WO2017047077A1 - ウレタン粘着剤、粘着シート、およびディスプレイ - Google Patents

ウレタン粘着剤、粘着シート、およびディスプレイ Download PDF

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Publication number
WO2017047077A1
WO2017047077A1 PCT/JP2016/004161 JP2016004161W WO2017047077A1 WO 2017047077 A1 WO2017047077 A1 WO 2017047077A1 JP 2016004161 W JP2016004161 W JP 2016004161W WO 2017047077 A1 WO2017047077 A1 WO 2017047077A1
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WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
urethane
polyol
polyols
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PCT/JP2016/004161
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English (en)
French (fr)
Japanese (ja)
Inventor
慎吾 田邉
秀平 齋藤
Original Assignee
東洋インキＳｃホールディングス株式会社
トーヨーケム株式会社
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Application filed by 東洋インキＳｃホールディングス株式会社, トーヨーケム株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Priority to CN201680004639.4A priority Critical patent/CN107109178B/zh
Priority to KR1020177017568A priority patent/KR101813846B1/ko
Publication of WO2017047077A1 publication Critical patent/WO2017047077A1/ja

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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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their 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

Definitions

  • the present invention relates to a urethane pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet and display using the same.
  • Flat panel displays such as liquid crystal displays (LCD) and organic electroluminescence displays (OELD), and touch panel displays in which such flat panel displays and touch panels are combined include televisions (TVs), personal computers (PCs), mobile phones, And widely used in electronic devices such as portable information terminals.
  • LCD liquid crystal displays
  • OELD organic electroluminescence displays
  • touch panel displays in which such flat panel displays and touch panels are combined include televisions (TVs), personal computers (PCs), mobile phones, And widely used in electronic devices such as portable information terminals.
  • OELD organic light emitting layer
  • organic charge transport layer organic charge transport layer
  • the organic EL element is thin as a whole, and its characteristics are considered to deteriorate due to oxidation of the electrode and modification of organic substances due to oxygen and moisture, etc., and oxidative decomposition of the organic material due to heat generation during driving.
  • interfacial delamination may occur between constituent elements due to interfacial stress or the like generated between the constituent elements due to the difference in thermal expansion coefficient between the constituent elements.
  • improvement of a sealing agent, a barrier layer, etc. is examined. For example, it has been studied to form a sealant and a barrier layer with a coating film.
  • the thin film / fragile member is preferably protected from impact and vibration.
  • pressure-sensitive adhesive sheets having a pressure-sensitive adhesive layer formed on a base sheet have been widely used as surface protective sheets for protecting various optical members from scratches and dust adhesion. There has been little research on the performance of protecting against the damage.
  • the “pressure-sensitive adhesive sheet” is a pressure-sensitive adhesive sheet having re-peelability (re-peelable pressure-sensitive adhesive sheet).
  • Patent Document 1 discloses an acrylic pressure-sensitive adhesive containing an acrylic acid derivative, an acrylic acid derivative polymer, and a high molecular weight crosslinking agent (Claim 1).
  • Patent Document 2 discloses an acrylic adhesive containing a monofunctional urethane acrylate oligomer having a specific weight average molecular weight (Mw), an acrylate monomer, and a free radical photoinitiator as an adhesive capable of thick film coating. (Claim 1).
  • Patent Document 3 as a pressure-sensitive adhesive capable of thick film coating, it comprises a modified polyisocyanate and a polyol, and the modified polyisocyanate has a polyisocyanate having an NCO functional group and one or more terminal activities per molecule.
  • a urethane pressure-sensitive adhesive which is a modified polyisocyanate obtained by reacting a hydrogen functional group and a polyether compound containing 6 or more ethyleneoxy (EO) units on average, and the polyol contains a liquid polycarbonate diol. (Claim 1).
  • Patent Document 4 discloses an adhesive sheet for temporarily fixing a brittle member including an adhesive layer obtained by curing a urethane adhesive containing a polyol and a polyfunctional isocyanate compound by a so-called one-shot method (Claim 1).
  • Patent Document 1 describes that the above-mentioned acrylic pressure-sensitive adhesive contains a high molecular weight polymer at a relatively high concentration, so that even a thin film is excellent in impact absorption (paragraph 0027).
  • the adhesive layer be well wetted and spread without involving air at the interface with the adherend. This property is also called “wetting”.
  • the optical member may be subjected to inspection in a state with an adhesive sheet. In such a case, the air entrained between the optical member / adhesive sheet hinders the inspection.
  • an acrylic pressure-sensitive adhesive is inferior in wettability as compared with a urethane pressure-sensitive adhesive, and is not suitable for an optical application that dislikes air entrainment.
  • Patent Document 2 describes that the above-mentioned acrylic pressure-sensitive adhesive can be made uniform in thickness because of less curing shrinkage during photopolymerization, and a pressure-sensitive adhesive sheet having a good surface appearance can be obtained (paragraph 0012).
  • the acrylic pressure-sensitive adhesive has the same problems as described above.
  • the acrylic pressure-sensitive adhesive described in Patent Document 2 has a particularly large film thickness because the amount of light such as ultraviolet rays that arrives from the surface to the inside of the coating layer gradually decreases when the coating layer is photocured. In the coating layer, uneven curing in the thickness direction tends to occur. Moreover, it cannot be said that the curing shrinkage is sufficiently suppressed. Therefore, thick film coating is not easy.
  • the urethane adhesive described in Patent Document 3 has high adhesive strength and is not suitable for re-peeling applications.
  • Patent Document 4 does not mention anything about the performance of protecting an adherend such as an optical member from impact and vibration, but generally, the one-shot method has a surface smoothness of the adhesive layer due to curing shrinkage. It tends to deteriorate and is not suitable for thickening.
  • the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer is exposed to a high-temperature and high-humidity environment, it may become cloudy (also called whitening) due to the influence of moisture in the external environment, and the appearance may deteriorate. Therefore, it is preferable that the pressure-sensitive adhesive layer has good moisture and heat whitening resistance.
