WO2014020878A1 - Couche adhésive, feuille adhésive et film optique avec une couche adhésive - Google Patents

Couche adhésive, feuille adhésive et film optique avec une couche adhésive Download PDF

Info

Publication number
WO2014020878A1
WO2014020878A1 PCT/JP2013/004556 JP2013004556W WO2014020878A1 WO 2014020878 A1 WO2014020878 A1 WO 2014020878A1 JP 2013004556 W JP2013004556 W JP 2013004556W WO 2014020878 A1 WO2014020878 A1 WO 2014020878A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
mass
acrylate
sensitive adhesive
pressure
Prior art date
Application number
PCT/JP2013/004556
Other languages
English (en)
Japanese (ja)
Inventor
清恵 重富
菅野　亮
昌之 岡本
真人 山形
Original Assignee
日東電工株式会社
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
Priority claimed from JP2013091597A external-priority patent/JP2016130270A/ja
Priority claimed from JP2013091598A external-priority patent/JP2016130271A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2014020878A1 publication Critical patent/WO2014020878A1/fr

Links

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
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (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
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and an optical film with a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet is used for the purpose of adhering adherends to each other or fixing an article to the adherends by firmly adhering to the adherends. At this time, if the adhesive strength is higher than that in the initial stage of adhesion, it is difficult to reattach the adhesive. Therefore, there is a demand for an adhesive tape that has low adhesive strength at the initial stage but increases in adhesive strength with time and can provide high adhesive strength.
  • liquid crystal displays Especially in recent years, liquid crystal displays, plasma displays, organic EL displays, etc. have become widespread. In these displays, it is indispensable to dispose various optical films on both sides of the glass substrate that forms the outermost surface. For example, a polarizing film is attached to the outermost surface of the liquid crystal panel.
  • various optical elements have been used to improve the display quality of the display, for example, a retardation film as an anti-coloring film, a viewing angle widening film for improving the viewing angle of a liquid crystal display, Furthermore, a brightness enhancement film for increasing the contrast of the display is used. These films are collectively called optical films.
  • an adhesive is usually used.
  • the adhesive is pre-adhesive layer on one side of the optical film. It is provided as. That is, an adhesive optical film is generally used for attaching the optical film to the outermost surface of the liquid crystal panel.
  • the pressure-sensitive adhesive acrylic pressure-sensitive adhesives that are excellent in terms of adhesiveness, transparency, weather resistance and the like are frequently used.
  • the pressure-sensitive adhesive used for adhering the optical film may be required to have a characteristic that it can be re-applied (reworked). This is because when the optical film is bonded to the outermost surface of the display, the bonding position is often wrong, or foreign objects are often caught in the bonding surface. This is a characteristic required to enable bonding.
  • the adhesiveness to the glass substrate on the outermost surface of the display is lower.
  • the adhesion via the pressure-sensitive adhesive layer has an adhesive strength that can sufficiently withstand use in a hot and humid atmosphere. Therefore, the adhesive strength is low enough to allow rework at the beginning of pasting, and after that, even in a hot and humid atmosphere, it adheres firmly so that it does not float or peel off at the interface between the adhesive layer and the display.
  • An agent is desired.
  • a pressure-sensitive adhesive composition containing 1 to 40 parts by mass of acrylate, a polymerization initiator, and a crosslinking agent, and a pressure-sensitive adhesive sheet obtained by irradiating the pressure-sensitive adhesive composition with light have been proposed (see Patent Document 1).
  • the conventional pressure-sensitive adhesive sheet is not satisfactory because it has poor adhesive strength over time and is inferior in adhesion reliability such as holding power and constant load peeling.
  • the present invention has been made in view of these problems, and the purpose thereof is a pressure-sensitive adhesive that can be reworked at the initial stage of bonding and then firmly adheres to the adherend, and has excellent adhesion reliability. In providing adhesives.
  • An embodiment of the present invention is an adhesive layer.
  • the pressure-sensitive adhesive layer contains a (meth) acrylic polymer having a weight average molecular weight of 1000 or more and less than 30000, and has an adhesive force of 1.0 N / 25 mm or less after 30 minutes after being attached to a glass plate, It is characterized by having an adhesive strength of 5.0 N / 25 mm or more after 2 days at 40 ° C. after being attached to a glass plate.
  • the (meth) acrylic polymer may contain a monomer having a polyoxyalkylene skeleton as a monomer unit.
  • the (meth) acrylic polymer further has a polyoxyalkylene skeleton monomer represented by the following general formula (1): It may be an oxyalkylene group-containing monomer having 3 to 40.
  • R 1 is hydrogen or a methyl group
  • R 2 is hydrogen or a monovalent organic group
  • m and p are integers of 2 to 4
  • n and q are 0 or integers of 2 to 40 , N and q cannot be 0 at the same time
  • the said adhesive layer consists of an adhesive composition of any aspect mentioned above.
  • the pressure-sensitive adhesive layer of this embodiment may contain 55.0% by mass to 99.0% by mass of a solvent-insoluble component.
  • Still another embodiment of the present invention is an adhesive film.
  • the pressure-sensitive adhesive sheet includes the pressure-sensitive adhesive layer according to any one of the above-described aspects.
  • the present invention it is possible to perform reworking (rework) in the initial stage of pasting, and thereafter firmly adhere to the adherend over time, so that the adhesion reliability evaluated by holding force, constant load peeling, etc.
  • An excellent pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, and optical sheet with a pressure-sensitive adhesive layer are provided.
  • the pressure-sensitive adhesive layer according to the embodiment includes a (meth) acrylic polymer (A) having a weight average molecular weight of 1000 or more and less than 30000, and is 30 minutes after being attached to a glass plate (immediately after being attached).
  • the adhesive strength is 1.0 N / 25 mm or less, and the adhesive strength after pasting on a glass plate at 40 ° C. for 2 days (during normal storage) is 5.0 N / 25 mm or more.
  • the (meth) acrylic polymer (A) will be described in detail.
  • the (meth) acrylic polymer (A) has a weight average molecular weight of 1000 or more and less than 30000, and functions as an additive for adjusting the adhesive strength in the adhesive composition.
  • the (meth) acrylic polymer (A) may contain a monomer having a polyoxyalkylene skeleton as a monomer unit.
  • monomers used in this case (oxy) alkylene adducts, anionic reactive surfactants having reactive substituents such as acryloyl group, methacryloyl group and allyl group in the molecule, nonionic reactivity Surfactants, cationic reactive surfactants and the like can be mentioned.
  • the polyoxyalkylene chain expresses an appropriate balance between incompatibility and incompatibility between the polymer (C) and the (meth) acrylic polymer (A), which will be described later. It is possible to moderately adjust the increase in adhesive strength.
  • an oxyalkylene group-containing monomer represented by the following general formula (2) can be suitably used.
  • R 1 is hydrogen or a methyl group
  • R 2 is hydrogen or a monovalent organic group
  • m and p are integers of 2 to 4
  • n and q are 0 or 2 to 40 Is an integer and n and q cannot be 0 at the same time
  • oxyalkylene group-containing monomer examples include, for example, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octoxy polyethylene glycol (meth) acrylate, and lauroxy polyethylene glycol.
  • These oxyalkylene group-containing monomers can be used alone or in combination of two or more.
  • the polymer (C) is an oxyalkylene group-containing monomer having an average addition mole number of oxyalkylene units (the sum of n and q in the general formula (2) of 3 to 40). From the viewpoint of the compatibility of the above and the balance of adhesion reliability as a pressure-sensitive adhesive composition.
