhesive of this embodiment includes a urethane polyol (A) having a weight average molecular weight of 100,000 to 500,000 as a reactant of the polyol (a) and the polyisocyanate (b), and an isocyanate hardener (B ), Antioxidant (D), antistatic agent (E), and multifunctional polyol (F). It is preferable that the adhesive agent of this embodiment forms an adhesive layer by application and uses it as an adhesive sheet. The adhesive sheet preferably includes a substrate.

By setting the weight average molecular weight of the urethane polyol (A) to be high, the adhesive of this embodiment can be combined with the polyfunctional polyol (F) to eliminate the hardening caused by the preparation of the antistatic agent (E). The disadvantage of speed reduction, which improves the decline in yield. Furthermore, the adhesive of this embodiment contains the antioxidant (D), and the adhesive layer which does not fall easily after high temperature over time is obtained.

The adhesive of the present embodiment can be used, for example, in displays such as LCDs and OLEDs having flat portions or curved portions, and touch panels using the displays. In addition, it can be widely used for surface protection of electronic devices such as mobile phones, smartphones, tablet terminals, and computers equipped with such displays or touch panels. In addition, the raw material of the joined body is not limited to glass, and for example, it can also be used to protect easily damaged raw materials such as polyolefin, gold, silver, copper, and indium tin oxide (ITO).

In addition to the use of the adhesive, in addition to displays, it can be used for members such as window glass, light emitting diodes (LEDs), vehicles, wiring, and their laminates. Moreover, the adhesive sheet of this embodiment can also be used for protection in the manufacturing process of various members, and a product after manufacture. It is needless to say that the adhesive of this embodiment can be used for applications other than surface protection applications.

(Urethane polyol (A)) The urethane polyol (A) is a urethane reaction in which one or more polyols (a) and one or more polyisocyanates (b) are subjected to a urethane reaction. The resulting reaction product. The polyisocyanate (b) is preferably a difunctional isocyanate (b1) (also referred to as a diisocyanate) having two isocyanate groups in one molecule. The polyol (a) is preferably a polyol (a1) having two or more hydroxyl groups in one molecule. The isocyanate group (isocyanate group) of the polyisocyanate (b) is used in a molar ratio (NCO / OH ratio) less than the hydroxyl group of the polyol (a). Thereby, a urethane polyol having a hydroxyl group can be obtained. In the urethane reaction, a catalyst is preferably used in order to promote the reaction. A solvent may be used in the urethane reaction if necessary. The urethane polyol (A) may be used alone or in combination of two or more.

<Polyol (a)> The polyol (a) is a compound having two or more hydroxyl groups. The polyol (a) is preferably a polyether polyol, a polyester polyol, a polybutadiene-modified polyol, a polycarbonate polyol, or a castor oil polyol, and more preferably a polyether polyol, a poly Ester polyol, polybutadiene modified polyol. The polyol (a) of the present embodiment may be one type, and if two or more types are used in combination, it is easy to adjust the cohesive force and the adhesive force of the adhesive layer. When using one type of polyol (a), it is preferable to use a polyol having three or more hydroxyl groups. When two or more polyols (a) are used, it is preferable to use a polyol having two hydroxyl groups and a polyol having three or more hydroxyl groups in combination. When a polyol having three or more hydroxyl groups is used in combination, the NCO / OH ratio (Molar ratio) of the polyisocyanate (b) and the polyol (a) is preferably set to 0.80 or less. When the NCO / OH ratio (Molar ratio) is used within an appropriate range, the reaction can be easily controlled in the synthesis of the urethane polyol (A).

Examples of the polyether polyol include reactants obtained by using an active hydrogen-containing compound having two or more active hydrogens in one molecule as an initiator and subjecting one or more oxetane compounds to addition polymerization.

The active hydrogen-containing compound is preferably a hydroxyl-containing compound, an amine, or the like. Examples of the hydroxyl-containing compound include ethylene glycol (Ethylene Glycol, EG), propylene glycol (Propylene Glycol, PG), 1,4-butanediol, neopentyl glycol, and butylethylpentanediol. Difunctional active hydrogen compounds; trifunctional active hydrogen compounds such as glycerol and trimethylolpropane; tetrafunctional active hydrogen compounds such as pentaerythritol. Examples of the amine include difunctional active hydrogen-containing compounds such as N-aminoethylethanolamine, isophoronediamine, and xylyldiamine; trifunctional active hydrogen-containing compounds such as triethanolamine; ethylenediamine, and aromatic Tetrafunctional active hydrogen-containing compounds such as family diamines; Pentafunctional active hydrogen-containing compounds such as diethylenetriamine.

Examples of the oxetane compound include alkylene oxide (Athylene oxide, AO) such as ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). ); Tetrahydrofuran (THF) and so on.

The polyether polyol is preferably an alkyleneoxy group derived from an active hydrogen-containing compound in the molecule (the polyol is also referred to as a "polyoxyalkylene polyol"). As the hydroxyl-containing compound constituting the polyoxyalkylene-based polyol, polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol are preferred, and low crystallinity is preferred, and flexibility is easily developed Polypropylene glycol.

The number average molecular weight (Mn) of the polyether polyol is not particularly limited. In terms of easily exhibiting transparency or flexibility, it is preferably 200 to 6,000, more preferably 400 to 5,000, and even more preferably 600 to 4,000. By setting Mn to 200 or more, reaction control at the time of synthesis of a urethane polyol (A) can be easily performed. In addition, by setting Mn to 6,000 or less, it is easy to adjust the cohesive force of the urethane polyol (A) to a moderate range.

The polyester polyol is preferably a compound (esterified product) obtained by esterifying one or more polyol components and one or more acid components, or a compound synthesized by ring-opening polymerization of a lactone (ring-opening polymerization). Things) and so on.

Examples of the lactone include polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

Examples of the polyol component include diethylene glycol, 1,3-butanediol, 3-methyl-1,5-pentanediol, and 2-butyl-2-, in addition to the active hydrogen-containing compound. 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, stearyl glycol, hexanetriol Wait.

Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, and 1,14-tetradecanedioic acid. Acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1 , 4-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid, dimer acid, trimer acid, and anhydrides thereof.

The number average molecular weight (Mn) of the polyester polyol is preferably 200 to 6,000, more preferably 500 to 6,000, still more preferably 500 to 4,000, and even more preferably 500 to 3,000. By setting Mn to 200 or more, reaction control at the time of synthesis of a urethane polyol (A) can be easily performed. In addition, by setting Mn to 6,000 or less, it is easy to adjust the cohesive force of the urethane polyol (A) to a moderate range.