  • the pressure-sensitive adhesive sheet can protect an adherend such as an optical member from adhesion of dust.
  • the pressure-sensitive adhesive sheet used for various displays has antistatic properties and has low dust adhesion. It is preferable.
  • the present invention has been made in view of the above circumstances.
  • a urethane pressure-sensitive adhesive capable of forming a thick film and capable of forming a pressure-sensitive adhesive layer with good resistance to moisture and heat whitening, and a pressure-sensitive adhesive sheet using the same It is intended to provide.
  • the present invention also provides a urethane pressure-sensitive adhesive that can form a pressure-sensitive adhesive layer capable of thick film coating, good moisture heat and whitening resistance, antistatic properties, and low dust adhesion, and uses the same. It is an object to provide a pressure-sensitive adhesive sheet.
  • the urethane pressure-sensitive adhesive of the first embodiment according to the present invention is One or more polyols (a-1) excluding a polyether polyol having one or more ethyleneoxy (EO) groups in one molecule, and one having one or more ethyleneoxy (EO) groups in one molecule
  • the urethane adhesive of the second embodiment according to the present invention is One or more polyols (a-1) excluding a polyether polyol having one or more ethyleneoxy (EO) groups in one molecule, and one having one or more ethyleneoxy (EO) groups in one molecule
  • the urethane pressure-sensitive adhesive of the first embodiment is preferably One or more polyols (a-1) excluding a polyether polyol having one or more ethyleneoxy (EO) groups in one molecule, and one having one or more ethyleneoxy (EO) groups in one molecule
  • a urethane prepolymer (A) obtained by reacting at least one polyether polyol (a-2) with at least one polyisocyanate (b); It can be produced by a production method in which ⁇ -diketone compound (X) is blended.
  • the pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive according to the first or second embodiment of the present invention.
  • the display of this invention contains the adhesion layer which consists of hardened
  • ethyleneoxy group is a group represented by the chemical formula “—CH 2 CH 2 O—” and may be abbreviated as “EO group”.
  • EO group ethylene oxide that forms an EO group by a ring-opening reaction.
  • a sheet-like material is referred to as “tape”, “film”, or “sheet” depending on the thickness and width.
  • staple a sheet-like material
  • film a sheet-like material
  • sheet a sheet-like material
  • these are not particularly distinguished, and the term “sheet” is used as a term representing a concept encompassing them.
  • a urethane pressure-sensitive adhesive capable of forming a thick film and capable of forming a pressure-sensitive adhesive layer having good moisture and heat whitening resistance, and a pressure-sensitive adhesive sheet using the same.
  • the pressure-sensitive adhesive of the first embodiment according to the present invention containing the urethane prepolymer (A) and the ⁇ -diketone compound (X) can be applied to a thick film, has good moisture and heat whitening resistance, and has an antistatic property. It is possible to form an adhesive layer having low dust adhesion.
  • the urethane pressure-sensitive adhesive of the present invention contains one or more specific urethane prepolymers (A).
  • the urethane pressure-sensitive adhesive according to the first embodiment of the present invention includes one or more specific urethane prepolymers (A) and one or more ⁇ -diketone compounds (X).
  • the urethane pressure-sensitive adhesive according to the second embodiment of the present invention includes one or more specific urethane prepolymers (A) and one or more fatty acid esters (B).
  • the urethane prepolymer (A) is a reaction product obtained by copolymerizing a plurality of types of polyol (a) and one or more types of polyisocyanate (b).
  • the urethane prepolymer (A) is a copolymer containing a plurality of types of monomer units derived from a plurality of types of polyol (a) and one or more types of polyisocyanate (b).
  • the plurality of types of polyol (a) include one or more types of polyol (a-1) excluding a polyether polyol having one or more ethyleneoxy (EO) groups in one molecule, and one molecule.
  • the polyol (a-1) is an arbitrary polyol excluding a polyether polyol having one or more EO groups in one molecule.
  • Examples of the polyol (a-1) include polyacryl polyol, polyester polyol, polyether polyol having no EO group, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol.
  • polyester polyols, polyether polyols having no EO group, polycaprolactone polyols, and polycarbonate polyols are preferable, and polyester polyols and polyether polyols having no EO group are more preferable.
  • the polyester polyol is a polyol having a polyester structure.
  • This polyol is a polycondensate of one or more acid components and one or more polyol components, and can be obtained by an esterification reaction of one or more acid components and one or more polyol components.
  • the acid component of the raw material include polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
  • the polyol component of the raw material includes ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3 Bifunctional polyols having two hydroxyl groups such as' -dimethylol heptane, butylethylpentanediol, polyoxyethylene glycol, and polyoxypropylene glycol (also referred to as glycol or diol); hydroxyl groups such as glycerin, trimethylolpropane, and pentaerythritol And a trifunctional or higher functional polyol having 3 or more.
  • a polyether polyol is a polyol having a polyether structure, and is a ring-opening polymer of one or more active hydrogen-containing compounds having two or more active hydrogens and one or more cyclic ethers.
  • the polyether polyol used as the polyol (a-1) does not have an EO group.
  • a cyclic ether that does not form an EO group is used as a raw material cyclic ether.
  • Examples of the active hydrogen-containing compound include a compound having a hydroxyl group, an amine, and a compound having a hydroxyl group and an NH group.
  • Examples of the compound having a hydroxyl group include two hydroxyl groups such as water and glycol (also referred to as diol) (specifically, propylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and the like).
  • Bifunctional polyols having trifunctional or higher functional polyols having three or more hydroxyl groups such as glycerin, trimethylolpropane, and pentaerythritol.
  • Examples of the amine include polyamines such as ethylenediamine, isophoronediamine, and xylylenediamine.
  • Examples of the compound having a hydroxyl group and an NH group include N-aminoethylethanolamine.
  • Examples of the cyclic ether that does not form an EO group include alkylene oxide (AO) excluding ethylene oxide (EO) such as propylene oxide and butylene oxide; tetrahydrofuran and the like.