  • oxyalkylene group-containing monomers include, for example, BLEMMER PME-400, BLEMMER PME-1000, BLEMMER 50POEP-800B (all of which are manufactured by NOF Corporation), LATEMUL PD-420, LATEMUL PD-430 (above, all manufactured by Kao Corporation), Adeka Soap ER-10, Adeka Soap NE-10 (above, both manufactured by Asahi Denka Kogyo Co., Ltd.), CD552 (Sartomer Co., Ltd.) and the like.
  • the reactive surfactant include, for example, an anionic reactive surfactant having a (meth) acryloyl group or an allyl group, a nonionic reactive surfactant, and a cationic reactive surfactant. Is mentioned.
  • anionic reactive surfactant examples include those represented by the formulas (A1) to (A10).
  • R 1 in Formula (A1) represents hydrogen or a methyl group
  • R 2 represents a hydrocarbon group having 1 to 30 carbon atoms or an acyl group
  • X represents an anionic hydrophilic group
  • R 3 and R 4 are They are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and the average added mole numbers m and n are 0 to 40, where (m + n) represents a number of 3 to 40.
  • R 1 in Formula (A2) represents hydrogen or a methyl group
  • R 2 and R 7 are the same or different, represent an alkylene group having 1 to 6 carbon atoms
  • R 3 and R 5 are the same or different
  • R 4 and R 6 are the same or different and represent hydrogen, an alkyl group, a benzyl group or a styrene group
  • X represents an anionic hydrophilic group
  • average added mole numbers m and n are 0 to 40, where (m + n) represents a number from 3 to 40.
  • R 1 in Formula (A3) represents hydrogen or a methyl group
  • R 2 represents an alkylene group having 1 to 6 carbon atoms
  • X represents an anionic hydrophilic group
  • the average number of added moles n is 3 to 40 Represents a number.
  • R 1 in Formula (A4) represents hydrogen or a methyl group
  • R 2 represents a hydrocarbon group or acyl group having 1 to 30 carbon atoms
  • R 3 and R 4 may be the same or different
  • 6 represents an alkylene group
  • X represents an anionic hydrophilic group
  • the average added mole number m and n are 0 to 40
  • (m + n) represents a number of 3 to 40.
  • R 1 in Formula (A5) represents a hydrocarbon group, an amino group, or a carboxylic acid residue
  • R 2 represents an alkylene group having 1 to 6 carbon atoms
  • X represents an anionic hydrophilic group, and average added mole
  • the number n represents an integer of 3 to 40.
  • R 1 represents a hydrocarbon group having 1 to 30 carbon atoms
  • R 2 represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms
  • R 3 represents hydrogen or a propenyl group
  • R 4 represents Represents an alkylene group having 1 to 6 carbon atoms
  • X represents an anionic hydrophilic group
  • the average added mole number n represents a number of 3 to 40;
  • R 1 in Formula (A7) represents hydrogen or a methyl group
  • R 2 and R 4 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms
  • R 3 represents a hydrocarbon having 1 to 30 carbon atoms.
  • M represents hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group, and the average number of added moles m and n is 0 to 40, where (m + n) represents a number of 3 to 40.
  • R 1 and R 5 in the formula (A8) represent a hydrogen or a methyl group
  • R 2 and R 4 are the same or different and each represents an alkylene group having a carbon number of 1 to 6
  • R 3 is Represents a hydrocarbon group having 1 to 30 carbon atoms
  • M represents hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group
  • the average number of added moles m and n is 0 to 40, provided that (m + n) is 3 to 40 Represents a number.
  • R 1 in Formula (A9) represents an alkylene group having 1 to 6 carbon atoms
  • R 2 represents a hydrocarbon group having 1 to 30 carbon atoms
  • M represents hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group.
  • the average added mole number n represents a number of 3 to 40.
  • R 1 , R 2 and R 3 in Formula (A10) are the same or different and represent hydrogen or a methyl group
  • R 4 represents a hydrocarbon group having 0 to 30 carbon atoms (in the case of 0 carbon atoms, R 4 R 5 and R 6 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms
  • X represents an anionic hydrophilic group
  • average added mole numbers m and n are 0 to 40, where (m + n) represents a number from 3 to 40.
  • X in the above formulas (A1) to (A6) and (A10) represents an anionic hydrophilic group.
  • anionic hydrophilic group examples include those represented by the following formulas (a1) to (a2).
  • M 1 in Formula (a1) represents hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group.
  • [M2 and M3 in Formula (a2) are the same or different and represent hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group. ]
  • nonionic reactive surfactant examples include those represented by the formulas (N1) to (N6).
  • R 1 in Formula (N1) represents hydrogen or a methyl group
  • R 2 represents a hydrocarbon group or an acyl group having 1 to 30 carbon atoms
  • R 3 and R 4 may be the same or different
  • 6 represents an alkylene group
  • average addition mole numbers m and n are 0 to 40, where (m + n) represents a number of 3 to 40.
  • R 1 in Formula (N2) represents hydrogen or a methyl group
  • R 2 , R 3 and R 4 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and the average number of added moles n, m, And l represents a number from 0 to 40, and (n + m + 1) is 3 to 40.
  • R 1 in Formula (N3) represents hydrogen or a methyl group
  • R 2 and R 3 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms
  • R 4 represents a hydrocarbon having 1 to 30 carbon atoms.
  • a group or an acyl group, and the average addition mole numbers m and n are 0 to 40, where (m + n) represents a number of 3 to 40.
  • R 1 and R 2 in formula (N4) are the same or different and each represents a hydrocarbon group having 1 to 30 carbon atoms, R 3 represents hydrogen or a propenyl group, and R 4 represents an alkylene having 1 to 6 carbon atoms
  • the average added mole number n represents a number of 3 to 40.
  • R 1 and R 3 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R 2 and R 4 are the same or different and represent hydrogen or a hydrocarbon having 1 to 30 carbon atoms; An average addition mole number m and n are 0 to 40, and (m + n) is a number of 3 to 40. ]
  • R 1 , R 2 and R 3 in Formula (N6) are the same or different and represent hydrogen or a methyl group
  • R 4 represents a hydrocarbon group having 0 to 30 carbon atoms (in the case of 0 carbon atoms, R 4 R 5 and R 6 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and the average added mole numbers m and n are 0 to 40, provided that (m + n) is 3 to The number of 40 is represented. ]
  • the (meth) acrylic polymer (A) may be a polymer composed only of a monomer having a polyoxyalkylene skeleton, but in addition to a monomer having a polyoxyalkylene skeleton, a (meth) acrylic acid ester monomer is used. It may be a copolymer.
  • Examples of such (meth) acrylic acid ester monomers include Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate , T-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, (meth ) Octyl acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (me
  • the (meth) acrylic polymer (A) may be a polymer composed only of a monomer having a polyoxyalkylene skeleton, but is represented by the following general formula (1) in addition to the monomer having a polyoxyalkylene skeleton. It may be a copolymer containing a (meth) acrylic monomer having an alicyclic structure.
  • CH 2 C (R 1 ) COOR 2 (1)
  • Examples of the alicyclic hydrocarbon group R 2 in the general formula (1) include alicyclic hydrocarbon groups such as a cyclohexyl group, an isobornyl group, and a dicyclopentanyl group.
  • Examples of such (meth) acrylic monomers having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate having a cyclohexyl group, isobornyl (meth) acrylate having an isobornyl group, and a dicyclopentanyl group. Mention may be made of esters of (meth) acrylic acid with alicyclic alcohols such as (meth) acrylic acid dicyclopentanyl.
  • the alicyclic hydrocarbon group of the (meth) acrylic monomer having an alicyclic structure constituting the (meth) acrylic polymer (A) preferably has a bridged ring structure.
  • the bridged ring structure refers to an alicyclic structure having three or more rings.
  • R 2 that is an alicyclic hydrocarbon group having a bridged ring structure
  • examples of R 2 that is an alicyclic hydrocarbon group having a bridged ring structure include a dicyclopentanyl group represented by the following formula (3a), a dicyclopentenyl group represented by the following formula (3b), Examples thereof include an adamantyl group represented by the following formula (3c), a tricyclopentanyl group represented by the following formula (3d), and a tricyclopentenyl group represented by the following formula (3e).