The polybutadiene-modified polyol has, for example, two or more hydroxyl ends, a 1,2-vinyl site, a 1,4-cis site, a 1,4-trans site, or these hydrogenated structures, and is Linear or branched polybutadiene.

The number average molecular weight (Mn) of the polybutadiene-modified polyol is preferably 200 to 6,000, more preferably 500 to 6,000, still more preferably 500 to 4,000, and even more preferably 500 to 3,000. By setting Mn to 200 or more, reaction control at the time of synthesis of a urethane polyol (A) can be easily performed. In addition, by setting Mn to 6,000 or less, it is easy to adjust the cohesive force of the urethane polyol (A) to a moderate range.

The degree of hydrogenation of the polybutadiene-modified polyol is preferably such that all the double bond sites existing before the hydrogenation are hydrogenated, but in the present invention, a small amount of double bond sites may remain.

Examples of other polyols other than the above include polycarbonate polyols and castor oil polyols. The other polyol is preferably used in combination with a polyether polyol or a polyester polyol. The number average molecular weight (Mn) of other polyols is about 200 to 6,000.

When the polyol (a) contains an acidic functional group such as a carboxyl group or a sulfo group, the bonded body may be corroded. Therefore, it is preferable to use a polyol having no acidic functional group.

Among these, the polyol (a) is preferably aliphatic, so that the re-peelability after the high temperature test is further improved, and the transparency of the adhesive layer is easily maintained.

<Polyisocyanate (b)> As the polyisocyanate (b), for example, a known polyisocyanate such as an aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, and an alicyclic polyisocyanate can be used.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4'-diphenylmethane. Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, diisocyanate Anisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4 ', 4' '-triphenylmethane triisocyanate.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 2,3 -Butylene diisocyanate, 1,3-butylene diisocyanate, dodecyl diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate, etc.

Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'- Diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylene diisocyanate, and 1,3-tetramethylxylene diisocyanate.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) , 1,4-bis (isocyanatemethyl) cyclohexane, and 1,4-bis (isocyanatemethyl) cyclohexane.

The polyisocyanate is a diisocyanate, but a triisocyanate modified with the diisocyanate may also be used. Examples of the triisocyanate include a trimethylolpropane adduct of the diisocyanate, a biuret body, and a trimer (the trimer includes an isotricyanate ring).

The polyisocyanate (b) is preferably 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophor Ketone diisocyanate), etc.

The polyisocyanate (b) can be used alone or in combination of two or more.

<Catalyst> The catalyst is preferably a tertiary amine compound, an organometallic compound, or the like.

Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo [5.4.0] -undecene-7 (1,8-Diazabicyclo [5.4.0] -undecene-7, DBU), etc.

The organometallic compound is preferably a tin-based compound, a non-tin-based compound, or the like. Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, and dibutyltin dilaurate (DBTDL). ), Dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, two Octyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and titanium butoxy trichloride; lead oleate, lead 2-ethylhexanoate, and lead benzoate And lead compounds such as lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetone; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate and 2 -Zinc compounds such as zinc ethylhexanoate; zirconium compounds such as zirconium naphthenate. Among these, a tin-based compound is more preferable because the reaction rate is increased or the coloration is small.

The catalysts can be used alone or in combination of two or more.

The catalyst is preferably used in an amount of 0.01 to 1.0 parts by mass based on 100 parts by mass of the total of the polyisocyanate (b) and the polyol (a).

<Solvent> In the production of the urethane polyol (A), one or more solvents may be used as necessary. Examples of the solvent include ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate; and hydrocarbon solvents such as toluene and xylene. Among these, in terms of the solubility of the urethane polyol (A) and the boiling point of the solvent, an ester-based solvent, a hydrocarbon-based solvent, and the like are preferred.

<The manufacturing method of a urethane polyol (A)> There is no restriction | limiting in particular in the manufacturing method of a urethane polyol (A), It can manufacture by well-known polymerization methods, such as a block polymerization method and a solution polymerization method. . The order of the production method includes, for example: (Sequence 1) one or more polyols (a), one or more polyisocyanates (b), one or more catalysts as required, and one or more solvents as required. Order in a flask; (Order 2) One or more polyols (a), one or more catalysts as needed, and one or more solvents as needed are put into the flask, and one or more polyisocyanates (b )Order. (Sequence 3) Put the remaining portion of the one or more polyols (a) after the final dropwise addition, if necessary, more than one catalyst, and if necessary, more than one solvent into the flask, and dropwise add one of them In the above polyisocyanate (b), an additional order of one or more polyols (a) is added dropwise. Among these, the control of reaction heat is easy (sequence 2) (sequence 3).

In the case of using a catalyst, the reaction temperature is preferably less than 100 ° C, and more preferably 70 ° C to 95 ° C. If the reaction temperature is less than 100 ° C, since side reactions other than the urethane reaction can be suppressed, it is easy to obtain a desired urethane polyol (A). In the case where no catalyst is used, the reaction temperature is preferably 100 ° C or higher, and more preferably 110 ° C or higher.

As for the isocyanate group (NCO) of the polyisocyanate (b) and the hydroxyl group (OH) of the polyol (a) when the urethane polyol (A) is produced, the molar ratio of NCO / OH is preferred. It is 0.3 to 0.95, more preferably 0.4 to 0.90, and even more preferably 0.5 to 0.80. When the NCO / OH ratio is within the above range, a urethane polyol (A) having a moderate molecular chain can be formed, and therefore wettability and productivity are further improved.

When a catalyst is used in the synthesis, the catalyst is preferably inert. The reaction stopper may be, for example, acetone or the like.

The reaction stoppers may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the urethane polyol (A) is preferably 100,000 to 500,000, more preferably 100,000 to 400,000, and even more preferably 150,000 to 400,000. By adjusting the weight-average molecular weight (Mw) to the above range, immediately after winding, the subsequent layer has a certain cohesive force, so that the indentation can be suppressed and the yield can be improved.

<Isocyanate hardener (B)> An isocyanate hardener (B) is a well-known compound which has a some isocyanate group. The isocyanate hardener (B) is preferably the polyisocyanate (b). Among them, aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates and alicyclic polyisocyanates, and their trimethylol groups are more preferred. Propane adducts, their biuret bodies, and trifunctional isocyanates as their trimers.

The isocyanate hardener (B) may be used alone or in combination of two or more.