  • the polyether polyol having no EO group is preferably an alkylene oxide adduct of an active hydrogen-containing compound (however, excluding the EO adduct) (also referred to as polyoxyalkylene polyol).
  • an alkylene oxide adduct of an active hydrogen-containing compound also referred to as polyoxyalkylene polyol.
  • Specific examples include bifunctional polyalkylene glycols such as polypropylene glycol (PPG) and polytetramethylene glycol; trifunctional or higher functional polyether polyols such as alkylene oxide adducts of glycerin.
  • Polycaprolactone polyol is a polyol having a polyester structure, and is a ring-opening polymer of one or more cyclic esters such as ⁇ -caprolactone and ⁇ -valerolactone. This polyol can be obtained by ring-opening polymerization of one or more cyclic esters.
  • Polycarbonate polyol is a polyol having a carbonate structure. This polyol is obtained by polycondensation of polyol and phosgene, polycondensation of polyol and dioxy compound bischloroformate, polycondensation of polyol and diester carbonate, polycondensation of polyol and dioxy compound biscarbonate, and the like. be able to.
  • the polyol (a-1) other than the polyether polyol may have an EO group.
  • the polyol (a-1) is a polyol having no EO group.
  • the polyol (a-1) is selected from the group consisting of a polyester polyol having no EO group, a polyether polyol having no EO group, a polycaprolactone polyol having no EO group, and a polycarbonate polyol having no EO group.
  • at least one polyol is preferable.
  • a polyester polyol having no EO group and a polyether polyol having no EO group are more preferable.
  • the number average molecular weight (Mn) of the polyol (a-1) is not particularly limited, and preferred ranges are as follows.
  • the Mn of the polyester polyol is preferably 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,000 to 3,000.
  • the Mn of the polyether polyol having no EO group is preferably 500 to 5,000, more preferably 1,000 to 4,000.
  • the Mn of the polycaprolactone polyol is preferably 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,000 to 3,000.
  • the Mn of the polycarbonate polyol is preferably 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,000 to 3,000.
  • gelatinization of a urethane prepolymer (A) is effectively suppressed because Mn is more than a minimum, and the cohesion force of a urethane prepolymer (A) becomes suitable because it is below an upper limit.
  • Polyether polyol (a-2) having one or more EO groups in one molecule is a compound obtained by addition polymerization of one or more cyclic ethers containing ethylene oxide (EO) to an active hydrogen-containing compound (Addition polymer).
  • EO ethylene oxide
  • Addition polymer an active hydrogen-containing compound
  • Examples of the cyclic ether other than the active hydrogen-containing compound and ethylene oxide (EO) are the same as those of the polyol (a-1).
  • polyether polyol having one or more EO groups in one molecule
  • one or more alkylene oxides (AO) containing ethylene oxide (EO) are added to an active hydrogen-containing compound having two active hydrogen groups.
  • AO alkylene oxides
  • EO ethylene oxide
  • the polyalkylene glycol obtained by making it contain is mentioned.
  • examples of such polyalkylene glycols include polyethylene glycol (PEG).
  • Examples of the trifunctional or higher functional polyether polyol having one or more EO groups in one molecule include one or more alkylene oxides (AO) containing ethylene oxide (EO) in an active hydrogen-containing compound having three or more active hydrogen groups.
  • AO alkylene oxides
  • EO ethylene oxide
  • the compound (addition polymerization product) obtained by addition-polymerizing can be mentioned.
  • glycerin EO adduct obtained by addition polymerization of one or more ethylene oxide (EO) to glycerin
  • one or more glycerin Examples include glycerin PO ⁇ EO adducts (also referred to as “glycerin polypropylene glycol-terminated ethylene glycol-modified”) obtained by addition polymerization of propylene oxide (PO) and one or more ethylene oxides (EO) in this order.
  • the number average molecular weight (Mn) of the polyether polyol (a-2) having one or more EO groups in one molecule is not particularly limited, preferably 500 to 5,000, more preferably 1,000 to 5, 000, particularly preferably 1,500 to 5,000.
  • Mn is 500 or more, gelation of the urethane prepolymer (A) is effectively suppressed.
  • Mn is 5,000 or less, the cohesion force of the urethane prepolymer (A) is suitable.
  • the urethane prepolymer (A) obtained using the polyether polyol (a-2) having one or more EO groups in one molecule is relatively easily cured. Therefore, after coating the pressure-sensitive adhesive of the present invention on the substrate sheet, the coating layer is cured relatively quickly, so that thick film coating is easy. In addition, since the coating layer cures relatively quickly even after thick film coating, against the hot air when the coating layer is heated and dried, or against the mechanical stress received when winding the adhesive sheet obtained after heating and drying The coating layer and the adhesive layer are not easily affected. Therefore, defects such as roll streaks and distortion can be suppressed, and an adhesive layer with good surface smoothness can be formed. Since the adhesive layer can be thickened, it is possible to form an adhesive layer that is excellent in impact resistance and excellent in the function of protecting adherends such as various optical members from impact and vibration.
  • the adhesive layer may become clouded (whitened) when exposed to a high temperature and high humidity environment.
  • the EO group is a hydrophilic group.
  • the adhesive layer using this has a surface resistance.
  • the value is relatively low and it can have a little antistatic property.
  • the urethane prepolymer (A) alone cannot exhibit an antistatic property that can effectively suppress the adhesion of dust to the adhesive layer.
  • the urethane prepolymer (A) and the ⁇ -diketone compound (X) are used in combination, the surface resistance value of the adhesive layer is effectively reduced and the antistatic property is effectively expressed. Dust adhesion to the surface of the adherend can be effectively suppressed.
  • any of a bifunctional polyol having two hydroxyl groups and a trifunctional or more functional polyol having three or more hydroxyl groups may be used. These may be used in combination.
  • the polyol (a-2) either a bifunctional polyol having two hydroxyl groups or a trifunctional or more functional polyol having three or more hydroxyl groups may be used. These may be used in combination.