  • UV polymerization is employed in the synthesis of the (meth) acrylic polymer (B) or in the preparation of the pressure-sensitive adhesive composition, it is difficult to cause polymerization inhibition.
  • (meth) acrylic monomers having a ring or higher alicyclic structure in particular, a dicyclopentanyl group represented by the following formula (3a), an adamantyl group represented by the following formula (3c), and the following formula
  • a (meth) acrylic monomer having a saturated structure such as a tricyclopentanyl group represented by (3d) can be suitably used as a monomer constituting the (meth) acrylic polymer (B).
  • (meth) acrylic monomers having a tricyclic or higher alicyclic structure having such a bridged ring structure include dicyclopentanyl methacrylate, dicyclopentanyl acrylate, and dicyclopentanyloxyethyl.
  • the (meth) acrylic polymer (A) contains, in addition to the monomer having a polyoxyalkylene skeleton, another monomer component (copolymerizable monomer) that can be copolymerized with a monomer having a polyoxyalkylene skeleton. It can also be obtained by polymerization.
  • a functional group having reactivity with an epoxy group or an isocyanate group may be introduced. Examples of such a functional group include a hydroxyl group, a carboxyl group, an amino group, an amide group, and a mercapto group, and a monomer having such a functional group when the (meth) acrylic polymer (A) is produced. May be used (copolymerization).
  • Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid;
  • Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate monomer;
  • (Meth) acrylic acid alkali metal salts and the like Di (meth) acrylic acid ester of ethylene glycol, di (meth) acrylic acid ester of diethylene glycol, di (meth) acrylic acid ester of triethylene glycol, di (meth) acrylic acid ester of polyethylene glycol
  • the weight average molecular weight of the (meth) acrylic polymer (A) is 1000 or more and less than 30000, preferably 1500 or more and less than 20000, more preferably 2000 or more and less than 10,000, and particularly preferably 2500 or more and less than 6000.
  • the weight average molecular weight is 30000 or more, the compatibility with the polymer (C) is lowered, and the initial adhesive strength may not be sufficiently lowered. Further, if the weight average molecular weight is less than 1000, the molecular weight becomes low, and thus there is a case where an increase in adhesive strength over time cannot be obtained.
  • a (meth) acrylic polymer having a weight average molecular weight of 1000 or more and less than 30000 a (meth) acrylic monomer having a homopolymer glass transition temperature of 0 ° C. or more is included as a monomer unit (meth).
  • An acrylic polymer (B) may be used in combination.
  • the (meth) acrylic polymer (B) is represented by the following general formula (1), and contains a (meth) acrylic monomer having a homopolymer glass transition temperature of 0 ° C. or higher as a monomer unit. In the pressure-sensitive adhesive composition, it functions as an additive for adjusting the adhesive strength.
  • CH 2 C (R 1 ) COOR 2 (1) [In Formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group]
  • Examples of the (meth) acrylic monomer represented by the general formula (1) having a glass transition temperature of 0 ° C. or higher include dicyclopentanyl methacrylate (Tg: 175 ° C.), dicyclopentanyl acrylate ( Tg: 120 ° C., isobornyl methacrylate (Tg: 173 ° C.), isobornyl acrylate (Tg: 97 ° C.), cyclohexyl methacrylate (Tg: 66 ° C.), cyclohexyl acrylate (Tg: 15 ° C.), isobutyl methacrylate (Tg) : 48 ° C), methyl methacrylate (Tg: 105 ° C), 1-adamantyl methacrylate (Tg: 250 ° C), 1-adamantyl acrylate (Tg: 153 ° C), and the like.
  • the (meth) acrylic polymer may be a copolymer of the above (meth) acrylic monomer and the following monomer (however, the glass transition temperature of the homopolymer is 0 ° C. or higher).
  • the monomer copolymerizable with the (meth) acrylic monomer include acryloylmorpholine (Tg: 145 ° C.), dimethyl acrylamide (Tg: 119 ° C.), diethyl acrylamide (Tg: 81 ° C.), dimethylaminopropyl acrylamide (Tg: Amide group-containing vinyl monomers such as isopropyl acrylamide (Tg: 134 ° C.), hydroxyethyl acrylamide (Tg: 98 ° C.); Nitrogen-containing heterocyclic monomers such as N-vinyl-pyrrolidone (Tg: 54 ° C.); Lactam monomers such as N-vinylcaprolactam such as N-vinyl-2-caprolactam
  • the adhesive force can be increased over time.
  • R 2 in the general formula (1) is preferably an alicyclic hydrocarbon group such as a cyclohexyl group, an isobornyl group, or a dicyclopentanyl group.
  • examples of such (meth) acrylic monomers having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate having a cyclohexyl group, isobornyl (meth) acrylate having an isobornyl group, and a dicyclopentanyl group.
  • Mention may be made of esters of (meth) acrylic acid with alicyclic alcohols such as (meth) acrylic acid dicyclopentanyl.
  • the alicyclic hydrocarbon group of the (meth) acrylic monomer having an alicyclic structure constituting the (meth) acrylic polymer (B) preferably has a bridged ring structure.
  • the bridged ring structure refers to an alicyclic structure having three or more rings.
  • R 2 that is an alicyclic hydrocarbon group having a bridged ring structure
  • examples of R 2 that is an alicyclic hydrocarbon group having a bridged ring structure include a dicyclopentanyl group represented by the following formula (3a), a dicyclopentenyl group represented by the following formula (3b), Examples thereof include an adamantyl group represented by the following formula (3c), a tricyclopentanyl group represented by the following formula (3d), and a tricyclopentenyl group represented by the following formula (3e).
  • UV polymerization is employed in the synthesis of the (meth) acrylic polymer (B) or in the preparation of the pressure-sensitive adhesive composition, it is difficult to cause polymerization inhibition.
  • (meth) acrylic monomers having a ring or higher alicyclic structure in particular, a dicyclopentanyl group represented by the following formula (3a), an adamantyl group represented by the following formula (3c), and the following formula
  • a (meth) acrylic monomer having a saturated structure such as a tricyclopentanyl group represented by (3d) can be suitably used as a monomer constituting the (meth) acrylic polymer (B).
  • (meth) acrylic monomers having a tricyclic or higher alicyclic structure having such a bridged ring structure include dicyclopentanyl methacrylate, dicyclopentanyl acrylate, and dicyclopentanyloxyethyl.
  • Examples of the (meth) acrylic polymer (B) include a copolymer of dicyclopentanyl methacrylate (DCPMA) and methyl methacrylate (MMA), isobornyl methacrylate (IBXMA) and methyl methacrylate (MMA).
  • Examples thereof include a copolymer, a copolymer of cyclohexyl methacrylate (CHMA) and methyl methacrylate (MMA), and a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA).
  • the weight average molecular weight of the (meth) acrylic polymer (B) is preferably 1000 or more and less than 30000, more preferably 1500 or more and less than 20000, still more preferably 2000 or more and less than 10,000.
  • the weight average molecular weight is 30000 or more, the compatibility with the polymer (C) is lowered, which may inhibit the initial reduction in adhesive strength. Further, if the weight average molecular weight is less than 1000, the molecular weight becomes low, and the effect of increasing the adhesive strength over time may not be obtained.
  • the (meth) acrylic polymer (B) has a glass transition temperature (Tg) of 30 ° C. to 300 ° C., preferably 50 ° C. to 280 ° C., more preferably 90 ° C. to 280 ° C., more preferably 110 ° C. to 250 ° C. It is desirable that If the glass transition temperature (Tg) is less than 30 ° C., the increase in adhesive strength over time may be small.
  • the glass transition temperature of the (meth) acrylic polymer (B) is a nominal value described in literatures, catalogs, or the like, or a value calculated based on the above Fox equation.
  • (Meth) acrylic polymer (A) and (meth) acrylic polymer (B) are, for example, solution polymerization method, bulk polymerization method, emulsion polymerization method, (meth) acrylic monomer having the above-described structure, It can be produced by polymerization by suspension polymerization, bulk polymerization or the like.
  • a chain transfer agent can be used during the polymerization in order to adjust the molecular weight of the (meth) acrylic polymer (A) and the (meth) acrylic polymer (B).
  • the chain transfer agent used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, ⁇ -thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate,