The blending amount of the isocyanate hardener (B) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 25 parts by mass based on 100 parts by mass of the urethane polyol (A). It is more preferably 3 to 20 parts by mass, and even more preferably 5 to 15 parts by mass. When an appropriate amount of the isocyanate hardener (B) is blended, it is easy to obtain a moderate adhesive force and cohesive force.

<Plasticizer (C)> The adhesive of this embodiment may further contain a plasticizer (C). By including the plasticizer (C), the wettability of the adhesive layer with respect to the adherend is further improved. From the viewpoint of compatibility with other components, the plasticizer (C) is preferably a fatty acid ester or a phosphate ester having 8 to 30 carbon atoms.

The fatty acid ester compound having 8 to 30 carbon atoms has a carbon number of 8 to 30 as a whole, and examples thereof include esters of mono- or polybasic acids having 6 to 18 carbon atoms and branched alcohols having 18 or less carbon atoms, and 14 to 13 carbon atoms. Ester of unsaturated fatty acid or branched acid of 18 with tetravalent or lower alcohol, ester of mono- or polybasic acid with 6 to 18 carbons and polyalkylene glycol, epoxidation of unsaturated sites by peroxide, etc. The obtained fatty acid ester.

Examples of the ester of a mono- or poly-acid having 6 to 18 carbons and a branched alcohol having 18 or less carbon include, for example, isostearyl laurate, isopropyl myristate, isocetyl myristate, Octyldodecyl myristate, isostearyl palmitate, isocetyl stearate, octyldodecyl oleate, diisostearyl adipate, diisosuccinate Cetyl ester, triolenylidene trimellitate, triisocetyl trimellitate and the like.

The unsaturated fatty acid having 14 to 18 carbons or an ester of a branched acid and an alcohol having a tetravalent or less, and the unsaturated fatty acid having 14 to 18 carbons and a branching acid and an alcohol having a tetravalent or less are described below. Examples of unsaturated fatty acids or branched acids having 14 to 18 carbon atoms include myristic oleic acid, oleic acid, linoleic acid, hypolinolenic acid, isopalmitic acid, and isostearic acid. Examples of the alcohol having a tetravalent or lower value include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitan.

Examples of the ester of a mono- or poly-acid having 6 to 18 carbon atoms and a polyalkylene glycol include dihexyl acid polyethylene glycol, di-2-ethylhexyl acid polyethylene glycol, and dilauric acid. Polyethylene glycol, polyethylene glycol dioleate, diethylene glycol adipic acid methyl ether, and the like.

Examples of fatty acid esters obtained by epoxidizing unsaturated sites with peroxide and the like include epoxidized fats such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized cottonseed oil, and unsaturated unsaturated carbons of 8 to 18. Compounds obtained by epoxidizing fatty acids, ester compounds with linear or branched alcohols having 1 to 6 carbon atoms, and the like.

Examples of the phosphoric acid ester include an ester compound of phosphorous acid or phosphoric acid and a linear or branched alcohol having 2 to 18 carbon atoms.

The plasticizer (C) may be used alone or in combination of two or more.

From the viewpoint of improving the wetting rate, the formula amount or number average molecular weight (Mn) of the plasticizer (C) is preferably 300 to 1,000, more preferably 300 to 900, and even more preferably 350 to 850.

The blending amount of the plasticizer (C) is preferably 0.1 to 100 parts by mass, more preferably 1 to 80 parts by mass, and more preferably 100 parts by mass of the urethane polyol (A). It is 5 to 60 parts by mass. When an appropriate amount of the plasticizer (C) is blended, the wettability is further improved.

<Antioxidant (D)> The adhesive of this embodiment contains an antioxidant (D). When the antioxidant (D) is included, thermal decomposition of the crosslinked network of the urethane polyol (A) and the isocyanate hardener (B) can be suppressed, and thus it is possible to obtain a peeling resistance which is not easily reduced after a high temperature over time. Next layer. Examples of the antioxidant (D) include radical chain inhibitors such as phenol-based antioxidants and amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. Among these, a phenolic antioxidant is preferable.

Examples of the phenol-based antioxidant include 2,6-di-third-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-third-butyl-4-ethylphenol, and β -(3,5-di-third-butyl-4-hydroxyphenyl) stearyl propionate and other monophenolic antioxidants; 2,2'-methylenebis (4-methyl-6-third Butylphenol), 2,2'-methylenebis (4-ethyl-6-third butylphenol), 4,4'-thiobis (3-methyl-6-third butylphenol) ), 4,4'-butylene bis (3-methyl-6-third butylphenol), and 3,9-bis [1,1-dimethyl-2- [β- (3- Bisphenol-based antioxidants such as tributyl-4-hydroxy-5-methylphenyl) propanyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-third-butyl-4-hydroxybenzyl) benzene, tetra- [methylene-3- (3 ', 5'-di-third-butyl-4'-hydroxyphenyl) propionate] Methane, bis [3,3'-bis- (4'-hydroxy-3'-third butylphenyl) butanoic acid] ethylene glycol esters, and 1,3,5-tris (3 ', 5'- Di-tertiary butyl-4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, polymer phenolic antioxidants such as tocopherol and the like.

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate dilauryl ester, 3,3'-thiodipropionate di-tetradecyl ester, and 3,3'-thiodipropionate. Distearyl propionate and the like.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, and phenyl diisodecyl phosphite.

The antioxidant (D) may be used alone or in combination of two or more.

The blending amount of the antioxidant (D) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 100 parts by mass of the urethane polyol (A). 0.5 to 3 parts by mass.

<Antistatic agent (E)> The adhesive agent of this embodiment contains an antistatic agent (E). If an antistatic agent (E) is included, it is easy to suppress the electrostatic discharge at the time of peeling an adhesive sheet, and for example, it is easy to prevent the electronic components incorporated in a display etc. from being damaged. Examples of the antistatic agent include inorganic salts, ionic liquids, ionic solids, and surfactants. Among these, an ionic liquid is preferable. In addition, "ionic liquid" is also called normal temperature molten salt, and shows a liquid property at 25 degreeC.

Examples of the inorganic salt include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, and nitric acid. Potassium, sodium nitrate, sodium carbonate, and sodium thiocyanate.

The ionic liquid is a salt of a cation and an anion. For example, the cation is preferably an imidazolium ion, a pyridinium ion, an ammonium ion, or the like.

Examples of the ionic liquid containing an imidazolium ion include 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine, and 1,3-dimethylimidazolium bis (trifluoromethyl) Sulfofluorenyl) fluorenimine, and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide, and the like.