  • the bifunctional polyol has a two-dimensional crosslinkability and can impart an appropriate flexibility to the adhesive layer.
  • a trifunctional or higher functional polyol has a three-dimensional crosslinkability and can impart an appropriate hardness to the adhesive layer.
  • the adhesive strength, cohesive strength, removability, etc. of the urethane pressure-sensitive adhesive of the present invention can be adjusted. It is preferable that at least one of the plural types of polyols (a) is a trifunctional or higher functional polyol because it is easy to achieve both adhesive force and removability.
  • the mass ratio between the one or more polyols (a-1) and the one or more polyether polyols (a-2) is not particularly limited.
  • the total amount of the one or more polyols (a-1) and the one or more polyether polyols (a-2) is 100 parts by mass.
  • the amount of the one or more polyether polyols (a-1) is preferably more than 0 parts by weight and 50 parts by weight or less, more preferably 20 to 50 parts by weight.
  • the amount of the one or more polyether polyols (a-2) is preferably 50 parts by weight or more and less than 100 parts by weight, more preferably 50 to 80 parts by weight.
  • the amount of the one or more polyether polyols (a-2) is 50 parts by mass or more, the heat-and-moisture whitening resistance and the antistatic property can be effectively expressed.
  • the amount of the one or more polyols (a-1) is more than 0 parts by mass, the effect of thick film coatability can be effectively expressed.
  • Polyisocyanate (b) examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate.
  • Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2 4,4-trimethylhexamethylene diisocyanate and the like.
  • the alicyclic polyisocyanates 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, 1,4-bis (isocyanatemethyl) cyclohexane, etc. .
  • examples of the polyisocyanate (b) include trimethylolpropane adducts, burettes, and trimers of the above polyisocyanates (this trimer includes an isocyanurate ring).
  • polyisocyanate (b) an aliphatic polyisocyanate and an alicyclic polyisocyanate are preferable, and an aliphatic polyisocyanate is more preferable.
  • a plurality of types of polyol (specifically, a combination of one or more types of polyol (a-1) and one or more types of polyether polyol (a-2)).
  • one or more polyisocyanates (b) are the number of moles of hydroxyl groups (OH) in the plurality of polyols (a) and the number of isocyanate (NCO) groups in the one or more polyisocyanates (b).
  • the reaction is preferably carried out at a ratio such that the functional group ratio (NCO / OH ratio) to the number of moles is 0.5 to 0.9.
  • Catalyst> For the polymerization of the urethane prepolymer (A), one or more catalysts can be used as necessary.
  • Known catalysts can be used as the catalyst, and examples thereof include tertiary amine compounds and organometallic compounds.
  • tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU).
  • organometallic compounds include tin compounds and non-tin compounds.
  • tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide.
  • DBTDL dibutyltin dilaurate
  • Tributyltin acetate triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
  • Non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; Other metal compounds such as zirconium naphthenate and bismuth carboxylate are listed.
  • the combination of two or more kinds of catalysts is not particularly limited, and examples thereof include tertiary amine / organometallic, tin / non-tin, and tin / tin.
  • Tin-based / tin-based is preferable, and dibutyltin dilaurate / 2-ethylhexanoic acid tin is more preferable.
  • the mass ratio of tin 2-ethylhexanoate / dibutyltin dilaurate is not particularly limited and is preferably more than 0 and less than 1, more preferably 0.2 to 0.6. If the mass ratio is less than 1, the catalyst activity is well balanced and gelation can be effectively suppressed.
  • the amount of the one or more catalysts used is not particularly limited, and is preferably 0.01 to 1% by mass based on the total amount of the plurality of polyols (a) and one or more polyisocyanates (b).
  • solvents For the polymerization of the urethane prepolymer (A), one or more solvents can be used as necessary.
  • solvents can be used, and examples include ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; aromatic hydrocarbons such as toluene and xylene. From the viewpoint of the solubility of the urethane prepolymer (A) and the boiling point of the solvent, ethyl acetate, toluene and the like are preferable.
  • the polymerization method of the urethane prepolymer (A) is not particularly limited, and known polymerization methods such as a bulk polymerization method and a solution polymerization method can be applied.
  • the polymerization procedure is not particularly limited, Procedure 1) A procedure in which a plurality of types of polyol (a), one or more types of polyisocyanate (b), one or more types of catalysts as necessary, and one or more types of solvents as necessary are reacted after batch mixing; Procedure 2) While mixing a plurality of types of polyol (a), one or more types of catalysts as required, and one or more types of solvents as required, adding one or more types of polyisocyanate (b) to this The procedure to make it react is mentioned. Procedure 2) is preferred because the reaction is easy to control.
  • the reaction temperature when using a catalyst is preferably less than 100 ° C., more preferably 85 to 95 ° C. If reaction temperature is less than 100 degreeC, it is easy to control reaction rate, a crosslinked structure, etc., and will produce
  • the reaction temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and the reaction time is preferably 3 hours or longer.
  • the weight average molecular weight (Mw) of the urethane prepolymer (A) is preferably 30,000 to 500,000, more preferably 50,000 to 400,000, and the molecular weight distribution (Mw) / Mn) is preferably 4 to 12, more preferably 6 to 10.
  • the pressure-sensitive adhesive of the present invention can contain one or more ⁇ -diketone compounds (X).
  • the ⁇ -diketone compound (X) is not particularly limited, and 2,4-pentanedione, 3-methyl-2,4-pentanedione, 2,4-hexanedione, 1,3-cyclohexanedione, 2,2- Dimethyl-3,5-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cycloheptanedione, 2 , 4-octanedione, 2,2,7-trimethyl-3,5-octanedione, 2,4-nonanedione, 3-methyl-2,4-nonanedione, 2-methyl-4,6-nonanedione, 1-phenyl -1,
  • the ⁇ -diketone compound (X) easily forms an enol form among keto-enol tautomers, and thus has a dielectric polarizability, thereby having a little conductivity. Therefore, the pressure-sensitive adhesive layer containing this compound has a relatively low surface resistance value and can have a little antistatic property.
  • the ⁇ -diketone compound (X) alone cannot exhibit an antistatic property that can effectively suppress dust adhesion on the adhesive layer.
  • the urethane prepolymer (A) having one or more EO groups in combination with the ⁇ -diketone compound (X), the surface resistance value of the adhesive layer is effectively reduced and the antistatic property is effectively exhibited. In addition, dust adhesion on the adhesive layer can be effectively suppressed.
  • the amount of the one or more ⁇ -diketone compounds (X) added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the one or more types of urethane prepolymer (A).
  • the amount is 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, and most preferably 0.5 to 5 parts by mass. If the addition amount is 0.01 parts by mass or more, the effect of suppressing adhesion of dust to the adhesive layer can be effectively exhibited. If the addition amount is 10 parts by mass or less, the amount of the urethane prepolymer (A), which is the main active ingredient of the pressure-sensitive adhesive that is originally necessary, is sufficiently secured, and the performance required as the pressure-sensitive adhesive is secured.
  • the pressure-sensitive adhesive of the present invention can contain one or more fatty acid esters (B).
  • the fatty acid ester (B) acts as a plasticizer and can improve the wettability of the adhesive layer.
  • the fatty acid ester (B) also increases the hydrophobicity of the adhesive layer, in particular, the surface layer portion of the adherend side such as the optical member of the adhesive layer, and adheres from the external environment when the adhesive sheet is exposed to a high temperature and high humidity environment. Intrusion of moisture into the layer can be suppressed, and white turbidity (whitening) of the adhesive layer can be suppressed.
  • the fatty acid ester (B) is not particularly limited, and is an ester obtained by reacting a monobasic acid or polybasic acid having 8 to 18 carbon atoms with a branched alcohol having 18 or less carbon atoms; an unsaturated fatty acid having 14 to 18 carbon atoms; Preferred are esters obtained by the reaction of alcohol with an alcohol having 4 or less hydroxyl groups.
  • Examples of the ester obtained by the reaction of a monobasic acid or polybasic acid having 8 to 18 carbon atoms with a branched alcohol having 18 or less carbon atoms include isostearyl laurate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, and palmitic acid.
  • Examples include isostearyl acid, isocetyl stearate, octyldodecyl oleate, diisostearyl adipate, diisocetyl sebacate, trioleyl trimellitate, and triisocetyl trimellitate.
  • isopropyl myristate, isocetyl myristate, and octyldodecyl myristate are preferable, and isopropyl myristate is particularly preferable.
  • unsaturated fatty acid having 14 to 18 carbon atoms include myristoleic acid, oleic acid, linoleic acid, linolenic acid, isopalmitic acid, and isostearic acid.
  • examples of the alcohol having 4 or less hydroxyl groups include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitan.
  • the number average molecular weight (Mn) of the fatty acid ester (B) is not particularly limited, and is preferably 200 or more and preferably 600 or less from the viewpoint of improving the wetting rate.
  • the addition amount of the one or more fatty acid esters (B) is not particularly limited, and is preferably 5 to 50 parts by mass, more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the one or more types of urethane prepolymer (A). Part. If the addition amount is 5 parts by mass or more, the effect of adding the fatty acid ester (B) (the effect of improving wettability) can be effectively expressed. If the addition amount is 50 parts by mass or less, the amount of the urethane prepolymer (A), which is the main active ingredient of the pressure-sensitive adhesive that is originally necessary, is sufficiently secured, and the performance required as the pressure-sensitive adhesive is secured.
  • the urethane adhesive of the present invention may be a third embodiment that combines the first embodiment and the second embodiment. That is, the urethane pressure-sensitive adhesive of the present invention may be a third embodiment including a urethane prepolymer (A), a ⁇ -diketone compound (X), and a fatty acid ester (B).
  • A urethane prepolymer
  • X ⁇ -diketone compound
  • B a fatty acid ester
  • the pressure-sensitive adhesive of the present invention can contain one or more isocyanate curing agents (I) as necessary. If it consists of an adhesive of this invention, a urethane prepolymer (A) will be hardened
  • the isocyanate curing agent (I) known compounds can be used, and compounds exemplified by the polyisocyanate (b) which is a raw material of the urethane prepolymer (A) (specifically, aromatic polyisocyanate, aliphatic polyisocyanate, An aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate, and a trimethylolpropane adduct body / a burette body / trimer) can be used.
  • the content of the one or more isocyanate curing agents (I) in the urethane pressure-sensitive adhesive of the present invention is not particularly limited, and preferably 3 to 30 masses per 100 mass parts of the one or more urethane prepolymers (A). Part, more preferably 10 to 20 parts by weight. When the content is 3 parts by mass or more, the cohesive force of the adhesive layer is good, and when the content is 30 parts by mass or less, the adhesive force of the adhesive layer is good.
  • the pressure-sensitive adhesive of the present invention can contain one or more curing accelerators as required.
  • a well-known thing can be used as a hardening accelerator, The catalyst etc. which were mentioned by the synthesis
  • the addition amount of the one or more curing accelerators is not particularly limited, and is preferably 0.0005 to 0.5 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A) from the viewpoint of effective curing acceleration. More preferably, the amount is 0.001 to 0.1 parts by mass, particularly preferably 0.003 to 0.05 parts by mass, and most preferably 0.005 to 0.03 parts by mass.
  • the pressure-sensitive adhesive of the present invention can contain one or more solvents as required.
  • a well-known thing can be used as a solvent, Acetone, methyl ethyl ketone, ethyl acetate, toluene, xylene, etc. are mentioned. From the viewpoints of the solubility of the urethane prepolymer (A) and the boiling point of the solvent, ethyl acetate and toluene are particularly preferable.
  • the pressure-sensitive adhesive of the present invention can contain one or more other optional components as necessary, as long as the effects of the present invention are not impaired.
  • any resin other than the urethane prepolymer (A), a curing retarder, a filler, a metal powder, a colorant, a foil, a softener, a conductive agent, an antioxidant, an ultraviolet absorber examples thereof include light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, antifoaming agents, and lubricants.
  • Filler examples include talc, calcium carbonate, and titanium oxide.
  • antioxidant examples include a radical chain inhibitor (primary antioxidant) and a peroxide decomposer (secondary antioxidant).
  • radical chain inhibitors examples include phenolic antioxidants and amine antioxidants.
  • peroxide decomposer examples include a sulfur-based antioxidant and a phosphorus-based antioxidant.
  • phenolic antioxidants include monophenolic, bisphenolic, and polymeric phenolic antioxidants.
  • Monophenol antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, and stearin- ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate.
  • bisphenol antioxidants examples include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis. (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), and 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane and the like.
  • Polymeric phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-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, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, and 1,3,5-tris (3 ′, 5′-di-t-butyl- 4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like.
  • IRGANOX L 135 manufactured by BASF
  • BASF is preferable in terms of good compatibility with the urethane prepolymer (A
  • sulfur-based antioxidants examples include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl 3,3′-thiodipropionate.
  • phosphorus antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, and phenyl diisodecyl phosphite.
  • the urethane pressure-sensitive adhesive of the present invention can be produced by applying a known method.
  • the urethane pressure-sensitive adhesive of the first embodiment is preferably One or more polyols (a-1) excluding a polyether polyol having one or more ethyleneoxy groups in one molecule, and one or more polyether polyols having one or more ethyleneoxy groups in one molecule
  • the urethane pressure-sensitive adhesive of the second embodiment is preferably One or more polyols (a-1) excluding a polyether polyol having one or more ethyleneoxy groups in one molecule, and one or more polyether polyols having one or more ethyleneoxy groups in one molecule
  • the pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer made of a cured product of the above-mentioned pressure-sensitive adhesive of the present invention.
  • the pressure-sensitive adhesive sheet of the present invention preferably includes a substrate sheet and a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive of the present invention.
  • An adhesion layer can be formed in the single side
  • FIG. 1 the schematic cross section of the adhesive sheet of 1st Embodiment which concerns on this invention is shown.
  • reference numeral 10 is an adhesive sheet
  • reference numeral 11 is a base sheet
  • reference numeral 12 is an adhesive layer
  • reference numeral 13 is a release sheet.
  • the pressure-sensitive adhesive sheet 10 is a single-sided pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed on one side of a base sheet.
  • FIG. 2 the schematic cross section of the adhesive sheet of 2nd Embodiment which concerns on this invention is shown.
  • reference numeral 20 is an adhesive sheet
  • reference numeral 21 is a base material sheet
  • reference numerals 22A and 22B are adhesive layers
  • reference numerals 23A and 23B are release sheets.
  • the substrate sheet is not particularly limited, and examples thereof include a resin sheet, paper, and metal foil.
  • the base sheet may be a laminated sheet in which any one or more layers are laminated on at least one surface of these base sheets.
  • the surface of the base sheet on the side where the adhesive layer is to be formed may be subjected to easy adhesion treatment such as corona discharge treatment and anchor coating agent application, if necessary.
  • ester resins such as polyethylene terephthalate (PET); olefin resins such as polyethylene (PE) and polypropylene (PP); vinyl resins such as polyvinyl chloride; nylon 66, etc. Amide resin; Urethane resin (including foam); and combinations thereof.
  • the thickness of the resin sheet excluding the polyurethane sheet is not particularly limited and is preferably 15 to 300 ⁇ m.
  • the thickness of the polyurethane sheet (including foam) is not particularly limited, and is preferably 20 to 50,000 ⁇ m.
  • the paper is not particularly limited, and examples thereof include plain paper, coated paper, and art paper.
  • the constituent metal of the metal foil is not particularly limited, and examples thereof include aluminum, copper, and combinations thereof.
  • the release sheet is not particularly limited, and a known release sheet in which a known release treatment such as application of a release agent is performed on the surface of a resin sheet or paper can be used.
  • An adhesive sheet can be manufactured by a well-known method.
  • the adhesive of the present invention is applied to the surface of the base sheet to form a coating layer made of the urethane adhesive of the present invention.
  • a known method can be applied as the coating method, and examples thereof include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, and a gravure coater method.
  • the coating layer is dried and cured to form an adhesive layer made of a cured product of the urethane adhesive of the present invention.
  • the heating and drying temperature is not particularly limited, and is preferably about 60 to 150 ° C.
  • a release sheet is attached to the exposed surface of the adhesive layer by a known method.
  • a single-sided adhesive sheet can be manufactured as described above.
  • a double-sided PSA sheet can be produced by performing the above operations on both sides.
  • the pressure-sensitive adhesive of the present invention is applied to the surface of the release sheet to form a coating layer made of the pressure-sensitive adhesive of the present invention, and then the coating layer is dried and cured to produce the pressure-sensitive adhesive of the present invention.
  • An adhesive layer made of a cured product of the agent may be formed, and finally a substrate sheet may be laminated on the exposed surface of the adhesive layer.
  • the urethane pressure-sensitive adhesive of the present invention can be suitably used for thin film coating and thick film coating, and has a higher degree of freedom in designing the thickness of the adhesive layer than in the past.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately designed depending on the application of the pressure-sensitive adhesive sheet, and may be a conventional level (5 to 30 ⁇ m) or a thick film level of 30 ⁇ m or more, which has been difficult in the past.
  • the upper limit of the thickness of the adhesive layer is not particularly limited, and is about 200 ⁇ m because an adhesive layer with good surface smoothness can be formed.
  • the thickness of the adhesive layer is preferably 30 to 200 ⁇ m, more preferably 40 to 150 ⁇ m, and particularly preferably 50 to 150 ⁇ m.
  • thickness of the adhesive layer is a thickness after drying unless otherwise specified.
  • the surface resistance value of the pressure-sensitive adhesive layer is reduced and antistatic is performed. Property can be improved and dust adhesion of the pressure-sensitive adhesive sheet can be effectively suppressed.
  • the antistatic property can be evaluated by the surface resistance value.
  • the surface resistance value of the pressure-sensitive adhesive layer obtained using the urethane pressure-sensitive adhesive of the present invention is preferably less than 1.0 ⁇ 10 11 ( ⁇ / ⁇ ). With this level of surface resistance, dust adhesion is effectively suppressed.
  • the “surface resistance value” can be measured by the method described in the section “Example”.
  • 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 and the like.
  • the pressure-sensitive adhesive sheet of the present invention is suitably used as a surface protective sheet, a cosmetic sheet, a non-slip sheet, and the like.
  • the pressure-sensitive adhesive sheet of the present invention is suitably used as a surface protective sheet for various displays (flat panel display, touch panel display, etc.), and substrates and optical members manufactured or used in these manufacturing processes.
  • a urethane pressure-sensitive adhesive capable of forming a thick film and capable of forming a pressure-sensitive adhesive layer having good moisture and heat whitening resistance, and a pressure-sensitive adhesive sheet using the same. be able to.
  • the pressure-sensitive adhesive of the first embodiment according to the present invention containing the urethane prepolymer (A) and the ⁇ -diketone compound (X) can be applied to a thick film, has good moisture and heat whitening resistance, and has an antistatic property. It is possible to form an adhesive layer having low dust adhesion.
  • the pressure-sensitive adhesive of the second embodiment according to the present invention containing the urethane prepolymer (A) and the fatty acid ester (B) has good wettability, can be applied to a thick film, and has good moisture and heat whitening resistance. A layer can be formed.
  • the display of this invention contains the adhesion layer which consists of hardened
  • the display of the present invention can preferably include an adhesive sheet including an adhesive layer made of a cured product of the adhesive of the present invention.
  • Examples of the display include flat panel displays such as a liquid crystal display (LCD) and an organic electroluminescence display (ELD), and a touch panel display in which such a flat panel display and a touch panel are combined.
  • Mw, Mn, Mw / Mn The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography (GPC) method. The measurement conditions were as follows. Mw and Mn are both polystyrene equivalent values.
  • the materials used are as follows. ⁇ Polyol (a-1)> (A-1-1): Kuraray Polyol P-1010 (manufactured by Kuraray Co., Ltd.), bifunctional polyester polyol having no EO group, Mn1000, hydroxyl number 2, (A-1-2): Kuraray Polyol P-2010 (manufactured by Kuraray), bifunctional polyester polyol having no EO group, Mn2000, hydroxyl number 2, (A-1-3): Kuraray Polyol P-3010 (manufactured by Kuraray Co., Ltd.), bifunctional polyester polyol having no EO group, Mn 3000, hydroxyl number 2, (A-1-4): Sannix GP-1500 (manufactured by Sanyo Chemical Industries), trifunctional polyether polyol having no EO group, Mn 1500, hydroxyl number 3, (A-1-5): SANNICS PP-2000 (manufactured by Sanyo Chemical Industries), bifunctional polyether polyol having no
  • ⁇ Polyether polyol having EO group (a-2)> Adeka polyether AM-302 (manufactured by ADEKA), trifunctional polyether polyol, glycerin PO ⁇ EO adduct, Mn 3000, hydroxyl number 3, (A-2-2): Adeka polyether GR-3308 (manufactured by ADEKA), trifunctional polyether polyol, glycerin PO ⁇ EO adduct, Mn 3400, hydroxyl number 3.
  • B-1 Hexamethylene diisocyanate (manufactured by Tosoh Corporation)
  • B-2 Takenate (registered trademark) 500 (manufactured by Mitsui Chemicals), 1,3-xylylene diisocyanate.
  • B-1 NIKKOL IPP (manufactured by Nikko Chemicals), isopropyl palmitate
  • B-2 NIKKOL IPM-100 (manufactured by Nikko Chemicals), isopropyl myristate.
  • ⁇ -diketone compound (X)> (X-1): 2,4-pentanedione, (X-2): 2,2-dimethyl-3,5-hexanedione.
  • Isocyanate curing agent (I-1): Coronate HL (manufactured by Tosoh Corporation), hexamethylene diisocyanate / trimethylolpropane adduct, (I-2) Sumidur N-3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), hexamethylene diisocyanate / isocyanurate, (I-3): Coronate L (manufactured by Tosoh Corporation), tolylene diisocyanate / trimethylolpropane.
  • Table 1-1 shows the types of polyol (a) and polyisocyanate (b) used, the blending ratio thereof, and the Mw of the obtained urethane prepolymer.
  • the unit of the blending amount of the polyol (a) is [part]
  • the blending amount of the polyisocyanate (b) is represented by an NCO / OH ratio (functional group ratio) (Table 1). -2 to Table 1-5).
  • the amount of the polyisocyanate (b-1) was calculated according to the following formula (the same applies to other synthesis examples).
  • Synthesis Examples 2 to 22 were the same as Synthesis Example 1 except that the types of polyol (a) and polyisocyanate (b) used and the blending ratios thereof were changed as shown in Table 1-1 to Table 1-5. Thus, urethane prepolymers (A-1) to (A-19) and comparative urethane prepolymers (D-1) to (D-3) were obtained. Tables 1-1 to 1-5 show the Mw of the urethane prepolymer and the non-volatile concentration of the urethane prepolymer solution in each synthesis example.
  • Example 1 100 parts of urethane prepolymer (A-1) obtained in Synthesis Example 1, 30 parts of fatty acid ester (B-1), 0.3 part of antioxidant “IRGANOX L 135” (BASF), UV Absorber “TINUVIN 571” (manufactured by BASF) 0.3 parts, light stabilizer “TINUVIN 765” (manufactured by BASF Corporation) 0.3 parts, isocyanate curing agent (I-1) 15 parts, and solvent
  • a urethane pressure-sensitive adhesive was obtained by blending 100 parts of ethyl acetate and stirring with a disper.
  • the usage-amount of each material except a solvent shows a non-volatile content conversion value (it is the same also in another Example and a comparative example).
  • Table 2-1 shows the types and mixing ratios of the materials used.
  • Example 2 to 26 were the same as Example 1-1, except that the types and blending ratios of the materials used were changed as shown in Tables 2-1 to 2-4 and Tables 3-1 to 3-2. Thus, a urethane pressure-sensitive adhesive was obtained.
  • Comparative Examples 1 to 3 In Comparative Examples 1 to 3, a urethane pressure-sensitive adhesive was obtained in the same manner as in Example 1-1 except that the types and blending ratios of the materials used were changed as shown in Tables 2-5 and 3-3. .
  • a first evaluation pressure-sensitive adhesive sheet (release sheet / adhesive layer / base material sheet) was obtained as follows.
  • a polyethylene terephthalate (PET) sheet (Lumirror T-60, manufactured by Toray Industries, Inc.) having a thickness of 50 ⁇ m was prepared as a base material sheet.
  • a comma coater (registered trademark)
  • the obtained urethane pressure-sensitive adhesive was coated on one surface of a base sheet so that the thickness after drying was 80 ⁇ m under the condition of a coating speed of 30 m / min.
  • the formed coating layer was dried at 100 ° C. for 2 minutes to form an adhesive layer.
  • the formed adhesive layer was evaluated for suitability for thick film coating.
  • a 38 ⁇ m-thick release sheet (Super Stick SP-PET38, manufactured by Lintec Corporation) is pasted on the formed adhesive layer, and cured for one week in an atmosphere of 23 ° C. and 50% RH. 1 evaluation pressure-sensitive adhesive sheet (release sheet / adhesive layer / base material sheet) was obtained.
  • This first pressure-sensitive adhesive sheet for evaluation was evaluated for adhesive strength, moisture and heat whitening resistance, wettability, and surface resistance. In the present specification, “RH” indicates relative humidity.
  • a second evaluation pressure-sensitive adhesive sheet (release sheet / adhesive layer / release sheet) was obtained as follows. Using a comma coater (registered trademark), a urethane pressure-sensitive adhesive obtained on a first release sheet (film binder 50E0010-DG3, manufactured by Fujimori Kogyo Co., Ltd.) having a thickness of 50 ⁇ m was applied at a coating speed of 3 m / min. The coating was performed so that the thickness after drying was 80 ⁇ m. The formed coating layer was dried at 100 ° C.
  • the evaluation criteria are as follows. ⁇ : Less than 3 seconds, good. ⁇ : 3 seconds or more and less than 5 seconds, practical use possible. X: 5 seconds or more, impractical.
  • the surface of the formed pressure-sensitive adhesive layer was visually observed based on the following criteria before the release sheet was stuck.
  • the evaluation criteria are as follows. ⁇ : The surface was smooth and good. ⁇ : Unevenness observed on the surface, practical use. X: Roll streaks or distortion was observed on the surface, impractical.
  • the gel fraction was measured as an index of thick film coating suitability. If the adhesive layer has a high fluidity state before curing for a long time during curing, the surface smoothness may decrease. When the pressure-sensitive adhesive layer obtained after the heat-drying treatment has a high gel fraction in a relatively short time, it is quickly cured and is suitable for thick film coating. A measurement sample having a width of 30 mm and a length of 100 mm was cut out from the second evaluation adhesive sheet. Next, the first release sheet was peeled from the measurement sample, and the exposed surface of the adhesive layer was attached to a 200-mesh wire net. Furthermore, after peeling the second release sheet, the entire adhesive layer was wrapped with the wire mesh.
  • the surface resistance value was measured as an index of dust adhesion.
  • a measurement sample having a width of 100 mm and a length of 100 mm was cut out from the first evaluation pressure-sensitive adhesive sheet. Next, this measurement sample was left in an atmosphere of 23 ° C. and 50% RH for 30 minutes, and then the release sheet was peeled from the measurement sample.
  • the measurement terminal was brought into contact with the exposed surface of the adhesive layer, and the surface resistance value ( ⁇ / ⁇ ) was measured.
  • the evaluation criteria are as follows.
  • ⁇ Less than 1.0 ⁇ 10 11 ⁇ / ⁇ , good (a level at which dust adhesion is effectively suppressed). ⁇ : 1 ⁇ 10 11 ⁇ / ⁇ or more and less than 1.0 ⁇ 10 12 ⁇ / ⁇ , practical use possible. ⁇ : Less than 1 ⁇ 10 12 ⁇ / ⁇ , impractical.
  • a comparative urethane prepolymer which is a reaction product of one or more polyols (a-1) excluding a polyether polyol having one or more EO groups in one molecule and one or more polyisocyanates (b).
  • a polymer (D) (a polyether polyol (a-2) having one or more EO groups in one molecule is not used);
  • a urethane adhesive containing fatty acid ester (B) was produced.
  • Comparative Example 5 a urethane pressure-sensitive adhesive containing three kinds of polyether polyols containing no urethane prepolymer and having no EO group and ⁇ -diketone compound (X) was produced.
  • the pressure-sensitive adhesive sheet obtained in Comparative Example 5 had a poor hydrophilicity and curability of the pressure-sensitive adhesive layer, and the results were poor in the evaluation items of pressure-sensitive adhesive strength, moisture and heat whitening resistance, thick film coating suitability, and gel fraction. It was. Further, the pressure-sensitive adhesive sheet obtained in Comparative Example 5 in which the ⁇ -diketone compound (X) was used but the urethane prepolymer (A) having an EO group was not used showed poor results in the evaluation items of the surface resistance value. Met.

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PCT/JP2016/004161 2015-09-17 2016-09-13 ウレタン粘着剤、粘着シート、およびディスプレイ WO2017047077A1 (ja)

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