  • the amount of the chain transfer agent to be used is not particularly limited, but is usually 0.1 to 20 parts by mass, preferably 0.2 parts by mass with respect to 100 parts by mass of the (meth) acrylic monomer. Part to 15 parts by weight, more preferably 0.3 part to 10 parts by weight.
  • the (meth) acrylic-type polymer (A) and (meth) acrylic-type polymer (B) of a suitable molecular weight can be obtained by adjusting the addition amount of a chain transfer agent.
  • a chain transfer agent can be used individually or in combination of 2 or more types.
  • the pressure-sensitive adhesive layer according to the embodiment may further include a polymer (C) described below.
  • the polymer (C) is not particularly limited as long as the glass transition temperature is lower than 0 ° C., and is generally used as an adhesive such as an acrylic polymer, a rubber polymer, a silicone polymer, a polyurethane polymer, and a polyester polymer.
  • Various polymers can be used.
  • an acrylic polymer that is easily compatible with the (meth) acrylic polymer (A) and the (meth) acrylic polymer (B) and has high transparency is preferable.
  • the glass transition temperature (Tg) of the polymer (C) is less than 0 ° C., preferably less than ⁇ 10 ° C., more preferably less than ⁇ 40 ° C., and usually ⁇ 80 ° C. or higher.
  • Tg glass transition temperature
  • the glass transition temperature is a nominal value described in literatures, catalogs, or the like, or a value calculated based on the following formula (X) (Fox formula).
  • Tg is the glass transition temperature (unit: K) of the polymer (C)
  • the above formula (X) is a calculation formula in the case where the polymer (C) is composed of n types of monomer components of monomer 1, monomer 2,.
  • glass transition temperature when homopolymer is formed means “glass transition temperature of homopolymer of the monomer”, and may be referred to as a certain monomer (“monomer X”). ) Is the glass transition temperature (Tg) of a polymer formed using only the monomer component. Specifically, “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc, 1989) lists numerical values. In addition, the glass transition temperature (Tg) of the homopolymer which is not described in the said literature says the value obtained by the following measuring methods, for example.
  • this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1 to 2 mg of this test sample is weighed in an aluminum open cell, and a nitrogen atmosphere of 50 ml / min is used using a temperature modulation DSC (trade name “Q-2000”, manufactured by T.A. Instruments Inc.). Under the heating rate of 5 ° C./min, the reversing heat flow (specific heat component) behavior of the homopolymer is obtained.
  • a temperature modulation DSC trade name “Q-2000”, manufactured by T.A. Instruments Inc.
  • the temperature at the point where the partial curve intersects is the glass transition temperature (Tg) when the homopolymer is used.
  • the weight average molecular weight (Mw) of the polymer (C) is, for example, about 30,000 to 5 million. If the weight average molecular weight (Mw) is less than 30,000, the cohesive force of the pressure-sensitive adhesive may be insufficient, resulting in poor adhesion reliability. On the other hand, when the weight average molecular weight (Mw) exceeds 5,000,000, the fluidity of the pressure-sensitive adhesive is lowered, and there are cases where the adhesive strength increases with time.
  • the acrylic polymer is, for example, a polymer containing 50% by mass or more of (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms as a monomer unit.
  • the acrylic polymer may have a configuration in which (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is used alone or in combination of two or more.
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods generally used as synthetic methods for acrylic polymers such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and radiation curing polymerization are applied. Thus, the polymer can be obtained.
  • the proportion of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms is 50% by mass to 99.9% by mass with respect to the total amount of monomer components for preparing the acrylic polymer. %, Preferably 60 mass% to 98 mass%, more preferably 70 mass% to 95 mass%.
  • Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acryl Isopentyl acid, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) Ison
  • Acrylic polymers can be copolymerized with other (meth) acrylic acid alkyl esters as needed for the purpose of modifying cohesion, heat resistance, crosslinkability, etc. Monomer). Therefore, the acrylic polymer may contain a copolymerizable monomer together with the (meth) acrylic acid alkyl ester as the main component. As the copolymerizable monomer, a monomer having a polar group can be suitably used.
  • Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as methacrylate; Acid anhydride group
  • (N- substituted) amide monomers Succinimide monomers such as N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyhexamethylenesuccinimide; Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; Itaconimides such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide System monomers; Vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2-pyrrolidone,
  • the acrylic polymer has at least one monomer selected from the group consisting of an N-vinyl cyclic amide represented by the following general formula (M1) and a hydroxyl group-containing monomer as a monomer unit. It is preferable to contain. In particular, it is preferable to use a monomer selected from the group consisting of N-vinyl cyclic amides.
  • R 1 is a divalent organic group.
  • N-vinyl cyclic amide examples include N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3 -Oxazin-2-one, N-vinyl-3,5-morpholinedione and the like. Particularly preferred are N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam.
  • the amount of the monomer selected from the group consisting of N-vinyl cyclic amides is not particularly limited, but is usually 0.01% by mass of the copolymerizable monomer based on the total amount of the monomer components for preparing the acrylic polymer. It can be contained in an amount of from 40 to 40% by mass, preferably from 0.1 to 30% by mass, and more preferably from 0.5 to 20% by mass.
  • the hydroxyl group-containing monomer 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and the like can be preferably used.
  • the amount of the hydroxy group-containing monomer used is not particularly limited, but is usually 40% by mass or less, preferably 20% by mass or less, and more preferably 20% by mass or less, based on the total amount of monomer components for preparing the acrylic polymer. Preferably it can contain 10 mass%.
  • the copolymerizable monomer By containing 0.01% by mass or more of the copolymerizable monomer, it is possible to prevent the cohesive force of the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed of the acrylic pressure-sensitive adhesive composition from being lowered. Moreover, by making content of a copolymerizable monomer into 40 mass% or less, it can prevent that cohesion force becomes high too much and can improve the tuck feeling in normal temperature (25 degreeC).
  • an acrylic material when used for an adherend made of metal or an adherend on which a metal film is formed (for example, a touch panel on which an electrically conductive film (ITO) is formed), an acrylic material is used. It is desirable that the polymer has no carboxyl group. Moreover, from a corrosive viewpoint, it is desirable not to contain substantially acidic functional groups other than a carboxyl group. Therefore, the monomer constituent unit constituting the acrylic polymer of the present embodiment may be substantially free of a monomer having a carboxyl group or an acidic functional group other than the carboxyl group.
  • the acidic functional group refers to a functional group having active hydrogen.
  • the acidic functional group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. “Substantially free” of an acidic functional group means that it is not actively incorporated unless it is inevitably incorporated.
  • the proportion (% by mass) of the monomer having an acidic functional group in the total amount of the constituent units constituting the acrylic polymer is less than 1% by mass, preferably less than 0.5% by mass. means.
  • the acrylic polymer may contain a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive composition to be formed.
  • polyfunctional monomer examples include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, and pentaerythritol.
  • trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used.
  • a polyfunctional monomer can be used individually or in combination of 2 or more types.