Examples of the ionic liquid containing a pyridinium ion include 1-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimide, and 1-butylpyridinium bis (trifluoromethylsulfonyl) fluorenimide , 1-hexylpyridinium bis (trifluoromethylsulfonyl) fluorenimine, 1-octylpyridinium bis (trifluoromethylsulfonyl) fluorenimine, 1-hexyl-4-methylpyridinium Bis (trifluoromethylsulfonyl) fluorenimine, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (trifluoromethylsulfonyl) Fluorenimine, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide, 1-methylpyridinium bis (perfluoroethylsulfonyl) fluorenimine, and 1-formyl Pyridinium bis (perfluorobutylsulfonyl) fluorenimine and the like.

Examples of the ionic liquid containing ammonium ions include trimethylheptylammonium bis (trifluoromethanesulfonyl) phosphonium imine, N, N-diethyl-N-methyl-N-propylammonium bis (tri Fluoromethanesulfonyl) fluorenimine, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-diethyl-N -Methyl-N-heptylammonium bis (trifluoromethanesulfonyl) fluorenimide, and tri-n-butylmethylammonium bistrifluoromethanesulfonimide.

In addition, a known ionic liquid whose cation is a pyrrolidinium ion, a sulfonium ion, a sulfonium ion, or the like can be suitably used.

Ionic solids are salts of cations and anions in the same way as ionic liquids, but they exhibit solid properties at 25 ° C under normal pressure. The cation is preferably, for example, an alkali metal ion, a sulfonium ion, a pyridinium ion, an ammonium ion, or the like.

Examples of the ionic solid containing an alkali metal ion include lithium difluorosulfimide, lithium bistrifluoromethylsulfonimide, lithium bispentafluoroethylsulfonimide, and lithium diheptafluoropropylsulfonimide. Amine, lithium dinonafluorobutylsulfonimide, sodium difluorosulfinimide, sodium ditrifluoromethylsulfinimide, sodium dipentafluoroethylsulfinimide, diheptafluoropropylsulfonium Sodium imine, Sodium dinonafluorobutylsulfonimide, Potassium difluorosulfimide, Potassium ditrifluoromethylsulfonimide, Potassium dipentafluoroethylsulfonimide, Diheptafluoropropyl Potassium sulfenimide, potassium dinonafluorobutylsulfonimide and the like.

Examples of ionic solids containing sulfonium ions include tetrabutylphosphonium bisfluorosulfimidine, tetrabutylphosphonium bistrifluoromethylsulfonylimide, tetrabutylphosphonium bispentafluoroethylsulfonylimide, and Butyl 鏻 bis heptafluoropropylsulfonimide, tetrabutyl 鏻 bisnonafluorobutylsulfonimide, tributylhexadecyl 鏻 bisfluorosulfimide, tributylhexadecyl 鏻Bistrifluoromethylsulfonimide, tributylhexadecylsulfonium dipentafluoroethylsulfonimide, tributylhexadecylsulfonium diheptafluoropropylsulfonimide, tributyldeca Hexylalkyl bisnonafluorobutylsulfonimide, tetraoctylfluoride bisfluorosulfimide, tetraoctylfluoride bistrifluoromethylsulfonimide, tetraoctylfluoride bispentafluoroethylsulfonium Imines, tetraoctylfluorene bis-heptafluoropropylsulfonimide, tetraoctylfluorene bisnonafluorobutylsulfonimide and the like.

Examples of ionic solids containing pyridinium ions include 1-hexadecyl-4-methylpyridinium bisfluorosulfimidine, 1-hexadecyl-4-methylpyridinium bistrifluoromethylsulfonate Fluorenimine, 1-hexadecyl-4-methylpyridinium bispentafluoroethylsulfonimide, 1-hexadecyl-4-methylpyridinium bis-heptafluoropropylsulfonimine, 1-hexadecyl-4-methylpyridinium bis nonafluorobutylsulfonimide and the like.

Examples of ionic solids containing ammonium ions include tributylmethylbistrifluoromethylsulfonimide, tributylmethylbispentafluoroethylsulfonimide, tributylmethylbisheptafluoropropylsulfonimide, and Butylmethylbisnonafluorobutylsulfonimide, octyltributylbistrifluoromethylsulfonimide, octyltributylbispentafluoroethylsulfonimide, octyltributylbisheptafluoro Propylsulfinoimide, octyltributylbisnonafluorobutylsulfimide, tetrabutyldifluorosulfimide, tetrabutylbistrifluoromethylsulfimide, tetrabutylbispenta Fluoroethylsulfonimide, tetrabutylbisheptafluoropropylsulfonimide, tetrabutylbisnonafluorobutylsulfonimide, and the like.

In addition, well-known ionic solids, such as a pyrrolidinium ion, an imidazolium ion, and a sulfonium ion, can be used suitably.

Surfactants can be classified into non-ionic, anionic, cationic, and amphoteric types.

Examples of nonionic surfactants include glycerin fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, and fatty acids. Diethanolamine, polyetheresteramine, ethylene oxide-epichlorohydrin, and polyetherester. Examples of the anionic surfactant (excluding ionic liquids and ionic solids) include alkylsulfonates, alkylbenzenesulfonates, alkyl phosphates, and polystyrenesulfonic acids. Examples of the cationic surfactant include a tetraalkylammonium salt, a trialkylbenzylammonium salt, and a quaternary ammonium salt-containing acrylate polymer type. Examples of the amphoteric surfactant include amino acid ampholytic surfactants such as alkyl beetamine, alkylimidazolium beetamine, and higher alkylaminopropionates, higher alkyldimethyl beetamine, and higher alkanes. Beetamidine type amphoteric surfactants such as dihydroxyethyl beetamidine.

Antistatic agents (E) are classified as liquid or solid at 25 ° C. The antistatic agent (E), which is liquid at 25 ° C, is easier to transfer to the interface between the adhesive layer and the bonded body than the solid, and therefore it is easy to obtain better antistatic properties.

In addition, a part of the antistatic agent (E) which is solid at 25 ° C is more likely to exist in the adhesive layer as an island with a sea-island structure than a liquid. As a result, the stress relaxation properties of the adhesive layer are improved, so that it is easy to obtain good substrate adhesion.

Among these, the antistatic agent (E) is preferably 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide or tetrabutylphosphonium bis (trifluoromethanesulfonimide).

The antistatic agent (E) may be used alone or in combination of two or more.

