WO2018047649A1 - Agent adhésif sensible à la pression, film adhésif sensible à la pression et stratifié optique - Google Patents

Agent adhésif sensible à la pression, film adhésif sensible à la pression et stratifié optique Download PDF

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Publication number
WO2018047649A1
WO2018047649A1 PCT/JP2017/030702 JP2017030702W WO2018047649A1 WO 2018047649 A1 WO2018047649 A1 WO 2018047649A1 JP 2017030702 W JP2017030702 W JP 2017030702W WO 2018047649 A1 WO2018047649 A1 WO 2018047649A1
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Prior art keywords
compound
sensitive adhesive
pressure
meth
polyoxyethylene
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PCT/JP2017/030702
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English (en)
Japanese (ja)
Inventor
小出　昌史
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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Priority claimed from JP2017009743A external-priority patent/JP6790865B2/ja
Priority claimed from JP2017017655A external-priority patent/JP2018044140A/ja
Priority claimed from JP2017133230A external-priority patent/JP2019014820A/ja
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
Publication of WO2018047649A1 publication Critical patent/WO2018047649A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers

Definitions

  • the present invention relates to a pressure-sensitive adhesive, a pressure-sensitive adhesive film, and an optical laminate.
  • Display devices such as liquid crystal displays used in various devices such as home and business appliances such as electronic computers, electronic watches, mobile phones, and televisions are becoming larger. In particular, the increase in the size of liquid crystal televisions and plasma televisions is remarkable. In recent years, touch panel type liquid crystal displays such as smartphones and tablets have rapidly spread, and organic EL displays are expected to expand greatly. On the other hand, liquid crystal displays are also used in in-vehicle devices such as car navigation systems, and are required to have durability that can be used in harsh interior environments such as high-temperature and high-humidity atmospheres.
  • a surface protective film is generally attached to an exposed surface side of an optical member such as a liquid crystal display in order to prevent surface contamination and scratches during processing, assembly, inspection, transportation, and the like.
  • an optical member such as a liquid crystal display
  • the surface protection film for optical members may be repeatedly applied and peeled off during the manufacturing process, the surface of the optical member is contaminated during ease of sticking (wetting and spreading to the adherend) and peeling. Re-peelability is not necessary.
  • the surface protective film needs to have a property (light peelability) that can be peeled with a weaker force in addition to the adhesiveness.
  • the surface protection film for in-vehicle devices is required to have high durability that does not foam or peel off from an adherend (optical member) even when exposed to a heated or wet heat state.
  • the surface protective film has a problem that when static electricity is generated at the time of re-peeling, when the adherend is an electronic component, the circuit of the electronic component is destroyed due to static electricity.
  • the adherend is an optical member, there is a problem that foreign matter adheres to the surface of the adherend due to static electricity and trouble occurs in inspection or the like.
  • the pressure-sensitive adhesive used for the surface protective film is made of various types of resins such as acrylic copolymers, silicone resins, and polyurethane resins. Acrylic resins are widely used because of their low cost. .
  • a trifunctional isocyanate crosslinking agent is mixed with a copolymer of an ethylenically unsaturated compound having an alkyl group having 12 or less carbon atoms and an ethylenically unsaturated compound containing a hydroxyl group.
  • a pressure sensitive adhesive is disclosed.
  • Patent Document 3 discloses a copolymer obtained by copolymerizing an ethylenically unsaturated compound containing an alkyl group having 8 carbon atoms and an ethylenically unsaturated compound having a long-chain ethyleneoxy unit, and an isocyanate-based crosslinking agent.
  • a pressure sensitive adhesive is disclosed.
  • JP-A-63-225677 JP 2005-023143 A Japanese Unexamined Patent Publication No. 2015-044945
  • Patent Documents 1 and 2 not only have high adhesive strength, but also the adhesive strength increases remarkably with the passage of time after application due to the lack of cohesive strength of the adhesive layer itself. Or adhesive residue may occur at the time of peeling. Therefore, there has been a problem in using it as a surface protective film for a member that dislikes mixing of foreign matters, such as an optical member and an electronic member.
  • the surface protective film using the pressure-sensitive adhesive of Patent Document 3 has a problem that the heat resistance and heat-and-moisture resistance deteriorate due to the copolymer having a long-chain ethyleneoxy group. Furthermore, when using a waterproof smartphone or the like in the bathroom, there is a problem that water resistance is insufficient because the adhesive layer is whitened and peeled in an environment where water drops are applied.
  • An object of the present invention is to provide a pressure-sensitive adhesive capable of producing a pressure-sensitive adhesive film having good water resistance in addition to heat resistance and moist heat resistance, a pressure-sensitive adhesive film using the pressure-sensitive adhesive, and an optical laminate. To do.
  • One embodiment of the pressure-sensitive adhesive of the present invention includes a copolymer (A) having a hydroxyl group and a reactive compound (B) having a functional group that reacts with the hydroxyl group,
  • a copolymer (A) having a hydroxyl group and a reactive compound (B) having a functional group that reacts with the hydroxyl group As the monomer unit constituting the copolymer (A), an ethylenically unsaturated compound (a1) unit having a hydroxyl group, an ethylenically unsaturated compound having a partition coefficient LogP of 6.5 or more and less than 12 having no polar group (A2) A unit and the ethylenically unsaturated compound (a3) unit which has an ethyleneoxy group and does not have a hydroxyl group are contained.
  • a pressure-sensitive adhesive capable of producing a pressure-sensitive adhesive film having good water resistance in addition to heat resistance and moist heat resistance, a pressure-sensitive adhesive film using the pressure-sensitive adhesive, and an optical laminate can be provided.
  • ethylenically unsaturated compound (a1) having a hydroxyl group is “compound (a1)”, “ethylenically unsaturated compound (a2) having a partition coefficient LogP of 6.5 or more and less than 12, and having no polar group. ) ”Is“ compound (a2) ”,“ ethylenically unsaturated compound having an ethyleneoxy group and no hydroxyl group (a3) ”is“ compound (a3) ”,“ other ethylenically unsaturated compound (a4) ”is Each may be abbreviated as “compound (a4)”.
  • acryl In addition, “(meth) acryl”, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” Unless otherwise specified, “acrylic or methacrylic”, “acryloyl or methacryloyl”, “acrylic acid or methacrylic acid”, “acrylate or methacrylate”, “acryloyloxy or methacryloyloxy”, and “allyl or methallyl”, respectively. ".
  • An ethylenically unsaturated compound is an ethylenically unsaturated compound capable of radical polymerization. Sheet, film, and tape are synonymous.
  • the pressure sensitive adhesive of the present invention is A copolymer (A) having a hydroxyl group and a reactive compound (B) having a functional group capable of reacting with the hydroxyl group
  • a copolymer (A) having a hydroxyl group and a reactive compound (B) having a functional group capable of reacting with the hydroxyl group As the monomer unit constituting the copolymer (A), an ethylenically unsaturated compound (a1) unit having a hydroxyl group, an ethylenically unsaturated compound having a partition coefficient LogP of 6.5 or more and less than 12 having no polar group (A2) a unit and an ethylenically unsaturated compound (a3) unit having an ethyleneoxy group and no hydroxyl group.
  • the pressure-sensitive adhesive of the present invention is preferably used as a pressure-sensitive adhesive film having a base layer and an adhesive layer formed by coating to form an adhesive layer.
  • the copolymer (A) having a hydroxyl group has an ethylenically unsaturated compound (a1) unit having a hydroxyl group as a monomer unit constituting the copolymer (A) and a distribution coefficient LogP having no polar group of 6.
  • the partition coefficient (LogP) is a dimensionless number that serves as an index representing the hydrophobicity and migration of a chemical substance, and the target substance is in an equilibrium state in a system where two phases are in contact with each other. Is the concentration ratio of each phase or its common logarithm.
  • the distribution coefficient is a distribution coefficient when 1-octanol / water is used, and is used as a basic numerical value for judging the hydrophilicity / hydrophobicity of a substance.
  • measurement is performed according to JIS Z 7260-107: 2000 (flask shaking method), LogP at 25 ° C. is calculated using the following general formula [1], and this is used as a distribution coefficient. Details of the distribution coefficient measurement are given in the examples.
  • LogP Log (C 0 / C w ) ⁇ Log (x o / x w )
  • C 0 test substance concentration in octanol phase (mol / L)
  • C w test substance concentration in water phase (mol / L)
  • x 0 in octanol phase
  • x w Test substance mole fraction in the aqueous phase.
  • the copolymer (A) constituting the pressure-sensitive adhesive of the present invention has an ethylenically unsaturated compound (a2) unit having a partition coefficient LogP of 6.5 or more and less than 12 having no polar group and an ethyleneoxy group. And having an ethylenically unsaturated compound (a3) unit having no hydroxyl group, a hydrophilic polar portion mainly composed of an ethyleneoxy group obtained from the compound (a3), and a hydrophobic non-ionic group obtained from the compound (a2). It forms an intramolecular microphase separation structure in which both polar sites exist. For this reason, in terms of thermodynamics, phase separation occurs when a hydrophobic nonpolar substance and a hydrophilic polar substance are randomly mixed.
  • the copolymer (A) contains both components in the copolymer, the copolymer (A) not only has both physical properties, but also has a reduced free energy and a low energy state domain structure (microdomain structure). ). Thereby, in addition to the viscosity reduction (coating property improvement) of the copolymer (A) and the further improvement of the removability, the wet spreading property to the adherend is further improved.
  • the compound (a1) is a compound having a hydroxyl group and an ethylenically unsaturated double bond group.
  • the compound (a1) includes a compound (a1-1) having no ethyleneoxy group and a compound (a1-2) having an ethyleneoxy group.
  • the said ethyleneoxy group means the repeating unit of ethyleneoxy (EO) 2 or more.
  • Examples of the compound (a1-1) include the following. 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, cyclohexanedimethanol mono (meth) acrylic acid ester , Ethyl (meth) acrylate- ⁇ - (hydroxymethyl), glycerol monofunctional (meth) acrylate, glycidyl laurate (meth) acrylate, glycidyl oleate (meth) acrylate, glycidyl (meth) acrylate Stearates, etc.
  • Fatty acid ester (meth) acrylate Hydroxyl groups and ethylenically unsaturated double bond groups, such as 2- (acryloyloxy) ethyl 6-hydroxyhexanoate, 6- ⁇ 2- (acryloyloxy) ethoxy ⁇ -6-oxohexyl 6-hydroxyhexanoate, and the like; (Meth) acrylic acid ester having a hydroxyl group at the terminal, obtained by ring-opening addition of ⁇ -caprolactone to a compound having For compounds having a hydroxyl group and an ethylenically unsaturated double bond group, such as tetrapropylene glycol monomethacrylate and tributylene glycol monomethacrylate, an alkyleneoxy group other than an ethyleneoxy group (such as a propyleneoxy group or a butyleneoxy group) ), An aliphatic (meth) acrylic acid ester having a hydroxyl group, such as a (meth) acrylic acid ester
  • An aliphatic vinyl ether having a hydroxyl group such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, glyceryl monovinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether;
  • (Meth) allyl alcohol isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, glyceryl (meth) allyl ether, etc.
  • Ethylenically unsaturated compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, glycerol di (meth) acrylate;
  • (Meth) acrylamide having a hydroxyl group such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide;
  • the compound (a1-1) preferably does not have an aromatic ring from the viewpoint of further improving the adhesion to the substrate and the heat and humidity resistance. More preferable examples of the compound (a1-1) include alkyl having 2 to 18 carbon atoms such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • (meth) acrylic acid polyoxypropylene (“polyoxypropylene” and “polypropyleneoxy group”) may be abbreviated as “PO”.
  • the number of moles of addition is sometimes referred to as “number of moles of addition of PO: 2 to 30); 1 to 2 moles of ⁇ -caprolactone, and ⁇ relative to a hydroxyl group-containing ethylenically unsaturated compound such as 2-hydroxyethyl (meth) acrylate.
  • -(Meth) acrylic obtained by ring-opening addition of caprolactone and having 2 to 18 carbon atoms and having a hydroxyl group at the terminal
  • Preferred are ethylenically unsaturated compounds having 2 to 18 carbon atoms in the side chain, such as acid esters; hydroxyethyl vinyl ethers and the like, aliphatic vinyl ethers having a hydroxyl group; and (meth) acrylamides having a hydroxyl group such as N-hydroxyethylacrylamide.
  • Examples of the compound (a1-2) include the following. Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, (meth) acrylic acid polyoxyethylene mono (meth) acrylate (EO addition moles: 5-30, “poly Unit units of “oxyethylene” and “polyethyleneoxy group” may be abbreviated as “EO”), poly (oxyethylene oxypropylene) mono (meth) acrylate (EO addition mole number: 2 to 30), Aliphatic groups having a hydroxyl group, such as poly (oxyethylene / oxybutylene) mono (meth) acrylate (EO addition mole number: 2 to 30), (meth) acrylic acid ester having ethyleneoxy group to which ethyleneoxy is repeatedly added ( (Meth) acrylic acid ester;
  • Diethylene glycol mono (meth) acrylate triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth)
  • Aliphatics having a hydroxyl group such as diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, polyoxyethylene monovinyl ether (EO addition mole number: 4 to 30), ethyleneoxy group-containing vinyl ether having a hydroxyl group at the terminal after repeated addition of ethyleneoxy Vinyl ether;
  • Diethylene glycol mono (meth) allyl ether triethylene glycol mono (meth) allyl ether, polyoxyethylene mono (meth) allyl ether (EO addition mole number: 4 to 30), etc.
  • hydroxyl group-containing aliphatic (meth) allyl ethers such as ethyleneoxy group-containing (meth) allyl ethers.
  • Compound (a1-2) may be used alone or in combination of two or more.
  • Compound (a1-2) is diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyoxyethylene mono from the viewpoint of improving wet spreadability and removability.
  • Preferred are aliphatic (meth) acrylates having a hydroxyl group, such as (meth) acrylates (meth) acrylates (meth) acrylates containing (oxy) moles of EO (EO addition mole number: 4 to 30).
  • the compound (a1) when used for copolymerization, for example, an appropriate polymerization rate can be obtained, so that the molecular weight and the crosslinking density of the copolymer (A) can be easily adjusted. Therefore, the adhesive layer of the pressure-sensitive adhesive film formed from the pressure-sensitive adhesive can obtain a high cohesive force. Moreover, since the copolymer (A) has a hydroxyl group, the crosslinking reactivity with the reactive compound (B) is improved, and the cohesive force is improved. With these actions, heat resistance, heat and humidity resistance, and water resistance are excellent.
  • Ethylenically unsaturated compound (a2) having a distribution coefficient LogP not having a polar group of 6.5 or more and less than 12 Compound (a2) is a nonpolar monomer having a partition coefficient (LogP) of 6.5 or more and less than 12, and has no polar group.
  • the obtained adhesive layer has suitable adhesiveness that is preferable as a surface protective film for polar adherends such as glass.
  • the compound (a2) does not have a polar group such as a hydroxyl group, a carboxyl group, a keto group, an amino group, an imino group, an epoxy group, or a silyl group.
  • the “polar group” refers to a group having polarity, and the para effect ⁇ p, which is one of Hammett's substituent constants, is mainly outside the range of ⁇ 0.20 to 0.24. It is the basis of. However, ester groups and vinyl ether groups are excluded from polar groups.
  • the compound (a2) is preferably an ethylenically unsaturated compound having a long chain hydrocarbon group.
  • the copolymer (A) exhibits pseudo-crystallinity due to molecular orientation, which improves cohesion and foams, floats and peels even in harsh environments such as high temperature and high humidity conditions. Moisture and heat resistance can be obtained.
  • the hydrocarbon group of compound (a2) preferably has 14 to 26 carbon atoms.
  • the long-chain hydrocarbon group may have a double bond or an alkyl chain having no double bond.
  • Examples of the compound (a2) include the following. (Meth) acrylic acid myristyl, (meth) acrylic acid cetyl, (meth) acrylic acid stearyl, (meth) acrylic acid isostearyl, (meth) acrylic acid nonadecyl, (meth) acrylic acid arachidyl, (meth) acrylic acid henicosyl, Aliphatic (meth) acrylic esters such as behenyl (meth) acrylate, tricosyl (meth) acrylate, lignoceryl (meth) acrylate, pentacosyl (meth) acrylate, ceryl (meth) acrylate;
  • Aliphatic vinyl ethers such as stearyl vinyl ether, isostearyl vinyl ether, nonadecyl vinyl ether, arachidyl vinyl ether, behenyl vinyl ether;
  • Aliphatic vinyl esters such as vinyl palmitate, vinyl stearate, vinyl isostearate, vinyl behenate, vinyl lignoselenate, and vinyl serotate;
  • alkyloyl acetate vinyl esters such as stearoyl vinyl acetate, behenoyl vinyl acetate, lignocellyloyl vinyl acetate;
  • Aliphatic allyl esters such as stearoyl acetate (meth) allyl, behenoyl acetate (meth) allyl, lignocellyloyl acetate (meth) allyl;
  • Alkenes such as 1-heptadecene, 1-octacosene, 1-nonadecene;
  • Aromatic (meth) acrylic acid esters such as tetradecylphenoxyethyl (meth) acrylate, hexadecylphenoxyethyl (meth) acrylate, octadecylphenoxyethyl (meth) acrylate;
  • Aromatic vinyl phenyl ethers such as vinyl phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl tridecyl ether;
  • Aromatic isopropenyl phenyl ethers such as isopropenyl phenyl methyl hexadecyl ether and isopropenyl phenyl methyl octadecyl ether;
  • a bifunctional (meth) acrylic acid ester having a long-chain alkylene linking group such as tetracosanediol and di (meth) acrylic acid 1,26-hexacosanediol.
  • a compound (a2) can be used individually by 1 type or in combination of 2 or more types.
  • the compound (a2) preferably has a partition coefficient LogP of 6.5 or more and less than 12, and more preferably 6.5 or more and less than 10.
  • LogP 6.5 to 12
  • the compound (a2) preferably has an aliphatic group. If it has an aromatic ring, the flexibility of the long-chain alkyl may decrease.
  • the adhesive layer can suppress tackiness, and thus, for example, the performance as a surface protective film is improved. Furthermore, the presence of the hydrophobic unit further improves the heat and moisture resistance and water resistance.
  • ⁇ ethylenically unsaturated compound (a3) having an ethyleneoxy group and no hydroxyl group Since compound (a3) has high hydrophilicity and a highly polar ethyleneoxy group, the heat resistance is improved. In addition, since the intramolecular cohesive force is improved, the ethyleneoxy group has improved durability and low adhesion that is easily peeled off.
  • the ethyleneoxy group means one or more repeating units of ethyleneoxy (EO).
  • the number of ethyleneoxy repeats (also referred to as added moles) is preferably 1 to 30 moles. When the number of repetitions is within the above range, the heat and moisture resistance and durability are improved and, for example, suitability as a surface protective film is easily obtained.
  • Compound (a3) is a compound other than compound (a1) and compound (a2).
  • Examples of the compound (a3) include the following. Methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyoxyethylene (meth) acrylate (EO addition moles: 3 to 40), methoxypolyoxyethylene / polyoxypropylene (meth) acrylate (EO addition mole) Number: 2-30, PO addition mole number: 1-20), ethoxydiethylene glycol (meth) acrylate, ethoxypolyoxyethylene (meth) acrylate (EO addition mole number: 3-40), ethoxypolyoxyethylene / polyoxypropylene (Meth) acrylate (EO addition moles: 2 to 30, PO addition moles: 1 to 20), butoxydiethylene glycol (meth) acrylate, butoxypolyoxyethylene (meth) acrylate (EO addition moles: 3 to 0), 2-ethylhexyloxypolyoxyethylene (meth) acrylate (EO addition mole number
  • Ethylene glycol methyl vinyl ether diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, diethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, triethylene glycol butyl vinyl ether, polyoxyethylene methyl vinyl ether (EO addition mole number: 4 to 30), polyoxyethylene ethyl vinyl ether (EO addition mole number: 4 to 30), polyoxyethylene butyl vinyl ether (EO addition mole number: 4 to 30), etc., ethyleneoxy group-containing vinyl ether having an alkoxy group;
  • Ethylene glycol methyl (meth) allyl ether diethylene glycol methyl (meth) allyl ether, diethylene glycol ethyl (meth) allyl ether, triethylene glycol butyl (meth) allyl ether, polyoxyethylene methyl (meth) allyl ether (EO addition moles: 3 to 30), ethyleneoxy group-containing (meth) allyl ether having an alkoxy group such as polyoxyethylene ethyl (meth) allyl ether (EO addition mole number: 3 to 30);
  • Phenoxypolyoxyethylene mono (meth) acrylate (EO addition mole number: 2 to 10), benzyloxypolyoxyethylene mono (meth) acrylate (EO addition mole number: 2 to 10), nonylphenol polyoxyethylene mono (meth) acrylate (EO addition mole number: 2 to 10), naphthaloxypolyoxyethylene mono (meth) acrylate (EO addition mole number: 2 to 10) and the like, an ethyleneoxy group-containing (meth) acrylic acid ester having an aromatic ring;
  • Methyl tetraethylene oxide vinyl phenyl ether methyl polyoxyethylene vinyl phenyl ether (EO addition mole number: 5 to 20), methyl polyoxyethylene vinyl phenyl ethyl ether (EO addition mole number: 5 to 20), ethyl polyoxyethylene vinyl Ethyleneoxy group-containing vinyl phenyl ether having an aromatic ring such as phenyl ethyl ether (EO addition mole number: 5 to 20);
  • Ethyleneoxy group-containing vinyl benzyl ether having an aromatic ring such as methyl polyoxyethylene vinyl benzyl ether (EO addition mole number: 2 to 20);
  • Ethyleneoxy group-containing isopropenyl phenyl ether having an aromatic ring such as methyl polyoxyethylene isopropenyl phenyl ether (EO addition mole number: 2 to 20);
  • Ethyleneoxy group-containing isopropenyl benzyl ether having an aromatic ring such as methyl polyoxyethylene isopropenyl benzyl ether (EO addition mole number: 2 to 20);
  • Vinyl phenyl polyoxyethylene succinate (EO addition moles: 2 to 30), vinyl phenylmethyl polyoxyethylene hexahydrophthalate (EO addition moles: 2 to 30), vinyl phenyl ethyl polypolyoxyethylene terephthalate (EO addition) Ethyleneoxy group-containing vinyl phenyl ester having an aromatic ring such as the number of moles: 2 to 30);
  • 4-vinylbenzoic acid methyl polyoxyethylene (EO addition mole number: 2 to 30), 4-isopropenylbenzoic acid methyl polyoxyethylene (EO addition mole number: 2 to 30), etc., vinyl benzoic acid having a polyethylene oxide moiety Ester or isopropenyl benzoate;
  • Diethylene glycol divinyl ether diethylene glycol divinyl ether, polyethylene glycol divinyl ether (EO addition mole number: 5 to 30), polyoxyethylene addition trimethylolpropane trivinyl ether (EO addition mole number: 3 to 30), polyoxyethylene addition pentaerythritol tetravinyl ether (EO addition)
  • An ethyleneoxy group-containing polyfunctional vinyl ether such as the number of moles: 3 to 30);
  • a compound (a3) can be used individually by 1 type or in combination of 2 or more types.
  • the compound (a3) is preferably aliphatic where there are aliphatic and aromatic ring compounds.
  • the aliphatic compound (a3) is used, the change with time of the adhesive layer can be easily suppressed.
  • the copolymer (A) may further contain other ethylenically unsaturated compound (a4) units as long as the effects of the present invention are not impaired.
  • the compound (a4) controls the viscosity and the glass transition temperature as desired from among known ethylenically unsaturated compounds that do not fall under any of the compound (a1), the compound (a2), and the compound (a3). Therefore, it can be appropriately selected and used.
  • a compound (a4) can be used individually by 1 type or in combination of 2 or more types.
  • the compound (a4) examples include compounds having a (meth) acryloyl group, a vinyl group, a (meth) allyl group, and the like.
  • the compound (a4) is preferably a compound having a (meth) acryloyl group, and more preferably a compound having an acryloyl group.
  • the compound (a4) has a Tg of -80 to 0 ° C. and a carbon number of the homopolymer of the compound (a4) from the viewpoint of controlling the glass transition temperature and adjusting the viscosity of the copolymer (A). It is preferable to use an ethylenically unsaturated compound (a4-1) having 2 to 13 alkyl groups.
  • Examples of such a compound (a4-1) include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, isoamyl acrylate, (meth ) Hexyl acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,4-dimethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as isononyl acrylate, 3,4-dimethylheptyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate; Among these, ethyl
  • an ethylenically unsaturated compound (a4-2) not corresponding to the above compound (a4-1) may be selected.
  • examples of such compound (a4-2) include, but are not limited to, methyl acrylate, methyl methacrylate, phenoxyethyl acrylate, methoxypolyoxypropylene acrylate, and the like.
  • the content is preferably 1% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 48% by mass or less with respect to the copolymer (A).
  • the copolymer (A) is a copolymer of the compound (a1), the compound (a2) and the compound (a3), and the weight average molecular weight (Mw) of the copolymer (A) is determined by applying the pressure-sensitive adhesive.
  • Mw weight average molecular weight
  • 100,000 to 2,000,000 is preferable, 200,000 to 1,800,000 is more preferable, and 400,000 to 1,500,000 is even more preferable.
  • Mw is in the above range, the cohesive force and the like are further improved, so that floating and peeling can be further suppressed, and the removability is further improved.
  • a weight average molecular weight and a number average molecular weight are the values of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in the Examples.
  • the ethyleneoxy group which a copolymer (A) has can be introduce
  • the ethyleneoxy group can also be introduced by using the compound (a1-2) having an ethyleneoxy group in combination. It is preferable that 0.1 to 99.9% by mass of an ethylenically unsaturated compound unit having an ethyleneoxy group is contained in 100% by mass of the monomer unit constituting the copolymer (A).
  • a copolymer (A) can be classify
  • the ethylenically unsaturated compound unit having an ethyleneoxy group is in the range of 0.1 to 50% by mass, an intramolecular microphase separation structure in which a polar portion that is hydrophilic exists in a hydrophobic nonpolar medium (Defined as a hydrophobic microphase separation structure).
  • the ethylenically unsaturated compound unit having an ethyleneoxy group is more preferably 0.5 to 40% by mass, and particularly preferably 1 to 35% by mass.
  • the mass ratio of a compound (a2) and a compound (a3) is the mass of a compound (a2)> the mass of a compound (a3).
  • the content of ethyleneoxy groups in the copolymer (A) is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass.
  • the ethylenically unsaturated compound unit having an ethyleneoxy group is in the range of 50 to 99.9% by mass, an intramolecular microphase in which a hydrophobic nonpolar site is present in a hydrophilic polar medium.
  • a separation structure (defined as a hydrophilic microphase separation structure) is formed.
  • the ethylenically unsaturated compound unit having an ethyleneoxy group is more preferably 60 to 99% by mass, and particularly preferably 65 to 98% by mass.
  • the content ratio of the compound (a2) is preferably 0.5 to 35% by mass.
  • the content of ethyleneoxy groups in the copolymer (A) is preferably 50 to 95% by mass, and more preferably 55 to 90% by mass.
  • phase separation occurs in a state where a hydrophobic non-polar substance and a hydrophilic polar substance are randomly mixed, but both components are contained in the copolymer.
  • a domain structure microdomain structure
  • the wet spreading property to the adherend is further improved.
  • the adhesive layer formed from the pressure-sensitive adhesive of the present invention is excellent in transparency. .
  • the hydroxyl value (sometimes referred to as OHV) of the copolymer (A) is preferably 1 to 60 mgKOH / g, and more preferably 2 to 40 mgKOH / g.
  • OHV is in the above range, it becomes easy to adjust the crosslink density with the reactive compound (B) having a functional group capable of reacting with a hydroxyl group, so that the heat and moisture resistance and the water resistance are further improved.
  • the glass transition temperature (Tg) of the copolymer (A) is preferably ⁇ 80 to 50 ° C., more preferably ⁇ 65 to 25 ° C. When Tg is adjusted to an appropriate range, both tack and cohesion can be easily achieved. Tg is a theoretical value calculated from the following FOX equation. In addition, the measured value using a differential scanning calorimeter (DSC) is used for Tg of a copolymer (A) in case Tg of an ethylenically unsaturated compound is not known.
  • DSC differential scanning calorimeter
  • Tg glass transition temperature
  • the copolymer (A) can be synthesized by, for example, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like, and solution polymerization with easy reaction control is preferred.
  • a polymerization initiator is usually used.
  • the polymerization initiator is preferably, for example, an azo compound or a peroxide.
  • the polymerization initiator is preferably used in an amount of about 0.001 to 20 parts by mass with respect to 100 parts by mass in total of the ethylenically unsaturated compounds.
  • azo compound examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) Dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1-acetoxy-1-phenylethane), and the like.
  • Peroxides include, for example, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, Examples thereof include tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybivalate, octanoyl peroxide, lauroyl peroxide and the like.
  • 2,2′-azobisisobutyronitrile dimethyl 2,2′-azobis (2-methylpropionate), dimethyl 2,2′-azobis Isobutyrate
  • benzoyl peroxide tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexa Noate is preferred.
  • the polymerization initiator can be used alone or in combination of two or more.
  • a chain transfer agent can be used to adjust the molecular weight.
  • the chain transfer agent include mercaptans such as lauryl mercaptan and n-dodecyl mercaptan; ⁇ -methylstyrene dimer, limonene and the like.
  • the solvent used for solution polymerization is preferably an organic solvent.
  • the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-butyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, and n-butyl acetate.
  • glycol ethers such as ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether; glycol acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; n-hexane, n-nonane, etc.
  • Solvents can be used alone or in combination of two or more.
  • the polymerization conditions for synthesizing the copolymer (A) may be appropriately set according to the polymerization method, and are not particularly limited.
  • the polymerization temperature is preferably 20 to 150 ° C, more preferably 40 to 120 ° C.
  • the reaction time may be appropriately set in the range of usually about 1 to 20 hours so that the polymerization reaction of each component of the ethylenically unsaturated compound is completed.
  • Reactive compound (B) having a functional group capable of reacting with a hydroxyl group can further increase the cohesive force by crosslinking the copolymer (A). Therefore, not only heat resistance and heat and humidity resistance are improved, but also the adhesion layer can be prevented from floating, peeling off or foaming in a harsh environment.
  • Examples of the functional group capable of reacting with the hydroxyl group of the reactive compound (B) include an isocyanate group, an alkoxysilyl group, and a methylol group.
  • the compound having an isocyanate group is preferably, for example, polyisocyanate (b1).
  • the compound having an alkoxysilyl group is preferably, for example, a silane compound (b2).
  • the compound having a methylol group is preferably, for example, a methylol melamine compound (b3).
  • Examples of the reactive compound (B) include polyisocyanate (b1), silane compound (b2), and methylolmelamine compound (b3).
  • the reactive compound (B) preferably has two or more functional groups in the molecule that can react with a hydroxyl group for a crosslinking reaction.
  • the reactive compound (B) is preferably polyisocyanate (b1) in terms of further improving the adhesion of the adhesive layer and the adhesion to the substrate.
  • Polyisocyanate (b1) is preferably aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, or other polyisocyanate.
  • Aliphatic diisocyanates include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
  • Alicyclic diisocyanates include, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 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, norbornene diisocyanate, dimer acid diisocyanate, octahydro-4 , 7-methano-1H-indenedimethyl diisocyanate and the like.
  • IPDI 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate
  • Aromatic diisocyanates include, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (also known as 2,4-TDI), 2,6- Tolylene diisocyanate (also known as 2,6-TDI), 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,3-phenylene bismethylene diisocyanate (alias: m-XDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2'- Diphenylmethane diisocyanate (alias: 2,2- DI), 4,4'-diphenylmethane di
  • polyisocyanates include, for example, polyisocyanates having three or more isocyanate groups such as lysine triisocyanate, triphenylmethane-4,4 ′, 4 ′′ -triisocyanate, and methylsilanetriyl trisisocyanate.
  • Polyisocyanate (b1) can be used alone or in combination of two or more.
  • More preferable polyisocyanate (b1) is a compound having three or more isocyanate groups.
  • the compound may be an adduct of an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an aromatic polyisocyanate and a polyol; an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an aromatic polyisocyanate.
  • a compound having an isocyanurate ring in a trimer a polyisocyanate-modified product of an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an aromatic polyisocyanate; Of these, adducts of HDI or IPDI having no aromatic ring and trimethylolpropane, burettes reacted with water, and trimers forming isocyanurate rings are more preferred.
  • the polyol examples include 2-methylpentane-2,4-diol and trimethylolpropane.
  • the modified polyisocyanate is, for example, a modified product obtained by reacting with a compound having a functional group such as a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, or an isocyanurate group.
  • the polyisocyanate (b1) can use the blocked isocyanate which blocked the isocyanate group using the blocking agent.
  • a known catalyst can be used as necessary for promoting the reaction between the hydroxyl group of the copolymer (A) and the isocyanate group.
  • the catalyst include tertiary amine compounds and organometallic compounds.
  • tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and the like.
  • organometallic compound examples include a tin compound and a non-tin compound.
  • tin compound examples include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples thereof include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
  • Non-tin compounds include, for example, titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, -Iron compounds such as iron ethylhexanoate and iron 2,4-pentadionate, cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate And zirconium compounds such as zirconium naphthenate.
  • titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride
  • lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead nap
  • DBU diazabicycloundecene
  • DBTDL dibutyltin dilaurate
  • tin 2-ethylhexanoate tin 2-ethylhexanoate and the like are preferable from the viewpoint of reactivity and hygiene.
  • a catalyst can be used individually by 1 type or in combination of 2 or more types.
  • silane compound (b2) examples include the following. Alkyl alkoxysilane, aryl alkoxysilane, carbamate alkoxysilane, vinyl alkoxysilane, halogen alkoxysilane, (meth) acryloyl alkoxysilane, mercapto alkoxysilane, imidazole alkoxysilane, isocyanate alkoxysilane, epoxy Alkoxysilanes having an alkoxyl group, such as alkoxysilanes and amino-based alkoxysilanes;
  • Carbamate alkoxysilanes such as (3-carbamateethyl) propyltriethoxysilane and (3-carbamateethyl) propyltrimethoxysilane;
  • Vinyl alkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane
  • Halogen-based alkoxysilanes such as chloromethyltrimethoxysilane and chloromethyltriethoxysilane;
  • (Meth) acryloyl-based alkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane;
  • Mercapto-based alkoxysilanes such as 3-mercaptopropyltrimethoxylane and 3-mercaptopropyltriethoxysilane;
  • Imidazole alkoxysilanes such as 3- (2-imidazolin-1-yl) propyltriethoxysilane;
  • Isocyanate isocyanate silanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane;
  • the silane compound (b2) can also be an oligomeric silane compound obtained by oligomerizing a mixture of two or more silanes by hydrolysis / condensation reaction.
  • isocyanate-based alkoxysilanes, amino-based alkoxysilanes, and epoxy-based alkoxysilanes are preferable in terms of wettability with respect to the adherend.
  • preferred silane compounds (b2) include amino-based alkoxysilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-cyclohexylaminoethylthiomethyltrimethoxysilane; Examples thereof include isocyanate-based alkoxysilanes such as ethoxysilane; epoxy-based alkoxysilanes such as 3-glycidoxypropyltrimethoxysilane.
  • a silane compound (b2) can be used individually by 1 type or in combination of 2 or more types.
  • methylol melamine compound (b3) examples include methylol melamine derivatives obtained by condensing melamine and formaldehyde, and ethers of methylol melamine derivatives and lower alcohols.
  • the lower alcohol is, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol or the like.
  • methylol melamine compound (b3) examples include monomethylol melamine, dimethylol melamine, trimethylol melamine (also known as cearicin), tetramethylol melamine, pentamethylol melamine, pentamethoxymethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, Examples include hexaethoxymethyl melamine, hexakis- (methoxymethyl) melamine, hexamethylol melamine pentamethyl ether and the like.
  • a methylol melamine type compound (b3) can be used individually by 1 type or in combination of 2 or more types.
  • the adhesion of the adhesive layer and the adhesiveness to the substrate are further improved, and the polyisocyanate (b1) is provided with a high level of flexibility and wettability of the adhesive layer. preferable.
  • the reactive compound (B) is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the copolymer (A). When the reactive compound (B) is in this range, the heat resistance and heat-and-moisture resistance are further improved by the crosslinking reaction with the hydroxyl group contained in the copolymer (A).
  • the pressure-sensitive adhesive of the present invention may contain an ester compound (C) as an optional component. Since the ester compound (C) can plasticize the adhesive layer, the wetting and spreading property of the pressure-sensitive adhesive film to an adherend such as a glass plate is further improved. In addition to improving the removability of the pressure-sensitive adhesive film, the adhesiveness between the adhesive layers (referred to as self-adhesiveness) can be suppressed, so that it is difficult for the pressure-sensitive adhesive film to be lost in the attaching operation of the operator (Called workability).
  • the ester compound (C) includes a fatty acid ester (c1) having 8 to 100 carbon atoms, a phosphoric acid ester (c2) having 4 to 80 carbon atoms, and a boric acid ester (c3) having 8 to 100 carbon atoms and their epoxies. Modified esters are preferred.
  • the ester compound (C) is a compound other than the copolymer (A) and the reactive compound (B).
  • the fatty acid ester (c1) having 8 to 100 carbon atoms is preferably an ester of monobasic acid or polybasic acid and alcohol having 22 or less carbon atoms.
  • An ester of a monobasic acid or polybasic acid having 22 or less carbon atoms and an alcohol is: (1) a monobasic acid or polybasic acid having 4 to 22 carbon atoms and a monovalent alcohol having 22 or less carbon atoms; And (2) an ester of a monobasic acid having 18 to 22 carbon atoms and a divalent to tetravalent alcohol.
  • an epoxy-modified ester obtained by further modifying the ester of (1) or (2) with an epoxy hereinafter referred to as an epoxy-modified ester is preferable.
  • ester of a monobasic acid or polybasic acid having 4 to 22 carbon atoms and a monohydric alcohol having 22 or less carbon atoms include the following. Isopropyl valerate, isopropyl caproate, lauryl caproate, stearyl caproate, stearyl caprylate, cetyl 2-ethyl caproate, stearyl 2-ethyl caproate, stearyl caprate, methyl laurate, butyl laurate, cetyl laurate, Stearyl laurate, isopropyl myristate, isocetyl myristate, stearyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, lauryl palmitate, isostearyl palmitate, butyl stearate, isopropyl isostearate, isostearyl behenate, polyoxy Ethylene lauric acid methyl ester, polyoxyethylene la
  • Unsaturated fatty acid monoesters of monobasic acids and monohydric alcohols such as methyl oleate, methyl oleate, isopropyl oleate, butyl oleate, octyl oleate, isopropyl linoleate, butyl linoleate, ethyl linolenate;
  • Unsaturated fatty acid diesters of dibasic acids and monohydric alcohols such as diisopropyl maleate, dibutyl maleate, diisopropyl fumarate;
  • Saturated fatty acid polyvalent esters of polybasic acids and monohydric alcohols such as trimethyl isocitrate, trimethyl 1,2,3-propanetricarboxylate, dimethyl butanetetracarboxylate, trimethylbutanetetracarboxylate;
  • saturated fatty acid monoesters of polybasic acids and monohydric alcohols such as monoisodecyl adipate, monoisopropyl sebacate, monoisostearyl sebacate and the like.
  • Examples of the ester of a monobasic acid having 4 to 22 carbon atoms and an alcohol having a valence of 4 or less include the following. Divaleric acid polyoxyethylene, dicaproic acid neopentyl glycol, dicaproic acid diethylene glycol, dicaproic acid polyoxyethylene, dicaproic acid polyoxypropylene, dicaprylic acid ethylene glycol, dicaprylic acid polyoxyethylene, di2-ethylcaproic acid neopentyl glycol, Diethylene glycol di-2-ethylcaproate, polyoxyethylene di-2-ethylcaproate, polyoxypropylene di-2-ethylcaproate, dipropylene glycol di2-ethylcaproate, polyoxyethylene dicaprate, neopentyl glycol dilaurate, Polyoxyethylene dilaurate, polyoxypropylene dimyristate, polyoxyethylene dimyristate, neopentyl glycol dipalm
  • Polyoxyethylene dicrotonate polyoxyethylene dioleate, neopentyl glycol dioleate, polyoxypropylene dioleate, neopentyl glycol dilinoleate, polyoxyethylene dilinolenate, polyoxyethylene dilinoleate, neopentyl glycol dilinolenate, etc.
  • Unsaturated fatty acid diesters of saturated monobasic acids and dihydric alcohols also known as diols
  • epoxy-modified ester examples include epoxidized soybean oil or epoxidized linseed oil.
  • the phosphoric acid ester (c2) having 4 to 80 carbon atoms is an ester compound obtained by dehydration condensation of phosphoric acid and alcohol.
  • Examples of the phosphate ester (c2) having 4 to 80 carbon atoms include the following. Phosphoric acid, such as monobutyl phosphate, mono-2-ethylhexyl phosphate, monooctyl phosphate, monocapryl phosphate, monolauryl phosphate, monopalmityl phosphate, monostearyl phosphate, monobehenyl phosphate, and alkylene oxide adducts thereof Saturated monoesters;
  • Phosphoric acid unsaturated monoesters such as monopalmitoleyl phosphate, monooleyl phosphate, monolinoleyl phosphate, monolinolenyl phosphate, and alkylene oxide adducts thereof;
  • Phosphoric acid saturated diesters such as diethyl phosphate, dipropyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, dilauryl phosphate, dimyristyl phosphate, dipalmityl phosphate, distearyl phosphate, and alkylene oxide adducts thereof;
  • Phosphounsaturated diesters such as dipalmitoleyl phosphate, dioleyl phosphate, dilinoleyl phosphate, and alkylene oxide adducts thereof;
  • Phosphoric acid unsaturated triesters such as tripalmitoleyl phosphate, trioleyl phosphate, trilinoleyl phosphate, trilinolenyl phosphate, and alkylene oxide adducts thereof;
  • Polyoxyethylene oleyl ether phosphate ester polyoxyethylene lauryl ether phosphate ester, polyoxyethylene cetyl ether phosphate ester, polyoxyethylene octyl ether phosphate ester, etc.
  • the number of added moles of ethylene oxide (EO) is 2 to 20
  • EO ethylene oxide
  • the boric acid ester (c3) having 8 to 100 carbon atoms is an ester compound obtained by dehydration condensation of boric acid and alcohol.
  • Examples of the boric acid ester (c3) having 8 to 100 carbon atoms include the following. Methoxytetraethylene glycol ether borate, ethoxytriethylene glycol ether borate, butoxytetraethylene glycol ether borate, butoxytriethylene glycol ether borate, butoxytetraethylene glycol ether borate, 2-ethylhexyloxydiethylene glycol Polyoxyalkylene alkyl ethers with 2 to 20 additions of ethylene oxide (EO), such as ether borate, polyethylene glycol monobutyl ether borate, polyethylene glycol monopropyl ether borate, polyethylene glycol monobutyl ether borate, etc. Borate esters;
  • EO ethylene oxide
  • PO propylene oxide
  • BO butylene oxide
  • the ester compound (C) can be used alone or in combination of two or more.
  • the ester compound (C) preferably has a molecular weight (formula weight) of 200 to 2,000.
  • the molecular weight is in the above range, the compatibility with the copolymer (A) is improved, so that the removability is improved by improving the transparency and cohesion, and the adherend is hardly contaminated.
  • the ester compound (C) is preferably contained in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the copolymer (A).
  • the adhesive layer can be sufficiently plasticized to improve flexibility, and further improve the maintenance of low adhesive strength in the microviscous region and the wet-spreading property of the pressure-sensitive adhesive film. be able to.
  • ester compound (C) is cetyl 2-ethylcaproate, 2-ethylcaprone in terms of compatibility with the copolymer (A), wettability, removability, and suppression of adherend contamination.
  • Neopentyl glycol acid polyoxyethylene di-2-ethylcaproate (EO addition mole number: 2 to 30), bis (methoxypolyoxyethylene) adipate (2 to 30 moles of EO addition), bis adipate ⁇ 2 -(2-butoxyethoxy) ethyl ⁇ , bis (2-butyl adipate)
  • the pressure-sensitive adhesive of the present invention may contain a surfactant (D) as an optional component.
  • Surfactant (D) contributes to compatibilization of the polar part and non-polar part of the copolymer (A), and can suppress whitening of the pressure-sensitive adhesive and further suppress whitening of the adhesive layer in the adhesive film.
  • an adhesive layer can be plasticized similarly to ester compound (C)
  • the wet spread property with respect to adherends, such as a glass plate of a pressure sensitive adhesive film improves more.
  • the removability of the pressure-sensitive adhesive film is further improved.
  • Surfactant (D) is a general term for substances that act on the interface of a substance (surface of the substance's boundary) and change the properties of the interface. In the molecule, there are two structural parts, a hydrophilic part and a hydrophobic part. Have Therefore, in order to uniformly mix the polar substance and the nonpolar substance, it has a function of weakening the surface tension.
  • the surfactant (D) is a compound other than the copolymer (A), the reactive compound (B), and the ester compound (C).
  • the surfactant (D) can be classified into an anionic surfactant (d1), a cationic surfactant (d2), an amphoteric surfactant (d3), and a nonionic surfactant (d4).
  • the anionic surfactant (d1) has a carboxylic acid type, a sulfonic acid type, a sulfate ester type, or a phosphate ester type, and has a structure as an unsubstituted, alkali metal salt, ammonium salt, or amine salt, respectively. It is. Further, those having an alkylene oxide chain such as a polyoxyethylene skeleton are also included. Examples of the anionic surfactant (d1) include the following.
  • anionic surfactants (d1) a nonionic surfactant (d4) described later, which has an ethyleneoxy group and has an addition mole number of ethyleneoxy (EO) in the range of 2 to 60 mol
  • a sulfonic acid, sulfuric acid, or phosphoric acid is added to “(2) an ester of a monobasic acid having 18 to 22 carbon atoms and a divalent to tetravalent alcohol” described in the above ester compound (C) to form ammonium.
  • a surfactant (d1-1) anionized with a salt or an amine salt is preferred.
  • Anionic surfactants other than the anionic surfactant (d1-1) belong to the anionic surfactant (d1-2).
  • the cationic surfactant (d2) is a compound having a cationic hydrophilic group in the molecule, and examples thereof include a quaternary ammonium salt type, an alkylamine salt type, and a pyridine salt type.
  • Examples of the cationic surfactant (d2) include the following. Quaternary ammonium salts having halogen such as tetramethylammonium chloride, tetrabutylammonium chloride, dodecyltrimethylammonium chloride, benzyltriethylammonium chloride, distearyldimethylammonium chloride, polyethylene glycol alkyl fatty acid ammonium chloride;
  • Quaternary ammonium salts having no halogen such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, alkylammonium hydrate, lauryldimethylethylammonium ethyl sulfate, palmityldimethylethylammonium ethyl sulfate;
  • Alkylamine salts such as monomethylamine chloride, dimethylamine chloride, trimethylamine chloride, alkyl imidazoline, coconut amine acetate, stearyl amine acetate;
  • Examples thereof include compounds having a pyridine ring, such as pyridium salts such as 1-dodecylpyridinium chloride, laurylpyridinium chloride, and hexapyridium chloride hydrate. These can be used alone or in combination of two or more.
  • pyridium salts such as 1-dodecylpyridinium chloride, laurylpyridinium chloride, and hexapyridium chloride hydrate.
  • the amphoteric surfactant (d3) is a surfactant having both an anion moiety such as a carboxylic acid structure and a cation moiety such as quaternary ammonium as a hydrophilic group.
  • examples of the amphoteric surfactant (d3) include betaine type, amino acid type, and amine oxide type structures. More specifically, examples include the following. Betaine surfactants such as lauryl betaine, stearyl betaine, lauryl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, dodecylaminomethyldimethylsulfopropylbetaine, lauryldimethylaminoacetic acid betaine, lauric acid amidopropyl betaine;
  • Amino acid type surfactants such as sodium lauroyl glutamate, potassium lauroyl glutamate, lauroylmethyl- ⁇ -alanine, sodium lauryliminodipropionate, N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium;
  • amine oxide surfactants such as lauryl dimethylamine oxide, oleyl dimethylamine oxide, stearyl dimethylamine oxide, and lauryl dihydroxyethylamine oxide. These can be used alone or in combination of two or more.
  • the nonionic surfactant (d4) is a surfactant that does not exhibit ionic properties even when dissolved in water, but exhibits surface activity.
  • Nonionic surfactant (d4) is a higher alcohol having 8 to 22 carbon atoms and a compound having an ether type or nitrogen-containing structure, and can be used by adjusting the balance between hydrophilic group and lipophilic group. In some cases, it may have a hydroxyl group.
  • ether type nonionic surfactants include polyoxyethylene 2-ethylcapryl ether, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether, 2-methyl-1-butene-polyoxyethylene polyoxybutylene ether, polyoxyethylene Oxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene branched decyl ether, polyoxyethylene castor oil ether, polyoxyethylene-1 -(Allyloxymethyl) alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene cumylphenyl ether, polyoxyethylene dodeci Phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene benzyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene polyoxy
  • nitrogen-containing nonionic surfactant examples include polyoxyethylene alkylamine, alkyl alkanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene alkylamine monostearate, polyoxyethylene stearic acid amide and the like. Is mentioned. These can be used alone or in combination of two or more.
  • the number of moles of EO added to the ethyleneoxy group is particularly preferably in the range of 2 to 60 mol, and more preferably in the range of 3 to 40 mol.
  • These nonionic surfactants may be saturated or unsaturated, and may be linear or branched.
  • the nonionic surfactant (d4) as described above has a number of OH groups or an ethyleneoxy group chain so that its HLB (abbreviation of Hydrophile-Lipophile Balance, sometimes referred to as HLB value) is 5 to 16. It is preferred that the length be adjusted. Further, it is particularly preferable that the HLB is adjusted to be in the range of 7 to 14.
  • HLB abbreviation of Hydrophile-Lipophile Balance
  • HLB is a value representing the degree of affinity of a surfactant to water and oil (an organic compound insoluble in water), and several methods for determining by calculation have been proposed.
  • the content of the surfactant (D) is preferably 0.01 to 100.0 parts by mass, more preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the copolymer (A) of the present invention. 0.0 part by mass. If the surfactant (D) is in the above range, the adhesive layer can be sufficiently plasticized to improve flexibility, and maintain low adhesive strength in the microviscous region and further improve the wetting and spreading of the pressure-sensitive adhesive film. can do.
  • the surfactant (D) preferably has a molecular weight (formula weight) of 200 to 2,000.
  • the molecular weight is in the above range, so that the compatibility with the copolymer (A) is improved, so that the removability is improved by improving the transparency and cohesion, and the adherend is hardly contaminated.
  • Surfactant (D) is easy to orient on the adhesive surface of the adhesive film, and it is possible to obtain stable wetting and spreading while maintaining flexibility from room temperature to low temperature over a long period of time.
  • An anionic surfactant (d1) or nonionic surfactant (d4) having an ethyleneoxy group having a mole number in the range of 2 to 60 mol is preferred, and an anionic surfactant (d1) is more preferred.
  • anionic surfactants (d1) an anionic surfactant containing one or more hydrophilic groups selected from the group consisting of sulfonic acid ester salts having a polyethyleneoxy group, sulfuric acid ester salts, and phosphoric acid ester salts ( d1-1) is particularly preferred.
  • surfactant (D) has an EO addition mole number of ethyleneoxy group from the viewpoint of suppression of the spread of wetness, removability and adherend in addition to industrial availability. It is an anionic surfactant (d1-1) containing at least one hydrophilic group selected from the group consisting of sulfonate ester salts, sulfate ester salts, and phosphate ester salts in the range of 2 to 60 mol. Is preferred.
  • suitable anionic surfactant (d1-1) include polyoxyethylene 2-ethylcapryl ether, polyoxyethylene lauryl ether, polyoxyethylene palmityl ether, polyoxyethylene stearyl ether and the like.
  • Oxyethylene alkyl ethers Polyoxyethylene alkenyl ethers such as polyoxyethylene oleyl ether, 2-methyl-1-butene-polyoxyethylene polyoxybutylene ether; Polyoxyethylene dialkyl glyceryl ethers such as polyoxyethylene dilauryl glyceryl ether, polyoxyethylene lauryl myristyl glyceryl ether; Polyoxyethylene glycerin such as polyoxyethylene monoglyceride laurate, polyoxyethylene diglyceride 2-ethylcaproate, polyoxyethylene diglyceride laurate, polyoxyethylene diglyceride oleate, polyoxyethylene diglyceride myristate, polyoxyethylene diglyceride stearate Fatty acid esters; Examples thereof include sulfonic acid ester salts such as polyoxyethylene alkyl ether glycerin such as polyoxyethylene-1- (allyloxymethyl) alkyl ether glycerin, sulfuric acid ester salt, phosphoric
  • the phosphoric acid or phosphoric acid derivative (E) forms pseudo-crosslinks with the ethyleneoxy group of the copolymer (A), and the moisture and heat resistance and water resistance are improved by suppressing the hydration of the ethyleneoxy group.
  • the pressure-sensitive adhesive of the present invention preferably contains at least one of phosphoric acid or phosphoric acid derivative (E).
  • the phosphoric acid or phosphoric acid derivative (E) is preferably contained in an amount of 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the copolymer (A).
  • phosphoric acid or phosphoric acid derivative (E) when used in the above range, when water is hydrated to the ethyleneoxy group of the adhesive layer, phosphoric acid or phosphoric acid derivative (E) causes dehydration to remove the water and suppresses hydration. To do.
  • a charge transfer interaction occurs between an oxygen atom and a phosphorus atom contained in the ethyleneoxy group, thereby forming a pseudo bridge. For this reason, it is effective in suppressing the ingress of water and removing the infiltrated water, and the moisture and heat resistance and the water resistance are improved.
  • Phosphoric acid includes orthophosphoric acid, phosphorous acid, and hypophosphorous acid.
  • Examples of phosphoric acid derivatives include pyrophosphoric acid, condensed triphosphoric acid, metaphosphoric acid, and polyphosphoric acid.
  • phosphorous acid, hypophosphorous acid, or pyrophosphoric acid, metaphosphoric acid, and polyphosphoric acid which are condensed phosphoric acids that easily adsorb water, are preferable in terms of improving the heat and moisture resistance and water resistance.
  • the pressure-sensitive adhesive of the present invention may further contain an ionic compound (F).
  • the ionic compound (F) is a liquid or solid ionic compound at room temperature (25 ° C.).
  • the ionic compound (F) is a compound other than the copolymer (A), the reactive compound (B), phosphoric acid or phosphoric acid derivative (E), and the ester compound (C).
  • Solid ionic compounds include alkali metal salts (inorganic salts of alkali metals, organic salts of alkali metals), surfactants, ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, etc. Also mentioned.
  • Examples of the inorganic salt of the alkali metal salt include metal salts composed of lithium, sodium, and potassium.
  • the alkali metal salt is composed of a cation portion composed of Li + , Na + , and K + and various anion portions. According to the kind of anion part, it can be divided into an inorganic salt and an organic salt.
  • Examples of inorganic salts of alkali metals include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate (LiClO 4 ), potassium chlorate, potassium nitrate, sodium nitrate, sodium carbonate, sodium thiocyanate, KPF 6 , LiBr, LiI, LiBF 4, LiPF 6, LiSCN, and the like. Among these, KPF 6 , LiPF 6 , lithium perchlorate, and the like are preferable from the viewpoint of conductivity and safety.
  • Organic salts of alkali metals include, for example, sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluenesulfonate, LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) IN, Li (C 2 F 5 SO 2) 2 N, Li (C 2 F 5 SO 2) IN, Li (CF 3 SO 2) 3 C and the like, LiCF 3 SO 3, Li ( CF 3 SO 2) 2 N Li (CF 3 SO 2 ) IN, Li (C 2 F 5 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) IN, Li (CF 3 SO 2 ) 3 C and the like are preferable, and Li (CF 3 SO 2) 2 N, Li ( CF 3 SO 2) iN, Li (C 2 F 5 SO 2) 2 N, Li (C 2 F 5 SO 2) fluorine-containing lithium imide salt iN. in particular (Bae Fluoroalkyl sulfonyl) imide lithium salts.
  • a liquid ionic compound is a compound that exhibits liquid properties at room temperature, and is composed of a cation component and an anion component.
  • the cation component include pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, and pyrazolium.
  • the anionic component may be a liquid ionic compound, for example, Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , F (HF) n ⁇ , (CN) 2 N ⁇ , C 4 F 9 SO 3 ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , C 3 F 7 COO ⁇ , ( CF 3 SO 2 ) (CF 3 CO) N — and the like.
  • liquid ionic compound examples include 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1 -Butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyridinium tetrafluoroborate, tetrabutylammonium tetrakis (perfluorophenyl) Borate, 2-methyl-1-pyrroline tetrafluoroborate, 1-octyl-3-methylimidazolium tetrafluoroborate, N, N-dimethyl-N-ethyl- -Hexy
  • the ionic compound (F) is preferably contained in an amount of 0.001 to 20 parts by mass with respect to 100 parts by mass of the copolymer (A). When the amount is within the above range, a sufficient antistatic function is exhibited, and whitening or bleeding out of the adhesive layer is unlikely to occur.
  • An ionic compound (F) can be used individually by 1 type or in combination of 2 or more types.
  • the pressure-sensitive adhesive of the present invention can contain other components as long as the problem can be solved.
  • Other components (P) include, for example, polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, oxidation-reduction suppression, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, and coloring improvement. From such viewpoints, organic or inorganic additives and fillers may be mentioned.
  • the filler is appropriately composed of a polymer, ceramics, metal, metal oxide, metal salt, and dye / pigment.
  • the shape of the filler is preferably, for example, particulate or fibrous.
  • Additives include antioxidants, flame retardants, storage stabilizers, antioxidants, UV absorbers, thixotropy imparting agents, dispersion stabilizers, fluidity imparting agents, thickeners, humectants, pH adjusters. , Leveling agents, hydrolysis inhibitors and antifoaming agents.
  • the pressure-sensitive adhesive of the present application comprises a copolymer (A), a reactive compound (B) having a functional group capable of reacting with a hydroxyl group, and, if necessary, an ester compound (C), a surfactant (D), The material of phosphoric acid or phosphoric acid derivative (E) and ionic compound (F) is included.
  • a known mixing device such as a Henschel mixer, a disper, an attritor, a high speed mixer, or a homomixer can be used.
  • the viscosity of the pressure-sensitive adhesive of the present invention is appropriately adjusted according to the usage form.
  • the pressure-sensitive adhesive of the present invention may additionally use a solvent to adjust the viscosity as necessary.
  • the solvent the solvents already described can be used.
  • the viscosity of the pressure-sensitive adhesive is preferably in the range of 500 to 10,000 mPa ⁇ s, more preferably 1,000 to 8,000 mPa ⁇ s, as measured with a B-type viscometer at 25 ° C.
  • an adhesive layer having an appropriate thickness can be easily formed by coating.
  • the pressure-sensitive adhesive film of the present invention includes a base material and an adhesive layer made of the pressure-sensitive adhesive of the present invention.
  • a release liner is usually bonded to the surface of the adhesive layer that does not contact the substrate until just before use.
  • the production of the pressure-sensitive adhesive film is, for example, (1) A method in which a pressure-sensitive adhesive is applied to a release liner and dried to form an adhesive layer, and the substrate is further bonded. Further, (2) a method in which a pressure-sensitive adhesive is applied to a substrate and dried to form an adhesive layer, and a release liner is attached to the pressure-sensitive adhesive layer is preferable.
  • the coating method is not particularly limited. Examples include a Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, kiss coater, lip coater, comma coater, blade coater, knife coater, reverse coater, spin coater, dip coater and the like.
  • the coating is usually dried. There is no restriction
  • the drying temperature is usually preferably about 60 to 180 ° C.
  • the thickness of the adhesive layer is preferably 0.5 to 300 ⁇ m, more preferably 1 to 100 ⁇ m. When the thickness is in an appropriate range, it is easy to obtain an adhesive force that is not excessive or insufficient.
  • the substrate of the pressure-sensitive adhesive film examples include wood, metal plate, plastic, film-like substrate, glass plate, and processed paper product.
  • the base material may be a single layer or a laminate in which two or more base materials are laminated.
  • the base material needs to be transparent. Therefore, it is preferable to use a material having good transparency such as a plastic or a glass plate.
  • a base material that is plastic and has good transparency is also referred to as a transparent film.
  • the transparent film is, for example, a polyvinyl alcohol film (also referred to as PVA film), a polytriacetyl cellulose film (also referred to as TAC film), a polypropylene film (also referred to as PP film), a polyethylene film (also referred to as PE film), or a polycycloolefin film.
  • a polyvinyl alcohol film also referred to as PVA film
  • a polytriacetyl cellulose film also referred to as TAC film
  • PP film polypropylene film
  • PE film polyethylene film
  • PE film polycycloolefin film
  • polyolefin resin film such as ethylene-vinyl acetate copolymer film (also referred to as EVA film), polyethylene terephthalate film (also referred to as PET film), polybutylene terephthalate film (also referred to as PBT film), etc.
  • Polyester resin film polycarbonate resin film (also called PC film), polynorbornene resin film, polyarylate resin Film, polyacrylic ester resin film, polyphenylene sulfide resin film (also referred to as PPS film), polystyrene resin film (also referred to as PST film), polyamide resin film (also referred to as PA film), polyimide resin Film (also referred to as PI film) and oxirane resin film.
  • PPS film polyphenylene sulfide resin film
  • PST film polystyrene resin film
  • PA film polyamide resin film
  • PI film polyimide resin Film
  • oxirane resin film also referred to as oxirane resin film.
  • a PVA film, a TAC film, a COP film, a polyester resin film, and a PC film are more preferable.
  • the thickness of the substrate is usually 5 ⁇ m to 300 ⁇ m, preferably 15 ⁇ m to 150 ⁇ m.
  • the surface of the substrate is subjected to physical treatment such as corona discharge, plasma treatment or flame treatment, chemical treatment for modifying the surface of the film with acid or alkali, etc.
  • Adhesion with the adhesive layer can be improved by performing a treatment for increasing the substantial surface area.
  • the substrate can be provided with functionality such as conductivity by depositing or sputtering a metal oxide or the like on the surface.
  • a metal oxide or the like examples include silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium.
  • a coating layer to which a fatty acid amide, polyethyleneimine, a long-chain alkyl additive or the like is added, or a release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based material is used for the surface not contacting the adhesive layer of the substrate.
  • the mold release process can be arbitrarily set.
  • the release liner usually has a release treatment layer formed on the surface of a film-like substrate such as cellophane, each plastic film, or paper.
  • the substrate can be a single layer or a laminate.
  • the constitution of the pressure-sensitive adhesive film is preferably, for example, a single-sided adhesive film such as a substrate / adhesive layer / release liner, or a double-sided adhesive film such as a release liner / adhesive layer / substrate / adhesive layer / release liner.
  • a cast adhesive film of release liner / adhesive layer / release liner is also preferred.
  • the structure of the laminated body mentioned later is also preferable.
  • substrate / adhesive layer / adhered body A laminate using an optical member as an adherend is referred to as an optical laminate.
  • a laminate using an electronic member as an adherend is referred to as an electronic component laminate.
  • Examples of the method of using the adhesive film include a method of creating an adhesive film, peeling off the release liner, and attaching it to an adherend. This method is preferable because re-sticking and “removability” are further improved.
  • a surface protective film will be described as an example of an embodiment of the pressure-sensitive adhesive film of the present invention.
  • the surface protective film preferably uses a transparent film as a substrate.
  • the transparent film can have an optical function.
  • the optical function includes, for example, light transmission, light diffusion, light collection, refraction, scattering, haze, and the like.
  • the transparent film may have a plurality of optical functions.
  • the transparent film can also use the laminated body using a single layer or two or more types of films.
  • the transparent film is preferably a polyester film, for example.
  • the surface protective film of the present invention preferably has high transparency.
  • “High transparency” means haze of 5% or less, preferably 2% or less. Taking advantage of this transparency, when the surface protective film is used for protecting an adherend at the time of manufacture on an optical member or an electronic component, these components can be inspected with the surface protective film attached. In addition, when using the adhesive film of this invention for the surface protection film use of an electronic member, transparency is not necessarily required.
  • the surface protective film examples include application to a liquid crystal cell or the like, or application to a display.
  • a surface protection film is preferably an optical application, it can also be used in other fields.
  • various electronic parts-related materials, glass materials such as building materials and vehicle window glass, surface protection of plastics such as polyolefin, ABS, polyacryl, etc., corrugated cardboard, wood, plywood, stainless steel, aluminum, etc. Can also be used.
  • the optical laminate of the present invention includes an optical film, an adhesive layer made of a pressure-sensitive adhesive, and glass.
  • the optical film is preferably a polyester resin film.
  • the thickness of the optical film is usually about 5 ⁇ m to 300 ⁇ m, preferably 15 ⁇ m to 150 ⁇ m.
  • the glass used in the optical laminate of the present invention is, for example, a surface glass plate constituting a part of a liquid crystal display, a surface glass plate for a touch panel, a glass plate for an optical filter, a glass plate for a plano-concave lens, a glass plate for an optical prism, Examples thereof include a glass plate for a light source reflector and a glass plate for an optical surface mirror.
  • the glass material is not limited as long as it is glass used in the display field.
  • the glass thickness is usually about 5 ⁇ m to 30 mm.
  • optical laminate of the present application examples include, for example, liquid crystal displays, plasma displays, touch panels, electrode peripheral members, and the like.
  • the polymerization was started by heating to 80 ° C. with stirring in a nitrogen atmosphere.
  • the mixture containing the ethylenically unsaturated compound, the polymerization initiator and the organic solvent was added dropwise from the dropping device at reflux temperature over 2 hours.
  • 0.03 parts of a polymerization initiator was added twice every hour while stirring, and then the reaction was continued for 5 hours. Thereafter, 57.14 parts of toluene was added and cooled to 25 ° C. to obtain a copolymer (A) solution.
  • This solution is colorless and transparent, has a non-volatile concentration (NV) of 50.1%, a solution viscosity (Vis) of 3,500 mPa ⁇ s (25 ° C.), and the copolymer (A) has a glass transition temperature (Tg).
  • NV non-volatile concentration
  • Vis solution viscosity
  • Tg glass transition temperature
  • the hydroxyl value (OHV) of the copolymer was 12.5 mgKOH / g, and the weight average molecular weight (Mw) was 750,000.
  • Synthesis Examples 2-33 In Synthesis Example 1, except that the types and blending amounts of the monomer, polymerization initiator, and organic solvent constituting the copolymer were changed according to Table 1-1, Table 1-2, and Table 1-3, respectively.
  • Synthesis Examples 2 to 33 copolymers were synthesized. Among these, the copolymers obtained in Synthesis Examples 1 to 12, 15 to 24, 27 to 28, 32 and 33 are the copolymer (A), Synthesis Examples 13, 14, 25, 26, 30 and 31.
  • the obtained copolymer is a copolymer (for comparative example) which is not the copolymer (A).
  • the polymerization was started by heating to 60 ° C. with stirring in a nitrogen atmosphere. While gradually raising the temperature in the polymerization tank to 80 ° C., the mixture containing the ethylenically unsaturated compound, the polymerization initiator and the organic solvent was added dropwise from the dropping device over 2 hours at a reflux temperature. While further stirring, 0.03 part of the polymerization initiator was added twice every hour after completion of the dropwise addition, and then aged for 4 hours to continue the reaction. Thereafter, 57.14 parts of toluene was added and cooled to 25 ° C. to obtain a copolymer (A) solution.
  • This solution is colorless and transparent, has a nonvolatile content concentration (NV) of 50.3%, a solution viscosity (Vis) of 4,200 mPa ⁇ s (25 ° C.), and the copolymer (A) has a glass transition temperature (Tg).
  • the copolymer had a hydroxyl value (OHV) of 7.9 mgKOH / g and a weight average molecular weight (Mw) of 680,000.
  • Synthesis Examples 35 to 66 In Synthesis Example 34, except that the types and blending amounts of the monomer, the polymerization initiator, and the organic solvent constituting the copolymer were changed according to Table 2-1, Table 2-2, and Table 2-3, respectively. In the same manner as in Synthesis Example 34, Synthesis Examples 35 to 66 copolymers were synthesized. Among these, the copolymers obtained in Synthesis Examples 34 to 45, 48 to 57, 60 to 62, 65 and 66 are copolymers (A), and Synthesis Examples 46, 47, 58, 59, 63 and The copolymer obtained in 64 is a copolymer that is not the copolymer (A).
  • Non-volatile content (NV) About 1 g of the copolymer solution obtained in each synthesis example was weighed into a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated, and the non-volatile concentration ( Solid unit) (unit:%).
  • ⁇ Average molecular weight The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography). The determination of the number average molecular weight (Mn) and the weight average molecular weight (Mw) was a conversion value of polystyrene as a standard substance.
  • Hydroxyl value (OHV)
  • About 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol 2/1) mixed solution was added and dissolved.
  • 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for 1 hour.
  • phenolphthalein test solution was added as an indicator and held for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
  • the hydroxyl value was determined by the following formula.
  • the hydroxyl value is a non-volatile content conversion value of the copolymer.
  • Hydroxyl value (mgKOH / g) [ ⁇ (ba) ⁇ F ⁇ 28.25 ⁇ / S] / (Nonvolatile content concentration / 100) + D
  • S Amount of sample collected
  • a Consumption of 0.1N alcoholic potassium hydroxide solution
  • b Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment
  • F Potency of 0.1N alcoholic potassium hydroxide solution
  • D Acid value (mgKOH / g)
  • AV Acid value
  • About 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol 2/1) mixed solution was added and dissolved. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
  • the acid value was determined by the following formula.
  • the acid value is a non-volatile content conversion value of the copolymer.
  • S Amount of sample collected
  • a Consumption of 0.1N alcoholic potassium hydroxide solution
  • F Potency of 0.1N alcoholic potassium hydroxide solution
  • Glass transition temperature (Tg) >> The glass transition temperature (Tg, unit: ° C.) was determined from the above theoretical formula (FOX formula).
  • Examples 1 to 190, Comparative Examples 1 to 20 A copolymer, a reactive compound (B), and the like were blended in accordance with the descriptions in Tables 3-1 to 8-2, and stirred and mixed, and the pressure-sensitive adhesives of Examples 1 to 190 and Comparative Examples 1 to 20, respectively. Obtained.
  • the pressure sensitive adhesive was adjusted to a non-volatile content concentration of 50% using ethyl acetate.
  • the obtained pressure sensitive adhesive was evaluated by the following method. The respective results are shown in Tables 9-1 to 9-6.
  • Viscosity increase rate (%) 100 ⁇ ⁇ (viscosity after 8 hours storage) ⁇ (viscosity immediately after adjustment) ⁇ / (viscosity immediately after adjustment)
  • the obtained pressure-sensitive adhesive was coated on a release liner (peeled polyethylene terephthalate film having a thickness of 38 ⁇ m, therapy MF: manufactured by Toray Film Processing Co., Ltd.) so that the thickness after drying was 25 ⁇ m.
  • the adhesive layer was formed by drying with hot air at 100 ° C. for 2 minutes.
  • PET film polyethylene terephthalate film
  • the obtained pressure-sensitive adhesive was applied onto a release liner so that the thickness after drying was 50 ⁇ m, and dried with hot air at 100 ° C. for 2 minutes to form an adhesive layer.
  • a separately prepared release liner was bonded to the adhesive layer to prepare a pressure-sensitive adhesive film in which the adhesive layer was sandwiched between the release liners, and was cured for 7 days in an environment of 23 ° C. and 50% relative humidity.
  • both release liners were removed, the appearance of the adhesive layer alone was visually judged, and the haze was measured with “NDH-300A (Nippon Denshoku Industries Co., Ltd.)”. In the case of “A” or “B” evaluation, there is no practical problem.
  • A No cloudiness or the like is observed, and HAZE: less than 0.5. Good.
  • B Clouding or the like is not observed, but HAZE: 0.5 or more and less than 2, can be used without any practical trouble.
  • C Cloudiness is observed, or HAZE: 2 or more. Bad.
  • the obtained pressure-sensitive adhesive was coated on a PET film having a thickness of 50 ⁇ m as a base material so that the thickness after drying was 15 ⁇ m, and dried with hot air at 100 ° C. for 2 minutes to form an adhesive layer. Formed.
  • a release liner was bonded to the adhesive layer to prepare a pressure-sensitive adhesive film having a structure of 50 ⁇ m thick PET film / adhesive layer / release liner, and cured for 7 days in an environment of 23 ° C. and 50% relative humidity.
  • the pressure-sensitive adhesive film was cut into a width of 100 mm and a length of 100 mm to obtain a measurement sample.
  • a float glass plate having a thickness of 2 mm ⁇ width 150 mm ⁇ length 150 mm is brought into contact with the float glass plate in a state where only one side of the adhesive layer exposed by peeling the release liner from the measurement sample is inclined by 45 °,
  • the time required for the entire surface of the sample to come into contact with the glass plate was taken as the wet spread property and evaluated in the following three stages. In the case of “A” or “B” evaluation, there is no practical problem.
  • B Wetting spread time is 2 seconds or more and less than 4 seconds. Can be used practically.
  • C Time to spread wet is 4 seconds or more. Bad.
  • the release liner was peeled off from the sample, and the exposed adhesive layer was attached to a non-alkali glass plate having a thickness of 1.2 mm using a laminator in an environment of 23 ° C. and a relative humidity of 50%. Then, it hold
  • peel strength was measured under the condition of 180 degrees (peel strength after 1 day of bonding).
  • a measurement sample separately prepared in the same manner as described above was allowed to stand for 14 days in an environment of 23 ° C. and a relative humidity of 50%, and then peel strength was measured by the same method (peel strength after 14 days of bonding). This peel strength was evaluated as an adhesive strength in three stages. In the case of “A” or “B” evaluation, there is no practical problem.
  • Adhesive strength is less than 10.0 (mN / 25 mm). Good.
  • B Adhesive strength is 10.0 (mN / 25 mm) or more and less than 15.0 (mN / 25 mm). Can be used practically.
  • C Adhesive force is 15.0 (mN / 25 mm) or more. Poor and impractical.
  • the release liner is peeled off from the sample, and the exposed adhesive layer is bonded to one side of a 1.2 mm-thick non-alkali glass plate by applying a pressure of 5 kg / cm 2 at 50 ° C. and holding it in an autoclave for 20 minutes. And then left in an atmosphere at 80 ° C. for 500 hours. After standing, the temperature was returned to 25 ° C., the pressure-sensitive adhesive film was floated / peeled, and the presence or absence of foaming was visually observed to evaluate the heat resistance in three stages.
  • the release liner was peeled from the sample, and the exposed adhesive layer was bonded to one side of a float glass plate having a thickness of 2 mm, a width of 50 mm, and a length of 50 mm in an atmosphere at 23 ° C. and a relative humidity of 50% to prepare a laminate. 5 minutes after sticking, the laminate was immersed in distilled water at 40 ° C. for 24 hours, and then the laminate was taken out in an atmosphere at 23 ° C. and 50% relative humidity.
  • the pressure-sensitive adhesive film from the laminate was visually observed for the presence or absence of peeling, and water resistance was evaluated in three stages. In the case of “A” or “B” evaluation, there is no practical problem.
  • the pressure-sensitive adhesives of the present invention were produced in Examples 1 to 17, 19 to 31, 37 to 40, 42 to 59, 61, 62, 64 to 77, 82 to 84, 86, 90 to 95,
  • 96-112 114-126, 132-135, 137-154, 156, 157, 159-172, 175-179, 181 and 185-190
  • pot life coatability, optical properties, workability, wet spread Property, peel strength (1 day after pasting, 14 days after pasting), re-peelability, heat resistance, moist heat resistance and water resistance
  • "B” evaluation practical level
  • the pressure-sensitive adhesive according to the present invention has excellent adhesive strength, it can be used in the construction field (eg, exterior, interior, equipment, etc.), electrical equipment field (eg, home appliances, kitchen equipment, air conditioning, etc.), and transport equipment field. It can also be used in various industrial fields other than the optical field, such as the ship field, automobiles, etc., the furniture field, and the sundries field.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un agent adhésif sensible à la pression avec lequel il est possible de produire un film adhésif sensible à la pression ayant une excellente résistance à l'eau en plus de la résistance à la chaleur et de la résistance à la chaleur humide, un film adhésif sensible à la pression dans lequel ledit agent adhésif sensible à la pression est utilisé, et un stratifié optique. L'agent adhésif sensible à la pression selon l'invention comprend un copolymère (A) qui comporte des groupes hydroxyle et un composé réactif (B) qui comporte des groupes fonctionnels capables de réagir avec des groupes hydroxyle, et contenant en tant qu'unités monomères constituant le copolymère (A) des unités de composé insaturé éthylénique (a1) qui ont des groupes hydroxyle, des unités de composé insaturé éthylénique sans groupe polaire (a2) qui ont un Log P de coefficient de partage supérieur ou égal à 6,5 et inférieur ou égal à 12, et des unités de composé insaturé éthylénique sans groupe hydroxyle (a3) qui ont des groupes éthylèneoxy.
PCT/JP2017/030702 2016-09-09 2017-08-28 Agent adhésif sensible à la pression, film adhésif sensible à la pression et stratifié optique WO2018047649A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2016-176678 2016-09-09
JP2016176678 2016-09-09
JP2017-009743 2017-01-23
JP2017009743A JP6790865B2 (ja) 2017-01-23 2017-01-23 感圧式接着剤及び接着フィルム
JP2017017655A JP2018044140A (ja) 2016-09-09 2017-02-02 感圧式接着剤及び接着フィルム
JP2017-017655 2017-02-02
JP2017133230A JP2019014820A (ja) 2017-07-07 2017-07-07 感圧式接着剤および感圧式接着フィルム
JP2017-133230 2017-07-07

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WO2018047649A1 true WO2018047649A1 (fr) 2018-03-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022507864A (ja) * 2019-01-25 2022-01-18 エルジー・ケム・リミテッド 表面保護フィルムおよび有機発光電子装置の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008248223A (ja) * 2007-03-07 2008-10-16 Ipposha Oil Ind Co Ltd 表面保護シート用粘着剤組成物及びこれを用いた表面保護シート
JP2009298916A (ja) * 2008-06-13 2009-12-24 Toyo Ink Mfg Co Ltd 制電性アクリル系樹脂組成物、制電性アクリル系感圧式接着剤組成物、及びそれを用いてなる光学部材保護用感圧式接着性保護フィルム
JP2015508431A (ja) * 2011-12-21 2015-03-19 エルジー・ケム・リミテッド 粘着剤組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008248223A (ja) * 2007-03-07 2008-10-16 Ipposha Oil Ind Co Ltd 表面保護シート用粘着剤組成物及びこれを用いた表面保護シート
JP2009298916A (ja) * 2008-06-13 2009-12-24 Toyo Ink Mfg Co Ltd 制電性アクリル系樹脂組成物、制電性アクリル系感圧式接着剤組成物、及びそれを用いてなる光学部材保護用感圧式接着性保護フィルム
JP2015508431A (ja) * 2011-12-21 2015-03-19 エルジー・ケム・リミテッド 粘着剤組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022507864A (ja) * 2019-01-25 2022-01-18 エルジー・ケム・リミテッド 表面保護フィルムおよび有機発光電子装置の製造方法
JP7191223B2 (ja) 2019-01-25 2022-12-16 エルジー・ケム・リミテッド 表面保護フィルムおよび有機発光電子装置の製造方法

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