  • the amount of the polyfunctional monomer used varies depending on the molecular weight and the number of functional groups, but is 0.01% by mass to 3.0% by mass, preferably 0%, based on the total amount of monomer components for preparing the acrylic polymer. It is added in an amount of 0.02 mass% to 2.0 mass%, more preferably 0.03 mass% to 1.0 mass%.
  • the cohesive force of the pressure-sensitive adhesive composition becomes too high, and the initial pressure-sensitive adhesive strength The suppression effect may be reduced.
  • the cohesive strength of the pressure-sensitive adhesive composition may be reduced, and the increase in the adhesive strength over time may be insufficient.
  • an acrylic polymer When preparing an acrylic polymer, it is possible to easily form an acrylic polymer by using a curing reaction by heat or ultraviolet rays using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator). it can. In particular, photopolymerization can be suitably used from the advantage of improving the adhesive property.
  • a polymerization initiator can be used individually or in combination of 2 or more types.
  • thermal polymerization initiator examples include azo polymerization initiators (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis ( 2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2 -(5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethylene) Isobutylamidine) dihydrochloride, etc.); peroxide polymerization initiators (eg, dibenzoyl peroxide, t-butylpermaleate, lauroy peroxide) Etc.); redox polymerization initiators, and the
  • the amount of the thermal polymerization initiator used is not particularly limited, but for example, 0.01 parts by mass to 5 parts by mass, preferably 0.05 parts by mass to 3 parts by mass with respect to 100 parts by mass of the monomer component for preparing the acrylic polymer. It mix
  • the photopolymerization initiator is not particularly limited, but for example, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator An agent or the like can be used.
  • examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- 1-one [trade name: Irgacure 651, manufactured by BASF Corporation], anisoin and the like can be mentioned.
  • acetophenone photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by BASF], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [trade name: Irgacure 2959, manufactured by BASF Corp.], 2-hydroxy-2-methyl-1-phenyl-propane- 1-one [trade name: Darocur 1173, manufactured by BASF], methoxyacetophenone, and the like can be given.
  • Irgacure 184 manufactured by BASF
  • 4-phenoxydichloroacetophenone 4-t-butyl-dichloroacetophenone
  • 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one trade name: Irg
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane-1- ON etc. are mentioned.
  • Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.
  • the benzoin photopolymerization initiator includes, for example, benzoin.
  • examples of the benzyl photopolymerization initiator include benzyl and the like.
  • examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
  • Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.
  • thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like are included.
  • acylphosphine photopolymerization initiator examples include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, bis ( 2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1- Methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) octylphosphine Oxides, bis (2 Methoxy
  • the amount of the photopolymerization initiator used is not particularly limited, but for example, 0.01 parts by mass to 5 parts by mass, preferably 0.05 parts by mass to 3 parts by mass with respect to 100 parts by mass of the monomer component for preparing the acrylic polymer. In an amount within the range of parts.
  • the amount of the photopolymerization initiator used is less than 0.01 parts by mass, the polymerization reaction may become insufficient.
  • an ultraviolet-ray may not reach the inside of an adhesive layer because a photoinitiator absorbs an ultraviolet-ray.
  • the polymerization rate is lowered, or the molecular weight of the produced polymer is reduced. And thereby, the cohesive force of the adhesive layer formed becomes low, and the adhesive force raise with time may become inadequate.
  • a photopolymerization initiator can be used individually or in combination of 2 or more types.
  • the polymer (C) is a partially polymerized product (acrylic polymer syrup) obtained by irradiating a mixture of the monomer component and the polymerization initiator with ultraviolet rays (UV) to partially polymerize the monomer component. It can also be prepared as.
  • the pressure-sensitive adhesive composition is prepared by blending the acrylic polymer syrup with the (meth) acrylic polymer (A) or (meth) acrylic polymer (A) and (meth) acrylic polymer (B) described later. It is also possible to complete the polymerization by preparing and applying this pressure-sensitive adhesive composition to a predetermined substrate and irradiating it with ultraviolet rays.
  • the acrylic polymer syrup is a polymer precursor, and the (meth) acrylic polymer (A) or the (meth) acrylic polymer (A) and the (meth) acrylic polymer ( The blend of B) also corresponds to the pressure-sensitive adhesive composition of the present embodiment.
  • the measurement of the weight average molecular weight of the polymer (C), the (meth) acrylic polymer (A), and the (meth) acrylic polymer (B) can be obtained in terms of polystyrene by gel permeation chromatography (GPC) method. it can. Specifically, it is measured according to the method and conditions described in the examples described later.
  • GPC gel permeation chromatography
  • the pressure-sensitive adhesive composition contains at least a (meth) acrylic polymer having a weight average molecular weight of 1000 or more and less than 30000.
  • the (meth) acrylic polymer having a weight average molecular weight of 1000 or more and less than 30000 may be the aforementioned (meth) acrylic polymer (A) or (meth) acrylic polymer (B).
  • a polymer (C) It is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and further preferably 0.5 to 15 parts by mass with respect to 100 parts by mass. Particularly preferred is 1 to 10 parts by mass.
  • the content of the (meth) acrylic polymer (B) is a polymer.
  • the amount is preferably 0.01 parts by weight to 40 parts by weight, more preferably 0.03 parts by weight to 20 parts by weight, still more preferably 0.05 parts by weight to 10 parts by weight with respect to 100 parts by weight.
  • the amount is particularly preferably 0.08 to 5 parts by mass.
  • the (meth) acrylic polymer (A) is interfaced immediately after bonding by introducing a polyoxyalkylene skeleton into the (meth) acrylic polymer (A).
  • the (meth) acrylic polymer (B) works to increase the adhesion at the interface and contributes to an increase in the adhesive strength over time. It is thought that. If the (meth) acrylic polymer (A) is added in excess of 50 parts by mass, the transparency of the pressure-sensitive adhesive layer formed with the pressure-sensitive adhesive composition according to the present embodiment is lowered.
  • the addition amount of (meth) acrylic-type polymer (A) is less than 0.05 mass part, the adhesive force suppression effect at the time of adherend bonding is weak, and the malfunction which cannot rework may arise. If the (meth) acrylic polymer (B) is added in excess of 40 parts by mass, the initial adhesive force suppressing effect by the (meth) acrylic polymer (A) may be inhibited. Moreover, when the addition amount of (meth) acrylic-type polymer (A) is less than 0.01 mass part, the adhesive force raise effect with time may be inadequate.
  • the pressure-sensitive adhesive composition may be any of various additives commonly used in the field of pressure-sensitive adhesive compositions, in addition to the above-described polymer, (meth) acrylic polymer (A), and (meth) acrylic polymer (B). It can be contained as a component.
  • Such optional components include tackifier resins, crosslinking agents, catalysts, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), antioxidants, leveling agents, stabilizers, preservatives, antistatic agents, etc. Is exemplified. Conventionally known additives can be used as such additives.
  • a crosslinking agent can be used in addition to the above-mentioned polyfunctional monomer.
  • a commonly used crosslinking agent can be used.
  • epoxy crosslinking agent, isocyanate crosslinking agent, silicone crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, silane crosslinking agent, alkyl etherification A melamine type crosslinking agent, a metal chelate type crosslinking agent, etc. can be mentioned.
  • an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, and a metal chelate-based crosslinking agent can be preferably used. These compounds may be used alone or in combination of two or more.