The blending amount of the antistatic agent (E) is preferably 0.01 to 3 parts by mass, more preferably 0.03 to 2 parts by mass, and more preferably 100 parts by mass of the urethane polyol (A). It is 0.06 mass part-1 mass part. When an appropriate amount of the antistatic agent (E) is blended, the re-peelability after high temperature over time does not easily decrease, and the yield at the time of manufacturing the adhesive sheet is further improved.

<Polyfunctional Polyol (F)> The polyfunctional polyol (F) and the urethane polyol (A) of this embodiment react with an isocyanate hardener (B) to form a crosslinked structure in an adhesive layer. Segments with high crosslink density. Since the segment having a high crosslink density has a low molecular weight immediately before the reaction, it has the following effects: it has excellent surface orientation, makes the surface of the coating film firm, and reduces indentation. The polyfunctional polyol (F) can be used as a residual polyol (a) during the synthesis of the urethane polyol (A), or it can be re-blended. Furthermore, the residual polyol (a) may be used in combination with the novel formulation.

The polyfunctional polyol (F) can be used in the polyol (a) described above, and a polyol having 3 or more hydroxyl groups in one molecule. By setting the number of hydroxyl groups in one molecule to 3 or more, a segment having a high crosslink density can be appropriately adjusted on the surface of the adhesive layer, so that the indentation is further reduced.

In the case of using a polyfunctional polyol (F) with a polyol having a primary hydroxyl group at the terminal, the curing speed with the isocyanate hardener (B) is increased, the indentation is suppressed, and the yield is easily further improved.

In the case of using a polyfunctional polyol (F) with a polyol having a secondary hydroxyl group at the molecular terminal, it takes time until the crosslinking is completed. Therefore, an adhesive layer with less hardening strain can be formed. As a result, the adhesive layer may be sufficiently adhered to a substrate that is not easily subjected to a bonding treatment such as a corona treatment.

The polyfunctional polyol (F) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, more preferably 4 to 100 parts by mass of the urethane polyol (A). Part by mass to 20 parts by mass. When the polyfunctional polyol (F) is contained in an amount of 2 to 50 parts by mass, the ratio of the segment having a high crosslink density can be appropriately adjusted on the surface of the adhesive layer, so that the indentation is further reduced.

As the polyfunctional polyol (F), the number of hydroxyl groups in one molecule of the polyols listed in the polyol (a) is 3 or more, and a primary hydroxyl group or a secondary hydroxyl group is present at the molecular terminal. Especially preferred are polyester polyols or polyether polyols.

The number average molecular weight (Mn) of the polyfunctional polyol (F) is preferably in the range of 500 to 6,000, more preferably 1,000 to 5,000, and even more preferably 1,000 to 4,000. If it is 500 or more, the formation of microgels that locally react with the isocyanate hardener (B) can be suppressed, and if it is 6,000 or less, the molecular weight between the crosslinks can be reduced. Therefore, indentation is suppressed and the temperature and time are maintained over time. The re-peelability is further improved.

<Solvent> The solvent which can be used at the time of manufacture of the said urethane polyol (A) can be used, However, An ester type solvent, a hydrocarbon type solvent, etc. are preferable. The solvent may be used alone or in combination of two or more.

<Other additives> As long as the adhesive of this embodiment is a range which can solve a problem, other additives may be contained as needed. Examples of other additives include resins, fillers, metal powders, pigments, foils, softeners, ultraviolet absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, Defoamers, lubricants, etc.

Examples of the filler include talc, calcium carbonate, and titanium oxide.

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, a chlorampanilide-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, And triazine-based ultraviolet absorbers.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. , 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-di Methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and bis (2-methoxy-4-hydroxy-5-benzylphenyl) methane Wait.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-third butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-third-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-third-butyl- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-third-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tertiarypentylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- [2'-Hydroxy-3 '-(3' ', 4' ', 5' ', 6' '-tetrahydrophthalimidemethyl) -5'-methylphenyl] benzotris Azole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], and 2 ( 2'-hydroxy-5 '-(meth) acryloxyphenyl) -2H-benzotriazole and the like.

Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenyl Acrylate, etc.

Examples of the light stabilizer include a hindered amine light stabilizer, an ultraviolet stabilizer, and the like.

Examples of the hindered amine light stabilizer include: [bis (2,2,6,6-tetramethyl-4-amidino) sebacate], bis (1,2,2,6,6-penta Methyl-4-amidinoyl) sebacate and methyl1,2,2,6,6-pentamethyl-4-amidinoylsebacate and the like.

Examples of the ultraviolet stabilizer include nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-third octylphenate)]-n-butylamine nickel, and nickel complex-3 , 5-Di-tert-butyl-4-hydroxybenzyl-phosphate monoethanolate, nickel-dibutyldithiocarbamate, benzoate type quencher, and nickel-dibutyl Dithiocarbamates and the like.

Examples of the leveling agent include acrylic leveling agents, fluorine-based leveling agents, and silicon-based leveling agents. If a commercially available leveling agent is listed, examples of the acrylic leveling agent include: Polyflow No. 36, Polyflow No. 56, and Polyflow No. .85HF, Polyflow No.99C (all manufactured by Kyoeisha Chemical Co., Ltd.), etc. Examples of the fluorine-based leveling agent include Megafac F470N and Megafac F556 (both manufactured by DIC Corporation). Examples of the silicon-based leveling agent include grandic PC4100 (manufactured by DIC Corporation).

<Adhesive sheet> The adhesive sheet of this embodiment includes a base material and an adhesive layer of a cured product as an adhesive. The adhesive layer may be formed on one or both sides of the substrate. In addition, the surface of the adhesive layer that is not in contact with the substrate is usually protected with a release sheet immediately before use in order to prevent foreign matter from adhering.

The substrate can be used without limitation as a soft sheet and a board. Examples of the substrate include plastic, paper, and metal foil, and a substrate obtained by laminating them. In order to improve the adhesiveness of the surface of the base material that is in contact with the adhesive layer, for example, a dry process such as a corona discharge process or a wet process such as anchor coating agent coating can be performed in advance to facilitate bonding.

Examples of the plastic of the substrate include ester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene (PE), and polyethylene Olefin resins such as polypropylene (PP) and cycio olefins polymer (COP); vinyl resins such as polyvinyl chloride; ammonium resins such as nylon 66; urethane resins (including foaming) Body) and so on.

The thickness of the substrate is usually about 10 μm to 300 μm. In addition, when a polyurethane sheet (including a foam) is used as the base material, the thickness is usually about 20 to 50,000 μm. Examples of the paper include plain paper, coated paper, and coated paper. Examples of the metal foil include aluminum foil and copper foil.

As the release sheet, a known release sheet that has been subjected to a known release treatment such as a silicone-based release agent on the surface of plastic, paper, or the like can be used.

A method for producing the adhesive sheet includes, for example, a method of applying an adhesive on the surface of the base material to form a coating layer, and then drying and curing the coating layer to form an adhesive layer. The heating and drying temperature is usually about 60 ° C to 150 ° C. The thickness of the adhesive layer is usually about 0.1 μm to 200 μm.

Examples of the coating method include a roll coater method, a comma coater method, a die coater method, a reverse coater method, and silk printing. screen) method and gravure coater method.

In addition, a method may be mentioned in which, contrary to the method described above, an adhesive is applied to the surface of the release sheet to form a coating layer, and then the coating layer is dried and hardened to form a cured product containing the adhesive of this embodiment. Finally, the substrate is bonded to the exposed surface of the adhesion layer. When a release sheet is bonded in place of the base material by the above method, a cast adhesive sheet of a release sheet / adhesive layer / release sheet can be obtained.

<Laminated body> The laminated body of this embodiment includes a member selected from the group consisting of a transparent conductive film, glass, acrylic plate, polycarbonate plate, olefin plate, and inorganic barrier layer, and an adhesive sheet. Since the laminated body includes an adhesive sheet formed of the adhesive of this embodiment, for example, when a display is manufactured, a member of the display that is easily damaged can be protected and easily peeled off after manufacturing. The display is, for example, an LCD, an OLED, or the like. Most of the other components include a touch panel.

The touch panel includes, for example, a transparent electrode film. The transparent electrode film is, for example, a film in which a conductive layer such as ITO (indium tin oxide) is formed to a thickness of about 0.1 μm to 0.3 μm on the surface of a transparent film such as polyethylene terephthalate (PET) by sputtering or evaporation. . The conductive layer (electrode layer) formed by ITO or the like is easily damaged. Therefore, if the adhesive layer is included, the conductive layer is less likely to be damaged during operations such as transportation and processing.

In order to protect a light-emitting element that is easily deteriorated, the OLED includes an inorganic barrier layer. The inorganic barrier layer is, for example, a layer having a thickness of about 15 nm to 100 nm in which an inorganic compound such as silicon nitride is formed by evaporation or sputtering. Therefore, if the adhesive sheet is included, the inorganic barrier layer is not easily damaged during operations such as handling and processing of the OLED.

Glass, an acrylic plate, a polycarbonate plate, and an olefin plate are optical members configured as a part of a laminated body of a display such as an LCD or an OLED. The optical member is used, for example, to protect a liquid crystal element or the outermost surface of a touch panel. Since the touch panel is required to be thin, the optical member is also thin and easily damaged. Therefore, if the adhesive sheet is included, the optical member is less likely to be damaged during operations such as handling and processing of the touch panel. The optical member may have optical functions such as a hard coat layer, a retardation, and a polarizing plate. The thickness of the optical member is about 10 μm to 1000 μm. [Example]

Hereinafter, embodiments of the present invention will be described with examples. It is needless to say that the embodiments of the present invention are not limited to the examples. Hereinafter, "part" means "part by mass". In addition, "%" means "mass%." In addition, the compounding quantity in a table | surface is a mass part.

[Synthesis Example of Urethane Polyol (A)] (Synthesis Example 1) A four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel was charged with Kuraray Polyol (Kuraray Polyol ) P-1010 (difunctional polyester polyol, manufactured by Kuraray) 500 parts, Kuraray Polyol F-1010 (trifunctional polyester polyol, manufactured by Kuraray) 500 parts, 140 parts of hexamethylene diisocyanate, 760 parts of toluene, and 0.05 part of dioctyltin dilaurate as a catalyst, the temperature was gradually raised to 75 ° C., and a reaction was performed for 3 hours. After confirming that the NCO characteristic absorption (2,270 cm ^-1 ) of the infrared spectrum (IR) chart disappeared, the temperature was cooled to 30 ° C., and the reaction was completed. The weight average molecular weight (Mw) of the urethane polyol (A1) was 150,000, and the conversion rate was over 99%.

(Synthesis Example 2 to Synthesis Example 36, Synthesis Example 38, Synthesis Example 39) Except that the materials and blending ratios of Example 1 were changed to those shown in Tables 1 to 4, the same procedures as in Synthesis Example 1 were performed to obtain Urethane polyols (A) of Synthesis Examples 2 to 36, 38 and 39. The Mw and conversion of the obtained urethane polyol (A) are shown in Table 1. In addition, the compounding quantity of the raw material which is included in a table | surface is a conversion of a non-volatile component, and the unit of the numerical value without a special description is "part".

(Synthesis Example 37) A four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel was charged with Kuraray Polyol P-1010 (a bifunctional polyester polyol, Kuraray ( (Kuraray) 200 parts), Excenol 240 (trifunctional polyether polyol, manufactured by Asahi Glass Co., Ltd.) 550 parts, hexamethylene diisocyanate 170 parts, toluene 547 parts, and dilauric acid as a catalyst 0.05 part of dioctyltin was gradually heated to 90 ° C. and reacted for 30 minutes. Then, a mixed solution of 100 parts of Kuraray Polyol P-1010, 240 150 parts of Excenol, and 167 parts of toluene was added dropwise from a dropping funnel over 30 minutes. After confirming that the NCO characteristic absorption (2,270 cm ^-1 ) of the IR chart disappeared, the temperature was cooled to 30 ° C., and the reaction was completed. The Mw of the urethane polyol (A37) was 210,000, and the conversion rate was over 90%.

[Material] The materials used in the table are as follows. <Polyol (a)> (a1): P1010 ("Kuraray Polyol P-1010", polyester polyol, Mn1000, hydroxyl number 2, primary hydroxyl group, manufactured by Kuraray)) ( a2): P3199 ("Priprast 3199", polyester polyol, Mn2000, hydroxyl number 2, primary hydroxyl, manufactured by Croda)) (a3): PP1000 ("Sannix" PP-1000 ", polyoxypropylene glycol, Mn1000, hydroxyl number 2, secondary hydroxyl, manufactured by Sanyo Chemical Industry Co., Ltd. (a4): PP2000 (" Sannix PP-2000 ", polyoxypropylene glycol, Mn2000, hydroxyl number 2, secondary hydroxyl, manufactured by Sanyo Chemical Industry Co., Ltd.) (a5): Exce 510 ("Excenol 510", polyether polyol, Mn4000, hydroxyl number 2, Primary hydroxyl, manufactured by Asahi Glass Co., Ltd.) (a6): GI1000 ("NISSO-PB GI-1000", two-terminal hydroxyl-hydrogenated polybutadiene, Mn1500, hydroxyl number 2, primary hydroxyl, manufactured by Japan Soda Corporation) ( a7): GI3000 ("NISO-PB GI-3000", Hydrogenated polybutadiene at both ends, Mn3100, hydroxyl number 2, primary hydroxyl, manufactured by Soda Co., Ltd. (a8): HLBH P2000 ("Krasol (registered trademark) HLBH P2000", terminal hydroxyl modified liquid) Polybutadiene, Mn2000, hydroxyl number 1.95, primary hydroxyl, manufactured by CRAY VALLEY) (a9): F1010 ("Kuraray Polyol F-1010", polyester polyol, Mn1000, hydroxyl number 3, primary hydroxyl group, manufactured by Kuraray) (a10): F3010 ("Kuraray Polyol F-3010", polyester polyol, Mn3000, hydroxyl number 3, primary hydroxyl group (Manufactured by Kuraray) (a11): Exce 1030 ("Excenol 1030", polyether polyol, Mn1000, hydroxyl number 3, secondary hydroxyl, manufactured by Asahi Glass Co., Ltd. ) (A12): Exce 240 ("Excenol 240", polyether polyol, Mn3000, hydroxyl number 3, primary hydroxyl, manufactured by Asahi Glass Co., Ltd.) (a13): Exce ( Exce) 4030 ("Excino Excenol) 4030 ", polyether polyol, Mn4000, hydroxyl number 3, secondary hydroxyl group, manufactured by Asahi Glass Co., Ltd. (a14): Exce 828 (" Excenol 828 ", polyether polyol Alcohol, Mn5000, hydroxyl number 3, primary hydroxyl group, manufactured by Asahi Glass Co., Ltd. (a15): P3010 ("Kuraray Polyol P-3010", polyester polyol, Mn1000, hydroxyl number 3, primary hydroxyl group, Cola (A16): GP3000 ("Sannix GP-3000", polyether polyol, Mn3000, hydroxyl number 3, secondary hydroxyl, Sanyo Chemical Industry Co., Ltd.) (a17): AM302 ("Adeka polyether AM-302", polyether polyol, Mn3000, hydroxyl number 3, primary hydroxyl, manufactured by ADEKA) (a18): PTMG1000 ("PTMG1000", poly Tetramethylene ether glycol, Mn1000, hydroxyl number 2, primary hydroxyl group, manufactured by Mitsubishi Chemical Corporation) (a19): S3011 ("Preminol S-3011", polyether polyol, Mn10000, hydroxyl number 3, secondary hydroxyl, manufactured by Asahi Glass Company ) (A20): GP1000 ("Sannix GP-1000", polyether polyol, Mn1000, hydroxyl number 3, secondary hydroxyl group, manufactured by Sanyo Chemical Industry Co., Ltd.)

<Polyisocyanate (b)> (b1): HDI (hexamethylene diisocyanate, "Desmodur H" manufactured by Sumika Covestro Urethane), (b2) : TDI (toluene diisocyanate, "Desmodur T-80" manufactured by Sumika Covestro Urethane),

<Isocyanate hardener (B)> (B1): HDI adduct ("Sumidur HT"), trimethylolpropane adduct of hexamethylene diisocyanate, Sumika Covestro polyurethane ( (Sumika Covestro Urethane) (B2): HDI urate ("Sumidur N3300", urethane body of hexamethylene diisocyanate, Sumika Covestro polyurethane Urethane)

<Plasticizer (C)> (C1): M182A ("unistar M182A", methyl oleate, manufactured by Nippon Oil Corporation) (C2): W262 ("Monocizer W262", ether Ester-based plasticizer, manufactured by DIC Corporation (C3): D55 ("ADEKACIZER D-55", epoxidized fatty acid alkyl ester, manufactured by ADEKA) (C4): TOP ("TOP", tris (2-ethylhexyl) phosphate, manufactured by Big Eight Industrial Chemicals) (C5): IPP ("Exceparl IPP", isopropyl palmitate, manufactured by Kao Corporation) )

<Antioxidant (D)> (D1): Irg1010 ("Irganox 1010", pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate ], Phenol-based antioxidant, manufactured by BASF) (D2): IrgL135 ("Irganox L135", phenylpropionic acid 3,5-bis (1,1-dimethyl-ethyl ) -4-Hydroxy-, C7-C9 side chain alkyl ester, phenolic antioxidant, manufactured by BASF)

<Antistatic agent (E)> (E1): TFSI · ammonium salt (tri-n-butylmethylammonium · bistrifluoromethanesulfonylimide, ionic liquid) (E2): TFSI · lithium salt (lithium · double triple Fluorethane methanesulfonimide, ionic solids) (E3): FSI · pyridinium salt (1-octyl-4-methylpyridinium · bisfluorosulfonimide, ionic liquid) (E4): FSI · Imidazolium salts (1-ethyl-3-methyl-imidazolium · bisfluorosulfimidine, ionic liquids) (E5): TFSI · phosphonium salts (tetrabutylphosphonium · bistrifluoromethanesulfonylimide) , Ionic solids)

<Polyfunctional polyol (F)> The said (a9)-(a20) is also used as a polyfunctional polyol, respectively.

[Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)] The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by a colloidal permeation chromatography (GPC) method. The measurement conditions are as follows. In addition, Mw and Mn are polystyrene conversion values. <Measurement conditions> Device: SHIMADZU Prominence (manufactured by Shimadzu Corporation), column: three Sodex (LF) -804 (manufactured by Showa Denko) are connected in series, detector: differential refractive index detection Solvent: Tetrahydrofuran (THF) Flow rate: 0.5 mL / min Solvent temperature: 40 ° C Sample concentration: 0.1% Sample injection volume: 100 μL

[Table 1]

[Table 2]

[table 3]

[Table 4]

(Example 1) 100 parts of urethane polyol (A1) obtained in Example 1, 2 parts of isocyanate hardener (B1), 30 parts of plasticizer (C1), and 0.7 part of antioxidant (D1) were prepared. 0.1 parts of an antistatic agent (E1), 10 parts of a polyfunctional polyol (F4 = a12), and 100 parts of ethyl acetate as a solvent, and stirred with a disperser to obtain an adhesive. In addition, the usage-amount of each material other than a solvent shows the nonvolatile content conversion value [part].

The substrate was prepared with polyethylene terephthalate (PET) with a thickness of 50 μm ("Lumirror T-60", manufactured by Toray Corporation). Using a comma coater (registered trademark), the obtained adhesive was applied to the base at a coating speed of 3 m / min, a width of 30 cm, and a thickness of 12 μm after drying. Coating on the substrate. Next, using a drying oven, the formed coating layer was dried at 100 ° C. for 1 minute to form an adhesive layer. A commercially available release sheet having a thickness of 38 μm was attached to the adhesive layer, and further cured for one week under the conditions of 23 ° C. to 50% RH to obtain an adhesive sheet.

(Example 2 to Example 73, Comparative Example 1 to Comparative Example 5) Except changing the material and blending ratio of Example 1 to those shown in Tables 5 to 13, the same procedures as in Example 1 were performed to obtain Adhesives and adhesive sheets of Examples 2 to 73 and Comparative Examples 1 to 5

[Evaluation Items and Evaluation Methods] The evaluation items and evaluation methods of the obtained adhesive and adhesive sheet are as follows.

(Indentation) Except that the coating speed of Example 1 was changed to 30 m / min and the width was changed to 150 cm, it was performed in the same manner as in Example 1 to produce an adhesive sheet, which was wound at a certain distance and visually inspected. The marks (indentations) of the adhesive tape connecting the roller to the adhesive sheet were evaluated. The evaluation criteria are as follows. ：: No trace of tape was observed at a location of 10 m. excellent. ○: No tape trace was observed at 25 m. good. △: No trace of tape was observed at a location of 50 m. Practical. ×: Tape marks were observed at a distance of 50 m. Not practical.

(Re-peelability after aging at high temperature) The obtained adhesive sheet was prepared as a measurement sample with a width of 25 mm and a length of 100 mm. Then, in a 23 ° C-50% RH environment, the release sheet was peeled from the measurement sample, the exposed adhesive layer was attached to a caustic soda glass plate, and a 2 kg roller was reciprocated once and pressure-bonded. Then, it was left to stand at 100 degreeC for 24 hours. Then, after air-cooling for 30 minutes in an environment of 23 ° C-50% RH, a tensile tester (Tensilon: Orientec) was used in accordance with Japanese Industrial Standards (JIS) Z0237. Manufactured by the company) The adhesive force was measured under conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °. In addition, in addition to changing the bonded body to an ITO film ("Tetolight TCF", manufactured by Oike Industry Co., Ltd.), PET ("Lumirror T-60", manufactured by Toray), It carried out similarly to the above, and measured the adhesive force. The evaluation criteria are as follows. ：: Less than 100 mN / 25 mm. excellent. ○: 100 mN / 25 mm or more and less than 200 mN / 25 mm. good. △: 200 mN / 25 mm or more and 300 mN / 25 mm or less. Practical. ×: More than 300 mN / 25 mm. Not practical.

(Contaminated body contamination property) The ITO surface after the "re-peelability after high temperature over time" was evaluated for the contamination property derived from the adhesive. Evaluation was performed by visually irradiating a to-be-joined body with an LED lamp in a dark room. The evaluation criteria are as follows. ○: No contamination was confirmed at all. good. △: Slight blur was confirmed. Practical. ×: Obvious blur was recognized. Not practical.

(Substrate Adhesion) The obtained adhesive sheet was prepared in a size of 50 mm in width and 50 mm in length, and was used as a measurement sample. Then, in an environment of 23 ° C.-50% RH, the peeling sheet was peeled from the measurement sample, and 11 cracks were cut at intervals of 2 mm with a knife to the adhesive layer to a depth that reached the base material without cutting. Then, 11 cracks were cut in the right-angle direction of the cracks in the same manner as described above, thereby forming 100 grids in a grid shape. The number of meshes remaining after the adhesive layer did not fall off from the substrate was evaluated when the finger was swiped ten times from above with a finger. The evaluation criteria are as follows. ：: 100 pieces remained. excellent. ○: 90 or more and less than 100 remain. good. △: 75 or more and less than 90 remain. Practical. ×: The remaining block is less than 75. Not practical.

(Antistatic property) The obtained adhesive sheet was prepared with a width of 50 mm and a length of 50 mm, and was used as a measurement sample. Then, in a 23 ° C-50% RH environment, the peeling sheet was peeled from the measurement sample, and the surface resistance value measuring device (Hiresta-UX MCP-HT800, Mitsubishi Chemical Analytech The probe made by the company) was contacted to the adhesion layer, and the surface resistance value was evaluated. The evaluation criteria are as follows. ：: The surface resistance value is less than 8 × 8. excellent. ：: The surface resistance value is not less than the power of 8 × 1 and not more than the power of 9 × 1. good. Δ: The surface resistance value is greater than or equal to the 9th power of 1 × 10 and less than the 10th power of 1 × 10. Practical. ×: The surface resistance value is 1 × 10 to the power of 10 or more. Not practical.

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Claims (8)

An adhesive includes: a urethane polyol (A) having a weight average molecular weight of 100,000 to 500,000 as a reactant of the polyol (a) and the polyisocyanate (b); an isocyanate hardener (B); Antioxidants (D); antistatic agents (E); and polyfunctional polyols (F). The adhesive according to item 1 of the scope of patent application, wherein the number of hydroxyl groups in one molecule of the polyfunctional polyol (F) is 3 or more. The adhesive according to item 1 or item 2 of the patent application scope, which further includes a plasticizer (C). The adhesive according to item 3 of the scope of patent application, wherein the plasticizer (C) is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the urethane polyol (A). The adhesive according to item 1 or item 2 of the scope of patent application, wherein the polyfunctional polyhydric polyhydric polyol is contained in an amount of 2 to 50 parts by mass based on 100 parts by mass of the urethane polyol (A). Alcohol (F). The adhesive according to item 1 or 2 of the scope of patent application, wherein the polyfunctional polyol (F) has a primary hydroxyl group at a terminal. An adhesive sheet comprising: a substrate; and an adhesive layer as a cured product of the adhesive according to any one of claims 1 to 6 of the scope of patent application. A laminated body comprising: a member selected from the group consisting of a transparent conductive film, glass, an acrylic plate, a polycarbonate plate, an olefin plate, and an inorganic barrier layer; and the component described in item 7 of the scope of patent application Follow the film.