[go: up one dir, main page]

WO2015151224A1 - Composition adhésive, adhésif, et feuille adhésive - Google Patents

Composition adhésive, adhésif, et feuille adhésive Download PDF

Info

Publication number
WO2015151224A1
WO2015151224A1 PCT/JP2014/059605 JP2014059605W WO2015151224A1 WO 2015151224 A1 WO2015151224 A1 WO 2015151224A1 JP 2014059605 W JP2014059605 W JP 2014059605W WO 2015151224 A1 WO2015151224 A1 WO 2015151224A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
adhesive composition
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/059605
Other languages
English (en)
Japanese (ja)
Inventor
祐樹 小澤
隆行 荒井
所司　悟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Priority to JP2016511243A priority Critical patent/JP6325653B2/ja
Priority to PCT/JP2014/059605 priority patent/WO2015151224A1/fr
Publication of WO2015151224A1 publication Critical patent/WO2015151224A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • 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
    • C09J133/04—Homopolymers or copolymers of esters

Definitions

  • the present invention relates to an adhesive composition, an adhesive and an adhesive sheet that can be used for a touch panel and the like.
  • a touch panel is often used as a display panel.
  • the types of touch panels include a resistive film method and a capacitance method, but the above-described mobile electronic devices mainly employ a capacitance method.
  • a capacitive touch panel an electric field is formed on the entire surface of the touch panel, and position detection is performed by detecting changes in the surface charge of the part touched by the finger. Therefore, the dielectric constant of the member used for the touch panel is important for the response and malfunction of the sensor of the touch panel.
  • Patent Document 1 by reducing the dielectric constant of the pressure-sensitive adhesive layer, a branched alkyl group having 10 to 24 carbon atoms is attached to the end of the ester group in order to improve the response speed of the touch panel and prevent malfunction.
  • a pressure-sensitive adhesive comprising a (meth) acrylic polymer obtained by polymerizing a monomer component containing 19 to 99.5% by weight of an alkyl (meth) acrylate having an alkyl group is proposed.
  • Patent Document 1 attempts to achieve a low dielectric constant of the pressure-sensitive adhesive layer by using a low-polarity monomer.
  • a low-polarity monomer are special and not readily available, and are not suitable for mass production.
  • the (meth) acrylic polymer of Patent Document 1 has low polarity, there arises a problem that the adhesiveness of the obtained adhesive to a glass plate, an acrylic plate, or the like is deteriorated.
  • the pressure-sensitive adhesive layer that can be used is limited. Moreover, if the composition of the (meth) acrylic polymer constituting the pressure-sensitive adhesive layer is changed in order to improve the heat and heat whitening resistance, the dielectric constant of the pressure-sensitive adhesive layer tends to increase.
  • the present invention has been made in view of the actual situation as described above, and does not change the dielectric constant of the pressure-sensitive adhesive layer resulting from the (meth) acrylic acid ester polymer in the pressure-sensitive adhesive composition, and is resistant to heat and heat whitening. It is an object of the present invention to provide a pressure-sensitive adhesive composition capable of improving the property, and a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet obtained using the pressure-sensitive adhesive composition.
  • the present invention provides a pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester polymer (A) and a cyclodextrin (B). (Invention 1).
  • the adhesive composition according to the invention (Invention 1) can suppress wet heat whitening in the obtained adhesive by containing the cyclodextrins (B).
  • cyclodextrins (B) are compounds with a low dielectric constant, even if cyclodextrin (B) is contained in the adhesive composition, an increase in dielectric constant is suppressed in the obtained adhesive. Therefore, the obtained pressure-sensitive adhesive has improved wet heat whitening resistance without changing the dielectric constant, and has an excellent balance between dielectric constant and wet heat whitening resistance.
  • the said (meth) acrylic acid ester polymer (A) contains the monomer which has a hydroxyl group, and / or the monomer which has a carboxyl group as a monomer unit which comprises the said polymer. (Invention 2).
  • the (meth) acrylic acid ester polymer (A) contains 0.1 to 15% by mass of the monomer having a hydroxyl group as a monomer unit constituting the polymer, or It is preferable to contain 0.1 to 8% by mass of a monomer having a carboxyl group (Invention 3).
  • the content of cyclodextrins (B) in the adhesive composition is 0.1 to 20 masses per 100 parts by mass of the (meth) acrylic acid ester polymer (A). Part (Invention 4).
  • the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 200,000 to 900,000 (Invention 5).
  • the cyclodextrins (B) are preferably modified cyclodextrins (Invention 6).
  • the modified cyclodextrin is preferably a partially methylated cyclodextrin (Invention 7).
  • the degree of substitution of the modified cyclodextrin is preferably 0.2 to 2.5 (Invention 8).
  • the present invention provides an adhesive obtained by curing the above-mentioned adhesive composition (Invention 1 to 9) (Invention 10).
  • the dielectric constant in 0.1 MHz of the said adhesive is 9.0 or less (invention 11).
  • the haze value is preferably 0.1 to 2.0% (Invention 12).
  • the present invention includes two release sheets and an adhesive layer sandwiched between the release sheets so as to be in contact with the release surfaces of the two release sheets, and the adhesive layer is the adhesive.
  • a pressure-sensitive adhesive sheet comprising (Inventions 10 to 12) is provided (Invention 13).
  • the said adhesive layer is arrange
  • the pressure-sensitive adhesive composition according to the present invention forms a pressure-sensitive adhesive with improved moisture and heat whitening resistance without changing the dielectric constant of the pressure-sensitive adhesive layer resulting from the (meth) acrylic acid ester polymer in the composition. can do. Moreover, the pressure-sensitive adhesive and pressure-sensitive adhesive sheet according to the present invention have an excellent balance between dielectric constant and resistance to moist heat whitening.
  • the pressure-sensitive adhesive composition according to this embodiment contains a (meth) acrylic acid ester polymer (A) and cyclodextrins (B), Furthermore, it contains at least one of a crosslinking agent (C) and an active energy ray-curable compound (D).
  • (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. The same applies to other similar terms.
  • the “polymer” includes the concept of “copolymer”.
  • a predetermined amount of hydroxyl groups derived from the cyclodextrins (B) remains in the obtained pressure-sensitive adhesive by containing the cyclodextrins (B).
  • a hydroxyl group is a hydrophilic group, and when such a hydrophilic group is present in a pressure-sensitive adhesive, even if the pressure-sensitive adhesive is placed under a high temperature and high humidity condition, it penetrates into the pressure sensitive adhesive under the high temperature and high humidity condition. As a result, the whitening of the pressure-sensitive adhesive is suppressed. Therefore, it is not necessary to change the composition or the like of the (meth) acrylic acid ester polymer constituting the pressure-sensitive adhesive layer in order to improve the moisture and heat whitening resistance.
  • cyclodextrins (B) are compounds having a low dielectric constant. Therefore, even if cyclodextrin (B) is contained in adhesive composition P, the resulting adhesive is obtained. An increase in dielectric constant is suppressed in the agent. Therefore, the resulting pressure-sensitive adhesive has improved heat and heat whitening resistance while suppressing changes in the dielectric constant due to the (meth) acrylic acid ester polymer (A). The balance is excellent.
  • the (meth) acrylic acid ester polymer (A) is an adhesive main agent in the adhesive composition P.
  • the (meth) acrylic acid ester polymer (A) usually contains a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms as the monomer unit constituting the polymer, preferably the main component Contained as. Thereby, the obtained adhesive can express preferable adhesiveness.
  • Examples of (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n- (meth) acrylate.
  • examples thereof include n-dodecyl, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
  • (meth) acrylic acid esters having an alkyl group having 1 to 8 carbon atoms are preferred, such as methyl (meth) acrylate, n-butyl (meth) acrylate and (meth) acrylic.
  • the acid 2-ethylhexyl is particularly preferred.
  • these may be used independently and may be used in combination of 2 or more type.
  • the (meth) acrylic acid ester polymer (A) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a monomer unit constituting the polymer, from the viewpoint of imparting adhesiveness.
  • the content is preferably 30% by mass or more, particularly preferably 60% by mass or more, and more preferably 80% by mass or more.
  • the content of the (meth) acrylic acid ester polymer (A) contains a hydroxyl group-containing monomer and / or a carboxyl group-containing monomer
  • the content of the (meth) acrylic acid alkyl ester whose alkyl group has 1 to 20 carbon atoms The upper limit is preferably the remainder excluding the hydroxyl group-containing monomer and the carboxyl group-containing monomer.
  • the (meth) acrylic acid ester polymer (A) preferably contains a monomer having a hydroxyl group and / or a monomer having a carboxyl group as a monomer unit constituting the polymer.
  • the (meth) acrylic acid ester polymer (A) containing a monomer having a hydroxyl group and / or a monomer having a carboxyl group as a monomer unit is excellent in compatibility with the cyclodextrins (B).
  • the adhesive composition P contains a crosslinking agent (C)
  • the reactivity with the crosslinking agent is excellent.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth And (meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate.
  • carboxyl group-containing monomer examples include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
  • carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
  • (Meth) acrylic acid is preferable from the viewpoint of copolymerization with other monomers, and acrylic acid is particularly preferable. These may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester polymer (A) contains 0.1 to 15% by mass, particularly 0.5 to 12% by mass, more preferably 1 to 10% by mass of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. %, Or 0.1 to 8% by mass, particularly 1 to 5% by mass of the carboxyl group-containing monomer.
  • the resulting adhesive has a sufficiently low dielectric constant.
  • the adhesive composition P according to this embodiment contains the cyclodextrins (B), even when the content of the hydroxyl group-containing monomer or the carboxyl group-containing monomer is defined in the low numerical range as described above, The resulting pressure-sensitive adhesive has excellent moisture and heat whitening resistance.
  • the pressure-sensitive adhesive composition P is a crosslinking agent (C ), The reaction with the crosslinking agent (C) is good.
  • the (meth) acrylic acid ester polymer (A) may contain other monomers as a monomer unit constituting the polymer, if desired.
  • the other monomer is preferably a monomer that does not contain a reactive functional group so as not to interfere with the action of the hydroxyl group-containing monomer or the carboxyl group-containing monomer.
  • Such other monomers include, for example, (meth) acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, and aliphatic rings such as cyclohexyl (meth) acrylate (meta Non-crosslinkable acrylamide such as acrylic ester, acrylamide, methacrylamide, etc.
  • Non-crosslinkable tertiary such as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate
  • examples thereof include (meth) acrylic acid ester having an amino group, vinyl acetate, and styrene. These may be used alone or in combination of two or more.
  • the polymerization mode of the (meth) acrylic acid ester polymer (A) may be a random copolymer or a block copolymer.
  • the (meth) acrylic acid ester polymer (A) preferably has a weight average molecular weight of 200,000 to 900,000, particularly preferably 250,000 to 700,000, and more preferably 300,000 to 600,000. preferable.
  • the weight average molecular weight in this specification is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the weight-average molecular weight of the (meth) acrylic acid ester polymer (A), which is the main component of the pressure-sensitive adhesive composition P, is 200,000 or more, so that the pressure-sensitive adhesive obtained has sufficient cohesive strength and is durable. It will be excellent.
  • a printed layer that becomes a step is often provided at the peripheral portion of the cover material, but the weight average of the (meth) acrylate polymer (A) When the molecular weight is 900,000 or less, the followability to the printing step is good.
  • the (meth) acrylic acid ester polymer (A) may be used alone or in combination of two or more.
  • Cyclodextrins (B) Cyclodextrin is a cyclic oligosaccharide having glucose as a structural unit, and has 3 hydroxyl groups per glucose structural unit.
  • cyclodextrins and modified dextrins in which some of the hydroxyl groups of cyclodextrins are substituted with other functional groups are collectively referred to as “cyclodextrins”.
  • the cyclodextrins (B) used in the present embodiment exclude those constituting a ring component having a rotaxane structure.
  • the pressure-sensitive adhesive composition P according to the present embodiment contains cyclodextrins (B), so that the resulting pressure-sensitive adhesive has heat and heat whitening resistance. It is excellent, specifically, whitening is suppressed when it is returned to room temperature and normal humidity after being subjected to high temperature and high humidity conditions (for example, under conditions of 85 ° C. and 85% RH for 72 hours).
  • cyclodextrins (B) are compounds having a low dielectric constant, in the pressure-sensitive adhesive obtained from the pressure-sensitive adhesive composition P, an increase in the dielectric constant is suppressed, and the balance between the dielectric constant and resistance to moist heat whitening is achieved. It will be excellent.
  • cyclodextrins those having 5 or more glucose structural units are known.
  • cyclodextrins (B) used in this embodiment ⁇ -cyclodextrins ( ⁇ -cyclodextrins having 6 structural units) are known.
  • Dextrin and modified ⁇ -cyclodextrin (the same shall apply hereinafter)), ⁇ -cyclodextrins having a structural unit of 7 and ⁇ -cyclodextrins having a structural unit of 8 can be preferably used.
  • ⁇ -cyclodextrins are preferred from the viewpoint of improving thermal whitening properties and lowering the dielectric constant.
  • cyclodextrins (B) from the viewpoint of compatibility with other components in the adhesive composition P (for example, (meth) acrylic acid ester polymer (A), etc.), some of the hydroxyl groups of cyclodextrin are It is preferable to use a modified cyclodextrin substituted with another functional group.
  • the other functional group include an alkoxy group such as a methoxy group and an ethoxy group, and an acyl group such as an acetyl group.
  • a methoxy group is particularly preferable from the viewpoint of compatibility with the (meth) acrylic acid ester polymer (A) and the diluent solvent.
  • a cyclodextrin in which one or a plurality of hydroxyl groups are left and another hydroxyl group is substituted with a methoxy group is a partially methylated cyclodextrin.
  • the degree of substitution in the modified cyclodextrin is preferably 0.2 to 2.5, particularly 0.5 to 2.0, from the viewpoint of compatibility with the other components in the adhesive composition P. preferable.
  • the degree of substitution of the modified cyclodextrin in this specification is the number of hydroxyl groups substituted with other functional groups per glucose constituent unit, and all three hydroxyl groups in one glucose constituent unit are substituted. If it is done, it becomes 3.0.
  • the content of the cyclodextrins (B) in the adhesive composition P is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A).
  • the amount is preferably 5 to 10 parts by mass, and more preferably 1 to 4 parts by mass.
  • the content of the cyclodextrins (B) is 100 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A)
  • the moisture and heat whitening resistance of the adhesive obtained from the adhesive composition P Is more preferable, and when it is 20 parts by mass or less, the pressure-sensitive adhesive properties and optical properties of the pressure-sensitive adhesive obtained are preferable.
  • the pressure-sensitive adhesive composition P preferably further contains at least one of a crosslinking agent (C) and an active energy ray-curable compound (D).
  • the adhesive composition P contains at least one of the crosslinking agent (C) and the active energy ray-curable compound (D)
  • the cohesive force of the obtained adhesive is improved.
  • the pressure-sensitive adhesive composition P further contains a cross-linking agent (C), thereby cross-linking the (meth) acrylic acid ester polymer (A) to form a three-dimensional network structure. Improve durability.
  • the crosslinking agent (C) may be any one that reacts with the reactive group (hydroxyl group or carboxyl group) of the (meth) acrylic acid ester polymer (A).
  • an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent for example, an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent.
  • a crosslinking agent (C) can be used individually by 1 type or in combination of 2 or more types.
  • the (meth) acrylic acid ester polymer (A) contains a hydroxyl group-containing monomer
  • an isocyanate-based crosslinking agent having excellent reactivity with the hydroxyl group.
  • the (meth) acrylic acid ester polymer (A) contains a carboxyl group-containing monomer
  • at least one selected from an epoxy-based crosslinking agent and an isocyanate-based crosslinking agent excellent in reactivity with a carboxyl group is used as a crosslinking agent ( It is preferable to use as C), and it is particularly preferable to use an epoxy-based crosslinking agent.
  • the isocyanate-based crosslinking agent contains at least a polyisocyanate compound.
  • the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, etc.
  • biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
  • low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
  • trimethylolpropane-modified aromatic polyisocyanate, particularly trimethylolpropane-modified tolylene diisocyanate is preferable from the viewpoint of reactivity with hydroxyl groups.
  • epoxy-based crosslinking agent examples include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl.
  • examples include ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like.
  • the content of the crosslinking agent (C) in the pressure-sensitive adhesive composition P is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A), particularly 0. .05 to 1 part by mass is preferred.
  • the content of the crosslinking agent (C) is 0.01 parts by mass or more, the cohesive force and durability of the obtained pressure-sensitive adhesive are more excellent.
  • the content of the crosslinking agent (C) is 5 parts by mass or less, the pressure-sensitive adhesive is obtained when the hydroxyl group or carboxyl group of the (meth) acrylic acid ester polymer (A) reacts with the crosslinking agent (C).
  • the hydroxyl group or carboxyl group in the residue remains sufficiently, and the moisture and heat whitening resistance is good.
  • the content of the crosslinking agent (C) is 5 parts by mass or less, the degree of crosslinking is not excessive, and the followability to a printing step becomes good.
  • the pressure-sensitive adhesive composition P further contains the active energy ray-curable compound (D), so that the obtained pressure-sensitive adhesive is excellent in durability when it is cured by irradiation with active energy rays.
  • the active energy ray-curable compound (D) may be either a monomer or an oligomer, or a mixture thereof. Among them, a polyfunctional acrylate monomer having a molecular weight of 1000 or less that is excellent in compatibility with the (meth) acrylic acid ester polymer (A) and the like can be preferably exemplified.
  • polyfunctional acrylate monomers having a molecular weight of 1000 or less examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene.
  • an active energy ray-curable acrylate oligomer can also be used.
  • the acrylate oligomer preferably has a weight average molecular weight of 50,000 or less.
  • examples of such acrylate oligomers include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, and silicone acrylate.
  • the active energy ray-curable compound (D) can be used by selecting one from among the above-mentioned polyfunctional acrylate monomers and acrylate oligomers, or can be used in combination of two or more. It can also be used in combination with other active energy ray-curable components.
  • the content of the active energy ray-curable compound (D) is 100 parts by mass of the (meth) acrylic acid ester polymer (A).
  • the amount is preferably 1 to 25 parts by mass, particularly preferably 3 to 20 parts by mass, and further preferably 5 to 15 parts by mass.
  • the adhesive composition P is optionally added with various additives such as a photopolymerization initiator, a silane coupling agent, a refractive index adjusting agent, an antistatic agent, a tackifier, an antioxidant, an ultraviolet absorber, a light It may contain stabilizers, softeners, fillers and the like.
  • the adhesive composition P contains the active energy ray-curable compound (D)
  • the adhesive composition P when ultraviolet rays are used as the active energy ray for curing the adhesive composition P, the adhesive composition P is a photopolymerization initiator. It is preferable to contain. By containing the photopolymerization initiator, the pressure-sensitive adhesive composition P containing the active energy ray-curable compound (D) can be efficiently cured, and the polymerization curing time and active energy ray irradiation amount are reduced. be able to.
  • photopolymerization initiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethyla Nobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthr
  • the photopolymerization initiator is preferably used in an amount in the range of 0.1 to 30 parts by mass, particularly 1 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (D).
  • the adhesive composition P preferably contains a silane coupling agent from the viewpoint of improving the adhesiveness of the obtained adhesive.
  • a silane coupling agent an organosilicon compound having at least one alkoxysilyl group in the molecule, having good compatibility with other components in the pressure-sensitive adhesive composition P, and having light transmittance is preferable.
  • silane coupling agents include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) silicon compounds having an epoxy structure such as ethyltrimethoxysilane, mercapto group-containing silicon compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane Amino group-containing compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, etc.
  • silicon compounds such as
  • the content of the silane coupling agent in the adhesive composition P is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A).
  • the amount is preferably 0.1 to 1.0 part by mass, and more preferably 0.2 to 0.5 part by mass.
  • Adhesive composition P produced (meth) acrylic acid ester polymer (A), and obtained (meth) acrylic acid ester polymer (A) and cyclodextrins (B). And a crosslinking agent (C), an active energy ray-curable compound (D), other additives, and the like, if desired.
  • the (meth) acrylic acid ester polymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by an ordinary radical polymerization method.
  • the polymerization of the (meth) acrylic acid ester polymer (A) can be performed by a solution polymerization method or the like using a polymerization initiator as desired.
  • the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone and the like, and two or more kinds may be used in combination.
  • Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more kinds may be used in combination.
  • Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like.
  • organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
  • organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
  • examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
  • the weight average molecular weight of the resulting polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
  • the solution of the (meth) acrylic acid ester polymer (A) is added to the cyclodextrin (B), and optionally a crosslinking agent (C), active energy rays.
  • a curable compound (D), another additive, a diluting solvent, and the like are added and mixed thoroughly to obtain a pressure-sensitive adhesive composition P (coating solution) diluted with a solvent.
  • the dilution solvent examples include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, Alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolve solvents such as ethyl cellosolve and the like are used.
  • aliphatic hydrocarbons such as hexane, heptane, and cyclohexane
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as methylene chloride and
  • the concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it is within a coatable range, and can be appropriately selected according to the situation. For example, dilution is performed so that the concentration of the adhesive composition P is 10 to 40% by mass.
  • a dilution solvent etc. is not a necessary condition, and if a viscosity etc. which can be coated with the adhesive composition P are not necessary, a dilution solvent does not need to be added.
  • the adhesive composition P becomes a coating solution using the polymerization solvent of the (meth) acrylic acid ester polymer (A) as a dilution solvent.
  • the pressure-sensitive adhesive according to this embodiment is obtained by curing the pressure-sensitive adhesive composition P.
  • the pressure-sensitive adhesive composition P does not contain the active energy ray-curable compound (D)
  • the pressure-sensitive adhesive composition P is applied to the release surface of the release sheet and then dried, preferably heat-treated to be cured.
  • An adhesive can be obtained. After the heat treatment, a curing period of about 1 to 2 weeks may be provided at room temperature (for example, 23 ° C., 50% RH) as necessary.
  • the adhesive composition P contains the active energy ray-curable compound (D)
  • the adhesive composition P is applied to the release surface of the release sheet and then dried, preferably heat-treated, and then activated.
  • An adhesive can be obtained by irradiating and curing energy rays.
  • a method for applying the coating solution of the adhesive composition P for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
  • drying of the adhesive composition P may be performed by air drying, it is usually performed by heat treatment (preferably hot air drying).
  • the heating temperature is preferably 50 to 150 ° C., particularly preferably 70 to 120 ° C.
  • the heating time is preferably 10 seconds to 10 minutes, particularly preferably 50 seconds to 2 minutes.
  • active energy rays ultraviolet rays, electron beams and the like are usually used.
  • the dose of the active energy ray varies depending on the type of the energy ray, for example, in the case of ultraviolet rays, preferably 50 ⁇ 1000mJ / cm 2 in quantity, especially 100 ⁇ 500mJ / cm 2 preferably.
  • an electron beam about 10 to 1000 krad is preferable.
  • the adhesive composition P contains a crosslinking agent (C)
  • the (meth) acrylic acid ester polymer (A) is crosslinked by the crosslinking agent (C) by drying (heating treatment) of the adhesive composition P.
  • the adhesive component of the adhesive composition P contains the active energy ray-curable compound (D)
  • D active energy ray-curable compound
  • the dielectric constant at 0.1 MHz of the pressure-sensitive adhesive according to this embodiment is preferably 9.0 or less.
  • the touch panel manufactured using the pressure-sensitive adhesive can contribute to suppression of malfunction and improvement of responsiveness. it can.
  • the pressure-sensitive adhesive according to the present embodiment is such that the pressure-sensitive adhesive composition P contains a cyclodextrin (B), so that the pressure-sensitive adhesive obtained in the pressure-sensitive adhesive composition P contains a cyclodextrin (B). In addition, it exhibits excellent moisture and heat whitening resistance without greatly changing the dielectric constant.
  • the monomer unit constituting the polymer has a hydroxyl group-containing monomer content of 15% by mass or less, or a carboxyl group-containing monomer. When the content is 8% by mass or less, the obtained adhesive has a sufficiently low dielectric constant, and the above-described dielectric constant at 0.1 MHz can be easily achieved.
  • the measuring method of the dielectric constant of an adhesive is as showing to the test example mentioned later.
  • the gel fraction of the pressure-sensitive adhesive according to this embodiment is preferably 15 to 95%, particularly preferably 40 to 90%, and more preferably 60 to 85%.
  • the cohesive force of the pressure-sensitive adhesive is sufficient and the durability is excellent.
  • the gel fraction is 95% or less, excellent step following performance is exhibited and the adhesiveness can be kept high.
  • the measuring method of a gel fraction is as showing to the test example mentioned later.
  • the pressure-sensitive adhesive sheet 1 As shown in FIG. 1, the pressure-sensitive adhesive sheet 1 according to this embodiment includes two release sheets 12a and 12b and the two release sheets 12a so as to be in contact with the release surfaces of the two release sheets 12a and 12b. , 12b and an adhesive layer 11 sandwiched between the two layers.
  • the release sheets 12a and 12b in the pressure-sensitive adhesive sheet 1 are not essential components, and are peeled and removed when the pressure-sensitive adhesive sheet 1 is used.
  • the release surface of the release sheet in this specification refers to a surface having peelability in the release sheet, and includes both a surface that has been subjected to a release treatment and a surface that exhibits peelability without being subjected to a release treatment. .
  • the adhesive layer 11 is comprised from the adhesive formed by bridge
  • the thickness of the pressure-sensitive adhesive layer 11 (value measured according to JIS K7130) is preferably 10 to 300 ⁇ m, particularly preferably 25 to 250 ⁇ m, and more preferably 50 to 100 ⁇ m. When the thickness of the pressure-sensitive adhesive layer 11 is 10 ⁇ m or more, excellent adhesive force is sufficiently exhibited, and when the thickness of the pressure-sensitive adhesive layer 11 is 300 ⁇ m or less, workability is improved. Further, when the thickness of the pressure-sensitive adhesive layer 11 is 25 to 100 ⁇ m, it is suitable for optical applications, particularly for touch panel applications.
  • the pressure-sensitive adhesive layer 11 may be formed as a single layer or may be formed by laminating a plurality of layers.
  • the haze value of the pressure-sensitive adhesive layer 11 is preferably 2.0% or less, particularly preferably 1.5% or less, and more preferably 1.0%. The following is preferable.
  • the pressure-sensitive adhesive according to this embodiment has very high transparency and is suitable for optical applications.
  • it is especially preferable that the haze value of the pressure-sensitive adhesive layer 11 is within the above range even after an evaluation test for resistance to heat and whitening described later.
  • the release sheets 12a and 12b are not particularly limited, and known plastic films can be used.
  • plastic films polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene acetate
  • a vinyl film, an ionomer resin film, an ethylene / (meth) acrylic acid copolymer film, an ethylene / (meth) acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, or the like is used.
  • These crosslinked films are also used.
  • these laminated films may be sufficient.
  • the release surface of the release sheets 12a and 12b (particularly the surface in contact with the pressure-sensitive adhesive layer 11) is preferably subjected to a release treatment.
  • the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.
  • one release sheet is preferably a heavy release release sheet having a high release force
  • the other release sheet is preferably a light release release sheet having a low release force.
  • the thickness of the release sheets 12a and 12b is not particularly limited, but is usually about 20 to 150 ⁇ m.
  • pressure-sensitive adhesive sheet As one production example of the pressure-sensitive adhesive sheet 1, a coating liquid of the above-mentioned pressure-sensitive adhesive composition P is applied to the release surface of one release sheet 12a (or 12b), and heat treatment is performed for adhesion. After the adhesive composition P is cured to form an application layer, the release surface of the other release sheet 12b (or 12a) is superimposed on the application layer. When a curing period is required, a curing period is set, and when the curing period is unnecessary, the coating layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained.
  • the conditions for the heat treatment and curing are as described above.
  • a coating liquid of the above-mentioned pressure-sensitive adhesive composition P is applied to the release surface of one release sheet 12 a, a heat treatment is performed to cure the pressure-sensitive adhesive composition P, and a coating layer To obtain a release sheet 12a with a coating layer.
  • the coating liquid of the said adhesive composition P is apply
  • a release sheet 12b is obtained. And the peeling sheet 12a with an application layer and the peeling sheet 12b with an application layer are bonded together so that both application layers may mutually contact.
  • the curing period is necessary, the curing period is set, and when the curing period is unnecessary, the above-mentioned laminated application layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained. According to this production example, even when the pressure-sensitive adhesive layer 11 is thick, it can be stably produced.
  • a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
  • a transparent conductive film made of tin-doped indium oxide (ITO) is provided on the pressure-sensitive adhesive layer 11 side of the laminate obtained by laminating the pressure-sensitive adhesive layer 11 on a base material made of a polyethylene terephthalate film having a thickness of 100 ⁇ m.
  • the adhesive strength of the laminate to the transparent conductive film is preferably 5 to 80 N / 25 mm, particularly 10 to 70 N / 25 mm. And more preferably 15 to 50 N / 25 mm.
  • the adhesive force here means the adhesive force measured by the 180 degree peeling method according to JIS200Z0237: 2009
  • the measurement sample has a width of 25 mm and a length of 100 mm, and the measurement sample is attached. After being applied to the body by applying pressure at 0.5 MPa and 50 ° C. for 20 minutes, the sample was left for 24 hours under conditions of normal pressure, 23 ° C. and 50% RH, and then measured at a peeling rate of 300 mm / min. To do.
  • the capacitive touch panel 2 shown in FIG. 2 can be manufactured.
  • the touch panel 2 includes a display module 3, a first film sensor 5 a laminated thereon via an adhesive layer 4 a, and a second film sensor 5 b laminated thereon via an adhesive layer 4 b. And the cover material 6 laminated
  • the pressure-sensitive adhesive layer 11 in the touch panel 2 is the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1.
  • Examples of the display module 3 include a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper.
  • LCD liquid crystal
  • LED light emitting diode
  • organic EL organic electroluminescence
  • the pressure-sensitive adhesive layers 4a and 4b may be formed of the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1, or may be formed of other pressure-sensitive adhesives or pressure-sensitive adhesive sheets.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 4 includes an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, and a polyvinyl ether-based pressure-sensitive adhesive.
  • an acrylic pressure-sensitive adhesive is preferable.
  • the first film sensor 5a and the second film sensor 5b are each generally composed of a base film 51 and a patterned transparent conductive film 52, respectively. Although it does not specifically limit as the base film 51, For example, a polyethylene terephthalate film, an acrylic film, a polycarbonate film etc. are used.
  • Examples of the transparent conductive film 52 include metals such as platinum, gold, silver and copper, oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
  • oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
  • Examples include composite oxides such as indium, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide, and non-oxidized compounds such as chalcogenide, lanthanum hexaboride, titanium nitride, and titanium carbide. Among these, those made of tin-doped indium oxide (ITO) are preferable.
  • One of the transparent conductive film 52 of the first film sensor 5a and the transparent conductive film 52 of the second film sensor 5b normally constitutes a circuit pattern in the X-axis direction, and the other constitutes a circuit pattern in the Y-axis direction. .
  • the transparent conductive film 52 of the second film sensor 5b is located above the second film sensor 5b in FIG.
  • the transparent conductive film 52 of the first film sensor 5a is positioned on the upper side of the first film sensor 5a in FIG. It may be located on the lower side.
  • the cover material 6 is mainly composed of a glass plate or a plastic plate.
  • the glass plate is not particularly limited. For example, chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, barium / strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass. Etc.
  • the plastic plate is not particularly limited, and examples thereof include an acrylic plate made of polymethyl methacrylate and the like, and a polycarbonate plate.
  • a functional layer such as a hard coat layer, an antireflection layer, or an antiglare layer may be provided on one side or both sides of the glass plate or plastic plate, or a hard coat film, an antireflection film, or an antiglare film.
  • Such optical members may be laminated.
  • the cover material 6 has a step on the surface on the pressure-sensitive adhesive layer 11 side, and specifically has a step due to the presence or absence of the printing layer 7.
  • the print layer 7 is generally formed in a frame shape on the pressure-sensitive adhesive layer 11 side of the cover material 6.
  • the material constituting the printing layer 7 is not particularly limited, and a known material for printing is used.
  • the thickness of the printing layer 7, that is, the height of the step, is preferably 3 to 45 ⁇ m, more preferably 5 to 35 ⁇ m, particularly preferably 7 to 25 ⁇ m, and preferably 7 to 15 ⁇ m. Further preferred.
  • the thickness (height of the step) of the printing layer 7 is preferably 3 to 30% of the thickness of the pressure-sensitive adhesive layer 11, particularly preferably 3.2 to 20%, and more preferably 3 It is preferably 5 to 15%.
  • the pressure-sensitive adhesive layer 11 can easily follow the step formed by the printing layer 7, and the occurrence of floating or bubbles in the vicinity of the step is suppressed.
  • One release sheet 12a is peeled from the pressure-sensitive adhesive sheet 1, and the exposed pressure-sensitive adhesive layer 11 is bonded to the second film sensor 5b so as to be in contact with the patterned transparent conductive film 52 of the second film sensor 5b.
  • the pressure-sensitive adhesive layer 4b provided on the release sheet is bonded to the first film sensor 5a so as to be in contact with the patterned transparent conductive film 52 of the first film sensor 5a.
  • the release film remaining on the pressure-sensitive adhesive layer 4b is peeled off, and the exposed pressure-sensitive adhesive layer 4b is opposite to the surface on which the pressure-sensitive adhesive layer 11 is laminated in the second film sensor 5b (second surface). Both are bonded so that it may touch the exposed surface of the base film 51 of the film sensor 5b. Thereby, the laminated body by which the peeling sheet 12b, the adhesive layer 11, the 2nd film sensor 5b, the adhesive layer 4b, and the 1st film sensor 5a are laminated
  • the pressure-sensitive adhesive layer 4a provided on the release sheet is bonded to the surface of the laminate on the first film sensor 5a side (exposed surface of the base film 51 of the first film sensor 5a).
  • the other release sheet 12b is peeled from the laminate, and the cover material 6 is pasted so that the printed layer 7 side of the cover material 6 contacts the pressure-sensitive adhesive layer 11 with respect to the exposed pressure-sensitive adhesive layer 11. Match.
  • the release sheet is peeled from the structure, and the structure is bonded to the display module 3 so that the exposed adhesive layer 4a is in contact with the display module 3. Thereby, the touch panel 2 shown in FIG. 2 is manufactured.
  • the dielectric constant of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 11 is low, malfunction caused by the pressure-sensitive adhesive layer 11 is effectively suppressed, and the responsiveness of the touch panel sensor is improved. is doing. Furthermore, since the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 11 is excellent in moisture and heat whitening resistance, whitening when the touch panel 2 returns to room temperature after being placed in a high temperature and high humidity condition is suppressed.
  • one of the release sheets 12a and 12b in the pressure-sensitive adhesive sheet 1 may be omitted.
  • Example 1 Preparation of (meth) acrylic acid ester polymer 70 parts by weight of n-butyl acrylate, 20 parts by weight of methyl acrylate and 10 parts by weight of 2-hydroxyethyl acrylate were copolymerized to give a (meth) acrylic acid ester polymer ( A) was prepared. When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method described later, it was a weight average molecular weight of 600,000.
  • Table 1 and Table 2 show the composition of the adhesive composition including Examples and Comparative Examples described later. Details of the abbreviations described in Table 1 and Table 2 are as follows.
  • [(Meth) acrylic acid ester polymer] BA: n-butyl acrylate MA: methyl acrylate MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate AA: acrylic acid
  • a pressure-sensitive adhesive sheet was obtained as a laminate composed of a heavy release type release sheet / adhesive layer (thickness: 50 ⁇ m) / light release type release sheet.
  • the thickness of the pressure-sensitive adhesive layer is a value measured using a constant pressure thickness measuring instrument (manufactured by Teclock, product name “PG-02”) in accordance with JIS K7130 (hereinafter the same).
  • Table 1 shows the ratio of each monomer constituting the (meth) acrylic acid ester polymer (A), the weight average molecular weight of the (meth) acrylic acid ester polymer (A), and the blending amount of the cyclodextrins (B).
  • a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the above was changed.
  • Example 4 Preparation of (meth) acrylate polymer
  • Polymer (meth) acrylate polymer (A) was prepared by copolymerizing 77 parts by weight of n-butyl acrylate, 20 parts by weight of methyl methacrylate and 3 parts by weight of acrylic acid. did. When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method described later, it was a weight average molecular weight of 600,000.
  • a pressure-sensitive adhesive sheet having a structure of mold release sheet / coating layer (thickness: 50 ⁇ m) / light release release sheet was prepared. Then, the adhesive sheet was obtained by irradiating an ultraviolet-ray through the peeling sheet on the following conditions, hardening the said application layer and making it an adhesive layer. In addition, the thickness of the formed adhesive layer was 50 micrometers. ⁇ Ultraviolet irradiation conditions> Fusion Co. electrodeless lamp H bulb used, illuminance 600 mW / cm 2, light quantity 150 mJ / cm 2 ⁇ UV illuminance / light meter uses "UVPF-36" manufactured by Eye Graphics.
  • Table 2 shows the ratio of each monomer constituting the (meth) acrylic acid ester polymer (A), the weight average molecular weight of the (meth) acrylic acid ester polymer (A), and the blending amount of the cyclodextrins (B).
  • a pressure-sensitive adhesive sheet was produced in the same manner as in Example 4 except that the above was changed.
  • the above-mentioned weight average molecular weight (Mw) is a polystyrene-reduced weight average molecular weight measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).
  • GPC measurement device manufactured by Tosoh Corporation, HLC-8020 GPC column (passed in the following order): TSK guard column HXL-H manufactured by Tosoh Corporation TSK gel GMHXL ( ⁇ 2) TSK gel G2000HXL ⁇ Measurement solvent: Tetrahydrofuran ⁇ Measurement temperature: 40 ° C.
  • a transparent conductive film (Oike Industry Co., Ltd., ITO film, thickness: 125 ⁇ m) in which a transparent conductive film (ITO film) made of tin-doped indium oxide (ITO) is provided on one side of a polyethylene terephthalate (PET) film
  • ITO film transparent conductive film
  • PET film polyethylene terephthalate
  • the heavy release type release sheet was peeled off from the sample, and the exposed adhesive layer was attached to the transparent conductive film. This pasting was performed by pressurizing at a pressure of 0.5 MPa for 20 minutes under a temperature condition of 50 ° C.
  • the pressure-sensitive adhesive wrapped in the polyester mesh was immersed in ethyl acetate at room temperature (23 ° C.) for 24 hours. Thereafter, the pressure-sensitive adhesive was taken out, air-dried for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and further dried in an oven at 80 ° C. for 12 hours. After drying, the mass was weighed with a precision balance, and the mass of the pressure sensitive adhesive alone was calculated by subtracting the mass of the mesh alone. The mass at this time is M2. The gel fraction (%) is represented by (M2 / M1) ⁇ 100. The results are shown in Table 3 and Table 4.
  • the laminate was stored for 72 hours under wet heat conditions of 85 ° C. and 85% RH. Then, it returns to normal temperature normal humidity of 23 degreeC and 50% RH, About the said laminated body, using a haze meter (the Nippon Denshoku Industries Co., Ltd. make, product name "NDH2000”), haze value (in accordance with JIS K7136: 2000) %). In addition, the said haze value was measured within 30 minutes after returning a laminated body to normal temperature normal humidity.
  • a haze value increase (points) after the wet heat condition was calculated by subtracting the haze value before the wet heat condition from the haze value after the wet heat condition. Based on the obtained increase in haze value, the resistance to moist heat whitening was evaluated according to the following criteria. The results are shown in Table 3 and Table 4.
  • A Very good (haze increase after wet heat condition is less than 1.0 point)
  • ⁇ Good (the increase in haze value after wet heat conditions is 1.0 point or more and less than 1.5 point)
  • ⁇ within suitability value (increase in haze value after wet heat condition is 1.5 points or more and less than 2.0 points)
  • X Defect (increased haze value after wet heat condition is 2.0 points or more)
  • ⁇ s (C3 ⁇ d) / ( ⁇ 0 ⁇ S) ⁇ s : dielectric constant of adhesive ⁇ 0 : dielectric constant of vacuum (8.854 ⁇ 10 ⁇ 12 )
  • C3 Capacitance of the adhesive S: Area of the adhesive layer d: Thickness of the adhesive layer
  • irradiation with ultraviolet rays 80 W / cm 2 , 2 metal halide lamps, lamp height 15 cm, belt speed 10 to 15 m / min
  • a level difference due to printing level difference
  • the light release type release sheet was peeled off from the pressure sensitive adhesive sheets obtained in Examples and Comparative Examples, and the exposed pressure sensitive adhesive layer was easily made of a polyethylene terephthalate film (PET A4300, thickness: 100 ⁇ m) having an easy adhesion layer. Bonded to the adhesive layer. Next, the heavy release type release sheet was peeled off to expose the pressure-sensitive adhesive layer. Then, using a laminator (product name “LPD3214”, manufactured by Fuji Plastics Co., Ltd.), the laminate is laminated on each stepped glass plate so that the adhesive layer covers the entire frame-like print, and this is used as an evaluation sample. did.
  • PET A4300 polyethylene terephthalate film
  • the pressure-sensitive adhesive sheets obtained in the examples were excellent in moisture and heat whitening resistance while keeping the dielectric constant low. Moreover, the adhesive sheets obtained in the examples and comparative examples were all good in adhesive strength, haze, and step following ability.
  • the pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet of the present invention can be suitably used for producing a touch panel with few malfunctions.

Landscapes

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

Abstract

Cette invention concerne une feuille adhésive (1) qui comprend deux feuilles anti-adhésives (12a, 12b) et une couche adhésive (11) qui est prise en sandwich entre les feuilles anti-adhésives (12a, 12b) de façon à être en contact avec les surfaces des deux feuilles anti-adhésives (12a, 12b), la couche adhésive (11) étant constituée d'un adhésif qui est obtenu par durcissement d'une composition adhésive qui contient un polymère d'ester d'acide (méth)acrylique (A) et une cyclodextrine (B). Cette feuille adhésive (1) présente un excellent équilibre entre constante diélectrique et résistance au blanchiment en présence de chaleur humide. Il est préférable que le polymère d'ester d'acide (méth)acrylique (A) contienne un monomère ayant un groupe hydroxyle et/ou un monomère ayant un groupe carboxyle à titre de motif monomère constitutif du polymère.
PCT/JP2014/059605 2014-03-31 2014-03-31 Composition adhésive, adhésif, et feuille adhésive Ceased WO2015151224A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2016511243A JP6325653B2 (ja) 2014-03-31 2014-03-31 粘着性組成物、粘着剤および粘着シート
PCT/JP2014/059605 WO2015151224A1 (fr) 2014-03-31 2014-03-31 Composition adhésive, adhésif, et feuille adhésive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/059605 WO2015151224A1 (fr) 2014-03-31 2014-03-31 Composition adhésive, adhésif, et feuille adhésive

Publications (1)

Publication Number Publication Date
WO2015151224A1 true WO2015151224A1 (fr) 2015-10-08

Family

ID=54239592

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/059605 Ceased WO2015151224A1 (fr) 2014-03-31 2014-03-31 Composition adhésive, adhésif, et feuille adhésive

Country Status (2)

Country Link
JP (1) JP6325653B2 (fr)
WO (1) WO2015151224A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019182928A (ja) * 2018-04-03 2019-10-24 王子ホールディングス株式会社 粘着剤組成物、粘着シート及び積層体
WO2022168714A1 (fr) * 2021-02-08 2022-08-11 リンテック株式会社 Agent adhésif, feuille adhésive, film optique pourvu d'un agent adhésif, et stratifié optique
JPWO2023012947A1 (fr) * 2021-08-04 2023-02-09
WO2023127219A1 (fr) * 2021-12-28 2023-07-06 リンテック株式会社 Adhésif à base de silicone, feuille adhésive et feuille adhésive double face
WO2023166775A1 (fr) * 2022-03-03 2023-09-07 リンテック株式会社 Feuille adhésive et dispositif flexible
CN116802252A (zh) * 2021-02-08 2023-09-22 琳得科株式会社 粘着剂、粘着片、带粘着剂层的光学膜及光学层叠体
WO2023223787A1 (fr) * 2022-05-17 2023-11-23 リンテック株式会社 Composition adhésive, adhésif, feuille adhésive, corps d'affichage et dispositif de pliage répété
WO2024202546A1 (fr) * 2023-03-28 2024-10-03 リンテック株式会社 Feuille recyclable

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09511782A (ja) * 1994-11-10 1997-11-25 ワッカー・ケミー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング シクロデキストリン又はシクロデキストリン誘導体を含んでなる再分散性ポリマー粉末組成物
JP2002502898A (ja) * 1998-02-03 2002-01-29 ミネソタ マイニング アンド マニュファクチャリング カンパニー デキストリンを用いる（メタ）アクリル酸モノマーの懸濁重合の方法、及びその方法から得られるポリマービーズ
JP2004509214A (ja) * 2000-09-14 2004-03-25 ローム　アンド　ハース　カンパニー グラフトコポリマーを含有する接着剤組成物
JP2005154602A (ja) * 2003-11-26 2005-06-16 Lintec Corp 抗菌性粘着製品
JP2007169629A (ja) * 2005-12-01 2007-07-05 Rohm & Haas Co 活性物質を安定化させるための水性ポリマー分散物
JP2011160916A (ja) * 2010-02-08 2011-08-25 Lion Corp 消臭機能付き粘着シートおよびこれを備えた粘着クリーナ
JP2013203854A (ja) * 2012-03-28 2013-10-07 Lintec Corp 粘着性組成物、粘着剤および粘着シート
JP2013209586A (ja) * 2012-03-30 2013-10-10 Lintec Corp 粘着性組成物、粘着剤および粘着シート

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09511782A (ja) * 1994-11-10 1997-11-25 ワッカー・ケミー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング シクロデキストリン又はシクロデキストリン誘導体を含んでなる再分散性ポリマー粉末組成物
JP2002502898A (ja) * 1998-02-03 2002-01-29 ミネソタ マイニング アンド マニュファクチャリング カンパニー デキストリンを用いる（メタ）アクリル酸モノマーの懸濁重合の方法、及びその方法から得られるポリマービーズ
JP2004509214A (ja) * 2000-09-14 2004-03-25 ローム　アンド　ハース　カンパニー グラフトコポリマーを含有する接着剤組成物
JP2005154602A (ja) * 2003-11-26 2005-06-16 Lintec Corp 抗菌性粘着製品
JP2007169629A (ja) * 2005-12-01 2007-07-05 Rohm & Haas Co 活性物質を安定化させるための水性ポリマー分散物
JP2011160916A (ja) * 2010-02-08 2011-08-25 Lion Corp 消臭機能付き粘着シートおよびこれを備えた粘着クリーナ
JP2013203854A (ja) * 2012-03-28 2013-10-07 Lintec Corp 粘着性組成物、粘着剤および粘着シート
JP2013209586A (ja) * 2012-03-30 2013-10-10 Lintec Corp 粘着性組成物、粘着剤および粘着シート

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019182928A (ja) * 2018-04-03 2019-10-24 王子ホールディングス株式会社 粘着剤組成物、粘着シート及び積層体
WO2022168714A1 (fr) * 2021-02-08 2022-08-11 リンテック株式会社 Agent adhésif, feuille adhésive, film optique pourvu d'un agent adhésif, et stratifié optique
CN116802252A (zh) * 2021-02-08 2023-09-22 琳得科株式会社 粘着剂、粘着片、带粘着剂层的光学膜及光学层叠体
KR20230145061A (ko) 2021-02-08 2023-10-17 린텍 가부시키가이샤 점착제, 점착 시트, 점착제층 부착 광학 필름, 및 광학적층체
US20240117222A1 (en) * 2021-02-08 2024-04-11 Lintec Corporation Adhesive agent, adhesive sheet, optical film provided with adhesive agent, and optical laminate
JPWO2023012947A1 (fr) * 2021-08-04 2023-02-09
WO2023012947A1 (fr) * 2021-08-04 2023-02-09 リンテック株式会社 Feuille adhésive et procédé de production de feuille adhésive
JP7728267B2 (ja) 2021-08-04 2025-08-22 リンテック株式会社 粘着シートおよび粘着シートの製造方法
WO2023127219A1 (fr) * 2021-12-28 2023-07-06 リンテック株式会社 Adhésif à base de silicone, feuille adhésive et feuille adhésive double face
WO2023166775A1 (fr) * 2022-03-03 2023-09-07 リンテック株式会社 Feuille adhésive et dispositif flexible
WO2023223787A1 (fr) * 2022-05-17 2023-11-23 リンテック株式会社 Composition adhésive, adhésif, feuille adhésive, corps d'affichage et dispositif de pliage répété
WO2024202546A1 (fr) * 2023-03-28 2024-10-03 リンテック株式会社 Feuille recyclable

Also Published As

Publication number Publication date
JPWO2015151224A1 (ja) 2017-04-13
JP6325653B2 (ja) 2018-05-16

Similar Documents

Publication Publication Date Title
JP6325653B2 (ja) 粘着性組成物、粘着剤および粘着シート
JP6356786B2 (ja) 粘着シートおよび積層体
JP6200065B2 (ja) 粘着剤および粘着シート
JP6093907B2 (ja) 粘着性組成物、粘着剤および粘着シート
JP6270988B2 (ja) 粘着剤層および飛散防止粘着シート
JP5789350B1 (ja) 粘着シートおよび積層体
JP6251293B6 (ja) 粘着シート、および表示体の製造方法
JP6374485B2 (ja) 粘着シート
JP6290377B2 (ja) 積層体
JP2017014379A (ja) 粘着性組成物、粘着シートおよび表示体
JPWO2016063405A6 (ja) 粘着シート、および表示体の製造方法
JP2018173549A (ja) 粘着性組成物、粘着剤、粘着シートおよび表示体
JP6270941B2 (ja) 粘着剤、粘着シート、および表示体の製造方法
JP2017066329A (ja) 粘着シート
JP6368410B2 (ja) タッチパネル
JP6145568B2 (ja) 粘着剤および粘着シート
JP6500077B2 (ja) 積層体
WO2017002218A1 (fr) Composition adhésive, adhésif, feuille adhésive et élément d'affichage
JP6934443B2 (ja) 粘着剤および粘着シート

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14887848

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016511243

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase
122 Ep: pct application non-entry in european phase

Ref document number: 14887848

Country of ref document: EP

Kind code of ref document: A1