  • examples of isocyanate-based crosslinking agents include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene.
  • examples include diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
  • a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule specifically, 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent.
  • 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent.
  • Can do These compounds may be used alone or in combination of two or more.
  • Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol propane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, etc. Can do. These compounds may be used alone or in combination of two or more.
  • metal chelate compound examples include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These compounds may be used alone or in combination of two or more.
  • the content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer (C). preferable.
  • content is less than 0.01 mass part, the cohesion force of an adhesive composition may become small and it may be inferior to adhesive reliability.
  • content exceeds 15 parts by mass, the cohesive force of the pressure-sensitive adhesive composition is large, the fluidity is lowered, and the increase in pressure-sensitive adhesive strength with time may be inferior.
  • the pressure-sensitive adhesive composition disclosed herein can further contain a crosslinking catalyst for causing any of the above-described crosslinking reactions to proceed more effectively.
  • a crosslinking catalyst for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used.
  • the amount of the crosslinking catalyst is not particularly limited, and can be, for example, about 0.0001 parts by mass to 1 part by mass with respect to 100 parts by mass of the polymer (C). .
  • Adhesive layer and adhesive sheet Then, the structure of the adhesive sheet which has an adhesive layer containing the adhesive composition which has the above-mentioned composition is demonstrated.
  • the pressure-sensitive adhesive layer can be a cured layer of the pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to a suitable support (for example, coating / coating) and then appropriately performing a curing treatment. When performing 2 or more types of hardening processes (drying, bridge
  • a pressure-sensitive adhesive composition using a partial polymer (acrylic polymer syrup) typically, as the curing treatment, a final copolymerization reaction is performed (the partial polymer is subjected to a further copolymerization reaction). A complete polymer is formed).
  • Application and coating of the pressure-sensitive adhesive composition can be carried out using a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, etc. it can.
  • the pressure-sensitive adhesive composition may be directly applied to the support to form a pressure-sensitive adhesive layer, or the pressure-sensitive adhesive layer formed on the release liner may be transferred to the support.
  • the pressure-sensitive adhesive layer has a solvent-insoluble component ratio of 55.0% to 99.0% by mass, preferably 60.0% to 95.0% by mass. If the solvent-insoluble component ratio is less than 55.0% by mass, the cohesive force may be insufficient, resulting in poor adhesion reliability. If the solvent-insoluble component ratio exceeds 99.0% by mass, the cohesive force becomes too high. In some cases, the increase in adhesive strength over time may be insufficient. In addition, the evaluation method of a solvent insoluble component rate is mentioned later.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but usually good adhesiveness can be realized by setting the thickness to, for example, 2 ⁇ m to 200 ⁇ m, preferably 3 ⁇ m to 150 ⁇ m. If the thickness of the pressure-sensitive adhesive layer is less than 2 ⁇ m, the increase in adhesive strength over time may be inferior. On the other hand, if the thickness of the pressure-sensitive adhesive layer exceeds 200 ⁇ m, the effect of suppressing the adhesive force immediately after bonding may be insufficient. is there.
  • the pressure-sensitive adhesive sheet according to this embodiment includes a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive sheet is provided with such a pressure-sensitive adhesive layer fixedly on at least one side of the support, that is, without intending to separate the pressure-sensitive adhesive layer from the support.
  • the concept of the pressure-sensitive adhesive sheet referred to here may include what are called pressure-sensitive adhesive tapes, pressure-sensitive adhesive films, pressure-sensitive adhesive labels, and the like. Further, it may be cut into a suitable shape, punched out, or the like according to the intended use.
  • the pressure-sensitive adhesive layer is not limited to those formed continuously, and may be a pressure-sensitive adhesive layer formed in a regular or random pattern such as a dot shape or a stripe shape.
  • polyethylene polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer
  • Polyolefin films such as polymers, ethylene / vinyl alcohol copolymers, polyester films such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyacrylate films, polystyrene films, nylon 6, nylon 6,6, partially aromatic polyamides, etc.
  • Plastic films such as polyamide film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film; Foam substrates such as polyurethane foam and polyethylene foam; Kraft paper, crepe paper, Japanese paper, etc .; Cotton, soft cloth, etc .; Nonwoven fabrics such as polyester nonwoven fabrics and vinylon nonwoven fabrics; Metal foil such as aluminum foil and copper foil; Can be appropriately selected and used depending on the application of the adhesive tape.
  • the support may be released with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., and antifouling treatment, acid treatment, alkali treatment, primer treatment. Further, easy adhesion treatment such as corona treatment, plasma treatment, and ultraviolet treatment can be performed.
  • the thickness of the support can be appropriately selected depending on the purpose, but is generally about 5 ⁇ m to 200 ⁇ m (typically 10 ⁇ m to 100 ⁇ m).
  • silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent release with silica powder and antifouling treatment, acid treatment, alkali treatment, primer treatment, Anti-adhesive treatment such as corona treatment, plasma treatment and ultraviolet treatment, coating type, kneading type, vapor deposition type and the like can also be carried out.
  • a release liner can be bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface as necessary.
  • the material constituting the release liner includes paper and plastic film, but a plastic film is preferably used because of its excellent surface smoothness.
  • the film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
  • polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the thickness of the release liner is usually about 5 ⁇ m to 200 ⁇ m, preferably about 10 ⁇ m to 100 ⁇ m. It is preferable for it to be in the above-mentioned range since it is excellent in workability for bonding to the pressure-sensitive adhesive layer and workability for peeling from the pressure-sensitive adhesive layer.
  • release and antifouling treatment with silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, etc., coating type, kneading type, vapor deposition An antistatic treatment such as a mold can also be performed.
  • the adhesive sheet has the characteristics that immediately after being bonded to an adherend, the adhesive strength is small and rework is possible, the adhesive strength increases with time, and the adhesive reliability is high.
  • a 180 ° peel adhesion test when peeled at a tensile speed of 300 mm / min and a peel angle of 180 °, and particularly 1.0 N / 25 mm. If it is below, it is judged as good. 180 degree peeling adhesive force becomes like this.
  • it is 0.8 N / 25mm or less, More preferably, it is 0.5 N / 25mm or less.
  • the 180 ° peel adhesion test is measured according to the method and conditions described in the examples described later.
  • the adhesive strength of the adhesive sheet after the elapse of time can be evaluated by a 180 ° peeling adhesive strength test when it is peeled off at a pulling rate of 300 mm / min and a peeling angle of 180 °, particularly 5.0 N / 25 mm or more. Is considered good. 180 degree peeling adhesive force becomes like this. Preferably it is 6.0 N / 25mm or more, More preferably, it is 7.0 N / 25mm or more.
  • the 180 ° peel adhesion test is measured according to the method and conditions described in the examples described later.
  • optical film with adhesive layer Furthermore, this invention provides the optical film with an adhesive layer formed by forming the said adhesive on the at least single side
  • an optical film that can be used in the present invention a polarizing plate, a wavelength plate, an optical compensation film, a light diffusion sheet, a reflection sheet, an antireflection sheet, used in an image display device such as a liquid crystal display, a plasma display, and an organic EL display, A brightness enhancement film, a transparent conductive film (ITO film), etc. can be mentioned.
  • the method for forming the pressure-sensitive adhesive layer on at least one surface of the optical film is not particularly limited, and the pressure-sensitive adhesive layer may be formed by directly applying the pressure-sensitive adhesive composition of the present embodiment to the surface of the optical film.
  • a pressure-sensitive adhesive layer may be formed on a release liner, and the pressure-sensitive adhesive layer surface may be bonded to the optical film to transfer the pressure-sensitive adhesive layer to the optical film.
  • the thickness of the pressure-sensitive adhesive layer in the optical film with the pressure-sensitive adhesive layer is preferably 2 ⁇ m to 200 ⁇ m, more preferably 3 ⁇ m to 150 ⁇ m, and still more preferably 5 to 100 ⁇ m.
  • the adhesive sheet of the present embodiment is low in adhesive strength to the extent that it can be reworked at the initial stage of attachment, and then adheres firmly to the adherend, and further has a pressure-sensitive adhesive layer that is also excellent in transparency.
  • it can be suitably used as a bonding material for members in mobile devices and other electric and electronic devices, or as a bonding material for various members in automobiles, home appliances, and the like.
  • the obtained (meth) acrylic polymer 1 had a weight average molecular weight of 3300.
  • the obtained (meth) acrylic polymer 2 had a weight average molecular weight of 4600.
  • the obtained (meth) acrylic polymer 3 had a weight average molecular weight of 5,600.
  • the obtained (meth) acrylic polymer 4 had a weight average molecular weight of 4,100.
  • the obtained (meth) acrylic polymer 5 had a weight average molecular weight of 4000.
  • Example 1 Preparation of acrylic pressure-sensitive adhesive composition
  • 5 parts by mass of the above-mentioned (meth) acrylic polymer (A) 1 and 0.1 part by mass of trimethylolpropane triacrylate (TMPTA) as a crosslinking agent were added to 100 parts by mass of the acrylic polymer syrup 1 described above. Then, these were mixed uniformly and the acrylic adhesive composition was prepared.
  • TMPTA trimethylolpropane triacrylate
  • the acrylic adhesive composition described above is applied to the release-treated surface of a 38 ⁇ m-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) having one surface peeled with silicone so that the final thickness is 50 ⁇ m.
  • a 38 ⁇ m thick polyester film (trade name: Diafoil MRE, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled off with silicone on the surface of the applied acrylic pressure-sensitive adhesive composition is peeled off.
  • the coating was performed so as to be on the coating layer side. Thereby, the application layer (acrylic adhesive composition layer) of the acrylic adhesive composition was shielded from oxygen.
  • the coating layer thus obtained was irradiated with ultraviolet rays having an illuminance of 5 mW / cm 2 (measured with Topcon UVR-T1 having a maximum sensitivity of about 350 nm) for 360 seconds using a chemical light lamp (manufactured by Toshiba Corporation).
  • a chemical light lamp manufactured by Toshiba Corporation.
  • Example 2 instead of using 5 parts by mass of the (meth) acrylic polymer (A) 1, 10 parts by mass of the (meth) acrylic polymer (A) 2 was used in the same manner as in Example 1
  • the pressure-sensitive adhesive composition was prepared, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 3 Instead of using the acrylic polymer syrup 2 instead of the acrylic polymer syrup 1 and using 5 parts by mass of the (meth) acrylic polymer (A) 1, a (meth) acrylic polymer (A ) An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by mass of 3 was used, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 4 instead of using 5 parts by mass of the (meth) acrylic polymer (A) 1, 10% by mass of the (meth) acrylic polymer (A) 4 was used in the same manner as in Example 1
  • the pressure-sensitive adhesive composition was prepared, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 5 In place of using 5 parts by mass of (meth) acrylic polymer (A) 1 and using 10 parts by mass of (meth) acrylic polymer (A) 5, acrylic adhesive as in Example 1.
  • the adhesive composition was prepared, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 6 Instead of using 5 parts by mass of the (meth) acrylic polymer (A) 1, 10 parts by mass of the (meth) acrylic polymer (A) 6 was used in the same manner as in Example 1
  • the pressure-sensitive adhesive composition was prepared, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 7 Instead of using 5 parts by mass of the (meth) acrylic polymer (A) 1, 10% by mass of the (meth) acrylic polymer (A) 7 was used, and the acrylic type was the same as in Example 1.
  • the pressure-sensitive adhesive composition was prepared, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 8 instead of using 5 parts by mass of (meth) acrylic polymer (A) 1, acrylic system was used in the same manner as in Example 1 except that 5 parts by mass of (meth) acrylic polymer (A) 8 was used.
  • the pressure-sensitive adhesive composition was prepared, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 9 Instead of using 5 parts by mass of (meth) acrylic polymer (A) 1, 4 parts by mass of (meth) acrylic polymer (A) 1 and (meth) acrylic polymer (B) 1 are used.
  • An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.1 part by mass was used, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 10 Instead of using 5 parts by mass of (meth) acrylic polymer (A) 1, 4 parts by mass of (meth) acrylic polymer (A) 3 and (meth) acrylic polymer (B) 2 are used.
  • An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.1 part by mass was used, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 11 Instead of using 5 parts by mass of (meth) acrylic polymer (A) 1, 4 parts by mass of (meth) acrylic polymer (A) 3 and (meth) acrylic polymer (B) 3 are used.
  • An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.1 part by mass was used, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 12 Instead of using 5 parts by mass of (meth) acrylic polymer (A) 1, 4 parts by mass of (meth) acrylic polymer (A) 3 and (meth) acrylic polymer (B) 4 are used.
  • An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.1 part by mass was used, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 13 Instead of using 5 parts by mass of (meth) acrylic polymer (A) 1, 4 parts by mass of (meth) acrylic polymer (A) 3 and (meth) acrylic polymer (B) 5 are used.
  • An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.1 part by mass was used, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 14 Instead of using 5 parts by mass of (meth) acrylic polymer (A) 1, 4 parts by mass of (meth) acrylic polymer (A) 3 and (meth) acrylic polymer (B) 1 are used.
  • An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.5 part by mass was used, and an acrylic pressure-sensitive adhesive layer was obtained in the same manner as in Example 1.
  • Example 1 The acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that (meth) acrylic polymer (A) 1 was not used and 0.12 parts by mass of TMPTA was added. An acrylic pressure-sensitive adhesive layer was obtained by the method described above.
  • the weight average molecular weight of the (meth) acrylic copolymer was measured using a GPC apparatus (manufactured by Tosoh Corporation, HLC-8220 GPC). The measurement conditions were as follows, and the molecular weight was determined by standard polystyrene conversion.
  • One release liner (polyester film) of the pressure-sensitive adhesive sheet according to each example and comparative example was peeled off, a polyethylene terephthalate film having a thickness of 50 ⁇ m was bonded, and the test piece was cut into a size of 25 mm in width and 60 mm in length. . Further, a 1.35 mm glass plate (product name: # 0050, manufactured by Matsunami Glass Industrial Co., Ltd.) cleaned with isopropyl alcohol was prepared.
  • the other release liner (polyester film) of the pressure-sensitive adhesive sheet was peeled off, the 2 kg roller was reciprocated once to attach the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet to the glass plate, and left in a 40 ° C. environment for 48 hours.
  • the present invention is applicable to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and an optical film with a pressure-sensitive adhesive layer.

Landscapes

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

Abstract

Un mode de réalisation de la couche adhésive de la présente invention contient un polymère (méth)acrylate ayant une masse moléculaire moyenne en poids d'au moins 1 000 et inférieure à 30 000, a un pouvoir adhésif quand 30 minutes se sont écoulées après collage à une plaque de verre de pas plus de 1,0 N/25 mm, et un pouvoir adhésif quand deux jours se sont écoulés à 40°C après collage à une plaque de verre d'au moins 5,0 N/25 mm.
PCT/JP2013/004556 2012-07-31 2013-07-26 Couche adhésive, feuille adhésive et film optique avec une couche adhésive WO2014020878A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2012170649 2012-07-31
JP2012-170649 2012-07-31
JP2013-091598 2013-04-24
JP2013091597A JP2016130270A (ja) 2013-04-24 2013-04-24 粘着剤組成物、粘着剤層、粘着シートおよび光学フィルム
JP2013091598A JP2016130271A (ja) 2013-04-24 2013-04-24 粘着剤組成物、粘着剤層、粘着シートおよび光学フィルム
JP2013-091597 2013-04-24

Publications (1)

Publication Number Publication Date
WO2014020878A1 true WO2014020878A1 (fr) 2014-02-06

Family

ID=50027585

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/004556 WO2014020878A1 (fr) 2012-07-31 2013-07-26 Couche adhésive, feuille adhésive et film optique avec une couche adhésive

Country Status (1)

Country Link
WO (1) WO2014020878A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014174733A1 (fr) * 2013-04-24 2014-10-30 日東電工株式会社 Composition d'adhésif sensible à la pression, couche d'adhésif sensible à la pression, feuille d'adhésif sensible à la pression, et film optique
WO2016021332A1 (fr) * 2014-08-08 2016-02-11 日東電工株式会社 Élément de construction comprenant une feuille adhésive autocollante et feuille adhésive autocollante pour élément de construction
JP2021155724A (ja) * 2020-03-27 2021-10-07 荒川化学工業株式会社 活性エネルギー線硬化型粘着剤組成物、粘着剤層、積層体

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031945A (ja) * 1999-05-19 2001-02-06 Nitto Denko Corp 接着力経日上昇性粘着剤、及び粘着テープ又はシート
JP2005281460A (ja) * 2004-03-29 2005-10-13 Panac Co Ltd リワーク性が優れた粘着剤および粘着フイルム
JP2009275128A (ja) * 2008-05-15 2009-11-26 Nippon Carbide Ind Co Inc 光学部材表面保護フィルム用粘着剤組成物及び光学部材表面保護フィルム
WO2011118181A1 (fr) * 2010-03-25 2011-09-29 日東電工株式会社 Composition adhésive acrylique et ruban adhésif acrylique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031945A (ja) * 1999-05-19 2001-02-06 Nitto Denko Corp 接着力経日上昇性粘着剤、及び粘着テープ又はシート
JP2005281460A (ja) * 2004-03-29 2005-10-13 Panac Co Ltd リワーク性が優れた粘着剤および粘着フイルム
JP2009275128A (ja) * 2008-05-15 2009-11-26 Nippon Carbide Ind Co Inc 光学部材表面保護フィルム用粘着剤組成物及び光学部材表面保護フィルム
WO2011118181A1 (fr) * 2010-03-25 2011-09-29 日東電工株式会社 Composition adhésive acrylique et ruban adhésif acrylique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014174733A1 (fr) * 2013-04-24 2014-10-30 日東電工株式会社 Composition d'adhésif sensible à la pression, couche d'adhésif sensible à la pression, feuille d'adhésif sensible à la pression, et film optique
WO2016021332A1 (fr) * 2014-08-08 2016-02-11 日東電工株式会社 Élément de construction comprenant une feuille adhésive autocollante et feuille adhésive autocollante pour élément de construction
JP2021155724A (ja) * 2020-03-27 2021-10-07 荒川化学工業株式会社 活性エネルギー線硬化型粘着剤組成物、粘着剤層、積層体

Similar Documents

Publication Publication Date Title
JP5951153B2 (ja) 粘着シート
JP6223836B2 (ja) 粘着剤組成物および粘着シート
JP2014043548A (ja) 粘着剤組成物、粘着剤層、粘着シート及び光学フィルム
JP5890596B1 (ja) 粘着シート
JP5430722B2 (ja) 粘着剤組成物、粘着剤層、粘着シート、表面保護シート、光学用表面保護シート及び表面保護シート付き光学フィルム
JP6022795B2 (ja) 粘着剤組成物、粘着剤層、粘着シート、表面保護シート、光学用表面保護シート、及び、表面保護シート付き光学フィルム
JP6067826B2 (ja) アクリル系粘着剤層およびアクリル系粘着テープ
JP2013079360A (ja) 再剥離用粘着剤組成物、再剥離用粘着剤層および再剥離用粘着シート
JP6373458B2 (ja) 粘着剤組成物、粘着剤層、および粘着シート
JP2011202012A (ja) アクリル系粘着剤組成物およびアクリル系粘着テープ
JP2012149179A (ja) 光学用アクリル系粘着剤組成物および光学用アクリル系粘着テープ
JP6133117B2 (ja) 粘着剤組成物、粘着シート、表面保護シート、及び光学フィルム
WO2016021332A1 (fr) Élément de construction comprenant une feuille adhésive autocollante et feuille adhésive autocollante pour élément de construction
WO2014020867A1 (fr) Composition adhésive, couche adhésive, feuille adhésive, feuille de protection de surface, feuille de protection de surface optique et film optique l'utilisant
WO2014174732A1 (fr) Composition adhésive, couche adhésive, feuille adhésive et film optique
JP2021121682A (ja) 粘着シート及び該粘着シートに用いられる粘着剤組成物
JP2016079232A (ja) 建築部材用粘着シート、および粘着シート付き建築部材
JP5730382B2 (ja) アクリル系粘着剤組成物およびアクリル系粘着テープ
JP6152451B2 (ja) 粘着剤組成物、粘着剤層、粘着シート、表面保護シート、光学用表面保護シート、及び、表面保護シート付き光学フィルム
WO2014020878A1 (fr) Couche adhésive, feuille adhésive et film optique avec une couche adhésive
JP2013079362A (ja) アクリル系粘着剤組成物、アクリル系粘着剤層およびアクリル系粘着テープ
WO2014174733A1 (fr) Composition d'adhésif sensible à la pression, couche d'adhésif sensible à la pression, feuille d'adhésif sensible à la pression, et film optique

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: 13825869

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13825869

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP