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WO2017029959A1 - Couche adhésive destinée à des plaques de polarisation, et composition adhésive - Google Patents

Couche adhésive destinée à des plaques de polarisation, et composition adhésive Download PDF

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Publication number
WO2017029959A1
WO2017029959A1 PCT/JP2016/072147 JP2016072147W WO2017029959A1 WO 2017029959 A1 WO2017029959 A1 WO 2017029959A1 JP 2016072147 W JP2016072147 W JP 2016072147W WO 2017029959 A1 WO2017029959 A1 WO 2017029959A1
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WIPO (PCT)
Prior art keywords
meth
sensitive adhesive
pressure
adhesive layer
photoelastic coefficient
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/JP2016/072147
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English (en)
Japanese (ja)
Inventor
忠史 三角
佐知 室井
貴啓 大久保
恵子 近藤
翔 黒澤
隆祐 田中
雄太 紺野
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.)
Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
Original Assignee
Soken Kagaku KK
Soken Chemical and Engineering Co Ltd
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 Soken Kagaku KK, Soken Chemical and Engineering Co Ltd filed Critical Soken Kagaku KK
Priority to CN201680046837.7A priority Critical patent/CN107924009B/zh
Priority to JP2017535310A priority patent/JP6886401B2/ja
Priority to KR1020187005471A priority patent/KR102243893B1/ko
Publication of WO2017029959A1 publication Critical patent/WO2017029959A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J133/06—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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a pressure-sensitive adhesive layer for a polarizing plate and a pressure-sensitive adhesive composition.
  • the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates (eg, a glass plate).
  • a polarizing plate is attached to the surface of the substrate constituting the liquid crystal cell via an adhesive layer.
  • a polarizing plate has a structure in which a polarizer protective film such as a triacetyl cellulose film is laminated on both surfaces of a polarizer having a polarizing function in order to improve its mechanical properties and optical durability. I came.
  • Patent Document 2 discloses a polarizing film having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition for a polarizing plate containing a large amount of an isocyanate compound
  • Patent Document 3 discloses positive photoelasticity. It describes about the pressure sensitive adhesive composition for polarizing plates containing the component which has a coefficient. However, these documents do not describe providing an adhesive layer directly on a polarizer.
  • a polarizing plate in which at least one of the polarizer protective films conventionally formed on both surfaces of the polarizer is omitted is required to be further excellent in light leakage prevention and durability.
  • An object of the present invention is applicable to a configuration in which at least one of the polarizer protective films conventionally formed on both sides of a polarizer is omitted, and provides an adhesive layer excellent in light leakage prevention and durability. There is.
  • the present inventors diligently studied to solve the above problems. As a result, it has been found that when a (meth) acrylic copolymer and a cross-linking agent described below are used, an adhesive layer excellent in the above light leakage prevention property and durability can be formed. That is, the present inventors have found that the above problems can be solved by using a polarizing plate pressure-sensitive adhesive layer having the following specific configuration, and have completed the present invention.
  • the present invention includes, for example, the following [1] to [10].
  • the photoelastic coefficient is ⁇ 200 ⁇ 10 ⁇ 12 having a structural unit derived from an aromatic ring-containing (meth) acrylate (a12) having an elastic modulus of + 500 ⁇ 10 ⁇ 12 to + 2000 ⁇ 10 ⁇ 12 (m 2 / N).
  • a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer (A1) of ⁇ + 200 ⁇ 10 ⁇ 12 (m 2 / N) and an isocyanate crosslinking agent (B1) having no aromatic ring.
  • a pressure-sensitive adhesive layer for a polarizing plate having a photoelastic coefficient of ⁇ 200 ⁇ 10 ⁇ 12 to + 200 ⁇ 10 ⁇ 12 (m 2 / N) and disposed in direct contact with a polarizer.
  • Adhesive layer Adhesive layer.
  • a pressure-sensitive adhesive sheet for polarizing plate having the pressure-sensitive adhesive layer according to any one of [1] to [6].
  • a polarizing plate with a pressure-sensitive adhesive layer comprising a polarizer and the pressure-sensitive adhesive layer according to any one of [1] to [6], which is directly laminated on at least one surface of the polarizer.
  • the photoelastic coefficient is ⁇ 200 ⁇ 10 ⁇ 12 having a structural unit derived from an aromatic ring-containing (meth) acrylate (a12) having an elastic modulus of + 500 ⁇ 10 ⁇ 12 to + 2000 ⁇ 10 ⁇ 12 (m 2 / N).
  • the adhesive composition for polarizing plates used in order to form the adhesive layer as described in said [4].
  • the pressure-sensitive adhesive composition for polarizing plate, the pressure-sensitive adhesive layer for polarizing plate, the pressure-sensitive adhesive sheet for polarizing plate and the polarizing plate with the pressure-sensitive adhesive layer will be described.
  • the pressure-sensitive adhesive composition for polarizing plate, the pressure-sensitive adhesive layer for polarizing plate and the pressure-sensitive adhesive sheet for polarizing plate of the present invention are also referred to as “pressure-sensitive adhesive composition”, “pressure-sensitive adhesive layer” and “pressure-sensitive adhesive sheet”, respectively.
  • the first pressure-sensitive adhesive composition for polarizing plate of the present invention comprises a (meth) acrylic copolymer (A1) having a photoelastic coefficient of ⁇ 200 ⁇ 10 ⁇ 12 to + 200 ⁇ 10 ⁇ 12 (m 2 / N), And an isocyanate-based cross-linking agent (B1) having no aromatic ring, and used to form an adhesive layer in direct contact with the polarizer.
  • A1 acrylic copolymer having a photoelastic coefficient of ⁇ 200 ⁇ 10 ⁇ 12 to + 200 ⁇ 10 ⁇ 12 (m 2 / N)
  • B1 isocyanate-based cross-linking agent having no aromatic ring
  • the photoelastic coefficient is obtained by crosslinking a (meth) acrylic copolymer having a photoelastic coefficient in the above range with an isocyanate-based crosslinking agent that does not have an aromatic ring and has a small contribution to the photoelastic coefficient of the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive layer having a thickness of ⁇ 200 ⁇ 10 ⁇ 12 to + 200 ⁇ 10 ⁇ 12 (m 2 / N) can be formed.
  • the second pressure-sensitive adhesive composition for polarizing plate of the present invention comprises a (meth) acrylic copolymer (A2) having a photoelastic coefficient of less than ⁇ 200 ⁇ 10 ⁇ 12 (m 2 / N), an aromatic ring. It is used for forming a pressure-sensitive adhesive layer in direct contact with the polarizer.
  • A2 acrylic copolymer having a photoelastic coefficient of less than ⁇ 200 ⁇ 10 ⁇ 12 (m 2 / N), an aromatic ring. It is used for forming a pressure-sensitive adhesive layer in direct contact with the polarizer.
  • a (meth) acrylic copolymer having a negative photoelastic coefficient is cross-linked with an isocyanate cross-linking agent having an aromatic ring that shifts the photoelastic coefficient of the pressure-sensitive adhesive layer to the plus side.
  • a pressure-sensitive adhesive layer having a size of ⁇ 10 ⁇ 12 to + 200 ⁇ 10 ⁇ 12 (m 2 / N) can be formed.
  • copolymers (A1) and (A2) are collectively referred to as “copolymer (A)”, and the first and second pressure-sensitive adhesive compositions for polarizing plates of the present invention are respectively referred to as “copolymer (A)”. These are also referred to as “first pressure-sensitive adhesive composition” and “second pressure-sensitive adhesive composition”, and are collectively referred to as “pressure-sensitive adhesive composition of the present invention”.
  • acrylic and methacryl are collectively referred to as “(meth) acryl”.
  • the structural unit derived from a certain monomer A contained in the polymer is also referred to as “monomer A unit”.
  • a certain ester (a) may be described as "monomer (a)" for convenience.
  • the unit of the photoelastic coefficient of the homopolymer, (meth) acrylic copolymer and pressure-sensitive adhesive layer formed from each monomer is “ ⁇ 10 ⁇ 12 m 2 / N”. is there. Further, for example, ⁇ 200 ⁇ 10 ⁇ 12 to + 200 ⁇ 10 ⁇ 12 (m 2 / N) is ⁇ 200 ⁇ 10 ⁇ 12 (m 2 / N) or more and + 200 ⁇ 10 ⁇ 12 (m 2 / N) or less. means. The same applies to other numerical ranges.
  • the photoelastic coefficient of the homopolymer formed from each monomer is determined as follows.
  • the homopolymer used for the measurement of the photoelastic coefficient is produced by the following procedure.
  • a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube is charged with 100 parts by mass of a monomer and 100 parts by mass of an ethyl acetate solvent, and heated to 80 ° C. while introducing nitrogen gas.
  • 0.1 part by mass of 2,2′-azobisisobutyronitrile is added, and a polymerization reaction is performed at 80 ° C. for 6 hours in a nitrogen gas atmosphere.
  • the mixture is diluted with ethyl acetate to prepare a homopolymer solution of the monomer having a solid concentration of 30% by mass.
  • the homoholomer solution is applied to the release-treated surface of the release-treated polyethylene terephthalate film and dried at 90 ° C. for 3 minutes to form a coating film (homopolymer layer) having a dry film thickness of 20 ⁇ m.
  • the homopolymer layers having a dry film thickness of 20 ⁇ m are bonded together several times in an environment of 23 ° C./50% RH, and processed for 20 minutes in an autoclave adjusted to 50 ° C./5 atm to form a homopolymer layer having a thickness of 1.0 mm. Make it.
  • a homopolymer layer having a thickness of 1.0 mm is cut into a size of 15 mm ⁇ 50 mm, and this is attached to an automatic wavelength scanning ellipsometer (model “M-220”, manufactured by JASCO Corporation) using a jig.
  • the retardation is measured at a measurement wavelength of 633 nm while changing the stress.
  • a plot when the stress is plotted on the horizontal axis and the retardation is plotted on the vertical axis is linearly approximated, and the slope is taken as the photoelastic coefficient of the homopolymer formed from the monomer.
  • Tg of the homopolymer formed from each monomer for example, a value described in Polymer Handbook Fourth Edition (Wiley-Interscience 2003) can be adopted.
  • combined on the following conditions is measured on the following conditions, for example.
  • a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube is charged with 100 parts by mass of a monomer and 100 parts by mass of an ethyl acetate solvent, and heated to 80 ° C. while introducing nitrogen gas.
  • the (meth) acrylic copolymer (A1) has a structural unit derived from (meth) acrylic acid alkyl ester (a11) having a homopolymer photoelastic coefficient of ⁇ 1000 to ⁇ 100, and a photopolymer coefficient of homopolymer of +500. And a structural unit derived from +2000 aromatic ring-containing (meth) acrylic acid ester (a12).
  • a copolymer (A1) is a copolymer obtained by copolymerizing the monomer component containing a monomer (a11) and a monomer (a12), for example.
  • the monomer component (that is, the raw material monomer component of (A1)) is preferably a polymerizable unsaturated double bond-containing monomer.
  • the photoelastic coefficient of the (meth) acrylic copolymer (A1) is ⁇ 200 to +200, preferably ⁇ 100 to +100, more preferably ⁇ 70 to +70.
  • a copolymer (A1) having a photoelastic coefficient in the above range is obtained. be able to.
  • the photoelastic coefficient of the pressure-sensitive adhesive layer can be brought close to the range described below, in particular, 0. Light leakage in the polarizing plate can be suppressed.
  • the monomer (a11) is a (meth) acrylic acid alkyl ester having a homopolymer photoelastic coefficient of ⁇ 1000 to ⁇ 100.
  • the monomer having a photoelastic coefficient of homopolymer in the range of ⁇ 750 to ⁇ 150 is preferable, and the monomer in the range of ⁇ 500 to ⁇ 200 is more preferable.
  • the pressure-sensitive adhesive layer is given softness and exhibits light leakage prevention properties. be able to.
  • the monomer (a11) is preferably a (meth) acrylic acid alkyl ester having a homopolymer Tg of ⁇ 30 ° C. or less, and the Tg is more preferably ⁇ 100 to ⁇ 30 ° C., and further preferably ⁇ 70 to ⁇ 30. ° C.
  • Examples of the monomer (a11) include compounds in which the photoelastic coefficient of the homopolymer is in the above range among the compounds represented by CH 2 ⁇ CR 1 —COOR 2 .
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group preferably has 2 to 16 carbon atoms, and more preferably 4 to 12 carbon atoms.
  • Examples of the monomer (a11) include n-butyl acrylate ( ⁇ 400; ⁇ 50), 2-ethylhexyl acrylate ( ⁇ 700; ⁇ 70), isodecyl methacrylate ( ⁇ 190; ⁇ 41), lauryl methacrylate ( ⁇ 460; -65).
  • the numerical values in parentheses indicate the photoelastic coefficient ( ⁇ 10 ⁇ 12 m 2 / N) on the left side and the Tg (° C.) on the right side of the homopolymer formed from each monomer.
  • Monomer (a11) may be used alone or in combination of two or more. When using 2 or more types of monomers (a11), it is preferable that each monomer satisfy
  • the amount of the monomer (a11) used is preferably 50 to 90% by mass, more preferably 55 to 85% by mass, and further preferably 60 to 80% by mass. %. It is preferable that the amount of the monomer (a11) used is in the above range in that the photoelastic coefficient of the copolymer (A1) obtained can be adjusted in the above range.
  • Aromatic ring-containing (meth) acrylic acid ester (a12) (monomer (a12))
  • the monomer (a12) is an aromatic ring-containing (meth) acrylic acid ester having a homopolymer photoelastic coefficient of +500 to +2000.
  • the monomer having a photoelastic coefficient of the homopolymer in the range of +700 to +1950 is preferred, and the monomer in the range of +800 to +1900 is more preferred.
  • the monomer (a12) is preferably an aromatic ring-containing (meth) acrylic acid ester having a homopolymer Tg of ⁇ 50 ° C. or more, and the Tg is more preferably ⁇ 40 to 130 ° C., further preferably ⁇ 30 to 120. ° C.
  • Examples of the monomer (a12) include compounds in which the photoelastic coefficient of the homopolymer is in the above range among the compounds represented by CH 2 ⁇ CR 3 —COOR 4 .
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is an aromatic ring-containing group.
  • the aromatic ring-containing group include aryl groups such as a phenyl group, arylalkyl groups such as a benzyl group, and aryloxyalkyl groups such as a phenoxyethyl group.
  • R 4 preferably has 6 to 12, more preferably 6 to 10, and even more preferably 7 to 9 carbon atoms.
  • Examples of the monomer (a12) include benzyl acrylate (1840; 6), benzyl methacrylate (1530; 54), and phenoxyethyl acrylate (1830; -22).
  • the numerical values in parentheses indicate the photoelastic coefficient ( ⁇ 10 ⁇ 12 m 2 / N) on the left side and the Tg (° C.) on the right side of the homopolymer formed from each monomer.
  • examples of the monomer (a12) include phenyl acrylate, phenyl methacrylate, and phenoxyethyl methacrylate.
  • Monomer (a12) may be used alone or in combination of two or more. When using 2 or more types of monomers (a12), it is preferable that each monomer satisfy
  • the amount of the monomer (a12) used is preferably 9 to 40% by mass, more preferably 12 to 35% by mass, and further preferably 15 to 30% by mass. %. It is preferable that the amount of the monomer (a12) used is in the above range in that the photoelastic coefficient of the copolymer (A1) obtained can be adjusted in the above range.
  • the raw material monomer component of the copolymer (A1) preferably further contains a monomer having a crosslinkable functional group capable of reacting with the isocyanate-based crosslinker (B1), that is, a crosslinkable functional group-containing monomer (a13). . That is, it is preferable that the copolymer (A1) further has a structural unit derived from the monomer (a13).
  • the monomer (a13) preferably has a polymerizable unsaturated double bond.
  • the crosslinkable functional group include a hydroxyl group and a carboxyl group.
  • examples of the monomer (a13) include a hydroxyl group-containing monomer and a carboxyl group-containing monomer.
  • hydroxyl group-containing monomer examples include a hydroxyl group-containing (meth) acrylate, and specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate.
  • the number of carbon atoms of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
  • carboxyl group-containing monomer examples include ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ⁇ -carboxypolycaprolactone mono (meth) acrylate.
  • Carboxyl group-containing (meth) acrylates such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.
  • a monomer (a13) may be used individually by 1 type, and may use 2 or more types.
  • the amount of the monomer (a13) used is preferably more than 0% by mass and 10% by mass or less, more preferably 0.5-7% by mass, More preferably, it is 1 to 5% by mass.
  • the usage-amount of a monomer (a13) is below the said upper limit, the crosslinking density formed with a copolymer (A1) and a crosslinking agent (B1) will not become high too much.
  • the usage-amount of a monomer (a13) is more than the said lower limit, a crosslinked structure is formed effectively and the adhesive layer which has suitable intensity
  • the raw material monomer component of the copolymer (A1) is, for example, an alkyl (meth) acrylate other than the monomer (a11), an alkoxyalkyl (meth) acrylate, an alkoxy, as long as the physical properties of the copolymer (A1) are not impaired.
  • Other monomers such as polyalkylene glycol mono (meth) acrylate, alicyclic group-containing (meth) acrylate, amino group-containing monomer and amide group-containing monomer can also be used. That is, the copolymer (A1) may further have structural units derived from other monomers.
  • alkyl (meth) acrylate other than the monomer (a11) examples include methyl acrylate (600; 8), t-butyl methacrylate (130; 118), n-butyl methacrylate (320; 20), 2-ethylhexyl methacrylate ( 420; -10).
  • the numerical values in parentheses indicate the photoelastic coefficient ( ⁇ 10 ⁇ 12 m 2 / N) on the left side and the Tg (° C.) on the right side of the homopolymer formed from each monomer.
  • alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
  • alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
  • Examples of the alicyclic group-containing (meth) acrylate include cyclohexyl (meth) acrylate.
  • Examples of the amino group-containing monomer include amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
  • amide group-containing monomer examples include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-hexyl (meth) acrylamide.
  • the total amount of the other monomers used is not particularly limited as long as the photoelastic coefficient of (A1) is in the above range, but it is 0 to 10% by mass. Preferably, it is 0 to 5% by mass.
  • the (meth) acrylic copolymer (A2) is a copolymer having a photoelastic coefficient of less than ⁇ 200, preferably from ⁇ 500 to less than ⁇ 200, more preferably from ⁇ 300 to less than ⁇ 200.
  • Such a copolymer has, for example, a structural unit derived from a (meth) acrylic acid alkyl ester (a21) having a photoelastic coefficient of less than ⁇ 200, for example, a monomer component containing the monomer (a21). Is obtained by copolymerization.
  • the monomer component (that is, the raw material monomer component of (A2)) is preferably a polymerizable unsaturated double bond-containing monomer.
  • the copolymer (A2) and the isocyanate-based cross-linking agent (B2) having an aromatic ring the photoelastic coefficient of the pressure-sensitive adhesive layer can be brought close to the range described below, in particular, 0. The light leak in can be suppressed.
  • ⁇ (Meth) acrylic acid alkyl ester (a21) (monomer (a21)) Examples of the monomer (a21) include an ester having a homopolymer photoelastic coefficient of less than ⁇ 200 in the above-mentioned (meth) acrylic acid alkyl ester (a11).
  • the monomer having a photoelastic coefficient of the homopolymer of ⁇ 750 or more and less than ⁇ 200 is preferred, and the monomer having a ⁇ 500 or more and less than ⁇ 200 is more preferred.
  • Monomer (a21) may be used alone or in combination of two or more. When using 2 or more types of monomers (a21), it is preferable that each monomer satisfy
  • the amount of the monomer (a21) used is preferably 59 to 99% by mass, more preferably 64 to 98% by mass, and further preferably 69 to 97% by mass. %. It is preferable that the amount of the monomer (a21) used is in the above range in that the photoelastic coefficient of the obtained copolymer (A2) can be adjusted in the above range.
  • the raw material monomer component of the copolymer (A2) preferably further contains a monomer having a crosslinkable functional group capable of reacting with the isocyanate-based crosslinker (B2), that is, a crosslinkable functional group-containing monomer (a22). . That is, it is preferable that the copolymer (A2) further has a structural unit derived from the monomer (a22).
  • monomer (a22) the crosslinkable functional group containing monomer (a13) mentioned above can be illustrated, and its preferable example is also the same.
  • a monomer (a22) may be used individually by 1 type, and may use 2 or more types.
  • the amount of the monomer (a22) used is preferably more than 0% by mass and 10% by mass or less, more preferably 0.5-7% by mass, More preferably, it is 1 to 5% by mass.
  • the usage-amount of a monomer (a22) is below the said upper limit, the crosslinking density formed with a copolymer (A2) and a crosslinking agent (B2) will not become high too much.
  • the usage-amount of a monomer (a22) is more than the said lower limit, a crosslinked structure is formed effectively and the adhesive layer which has appropriate intensity
  • the raw material monomer component of the copolymer (A2) is, for example, an alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxy other than the monomer (a21) as long as the physical properties of the copolymer (A2) are not impaired.
  • Other monomers such as polyalkylene glycol mono (meth) acrylate, alicyclic group-containing (meth) acrylate, aromatic ring-containing (meth) acrylate, amino group-containing monomer and amide group-containing monomer can also be used. That is, the copolymer (A2) may further have structural units derived from other monomers.
  • Examples of these monomers include the respective compounds described in ⁇ Other monomers >> in the copolymer (A1) column.
  • Examples of the aromatic ring-containing (meth) acrylate include phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
  • the (meth) acrylic acid alkyl ester having a homopolymer photoelastic coefficient of +100 to +1000, and the aromatic ring-containing (meth) acrylic acid ester having a photoelastic coefficient of +500 to +2000 (the monomer (a12) described above)
  • the amount of use it is preferable to adjust the amount of use as appropriate.
  • Examples of the (meth) acrylic acid alkyl ester having a homopolymer photoelastic coefficient of +100 to +1000 include, for example, methyl acrylate (600), t-butyl methacrylate (130), n-butyl methacrylate (320), 2-ethylhexyl methacrylate ( 420).
  • the numerical value in the parenthesis indicates the photoelastic coefficient ( ⁇ 10 ⁇ 12 m 2 / N) of the homopolymer formed from each monomer.
  • the total use amount of the other monomers is not particularly limited as long as the photoelastic coefficient of (A2) is in the above range, but is 0 to 35% by mass.
  • the content is preferably 0 to 30% by mass, more preferably 0 to 26% by mass.
  • the manufacturing conditions of a (meth) acrylic-type copolymer (A) are not specifically limited, For example, it can manufacture by a solution polymerization method. Specifically, a polymerization solvent and a monomer component are charged into a reaction vessel, a polymerization initiator is added, the reaction start temperature is usually set to 40 to 100 ° C., preferably 50 to 90 ° C., and the reaction system is usually used. The reaction is carried out for 2 to 20 hours while maintaining the temperature at 50 to 90 ° C., preferably 70 to 90 ° C.
  • the polymerization reaction can be performed, for example, in an inert gas atmosphere such as nitrogen gas.
  • the copolymer (A) is obtained, for example, by copolymerizing the monomer components described above, but may be a random copolymer or a block copolymer. Among these, a random copolymer is preferable.
  • polymerization solvent examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, cyclohexane, and cycloheptane.
  • Cycloaliphatic hydrocarbons such as cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, Halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexane Ketones such as Sanone; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Nitriles such as aceton
  • Examples of the polymerization initiator include azo initiators and peroxide initiators. Specific examples include azo compounds such as 2,2′-azobisisobutyronitrile, and peroxides such as benzoyl peroxide and lauroyl peroxide. Among these, an azo compound is preferable. Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropyl).
  • the polymerization initiator is usually in the range of 0.01 to 5 parts by weight, preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the raw material monomer component of the (meth) acrylic copolymer (A). Used in quantity. Moreover, you may add suitably a polymerization initiator, a chain transfer agent, a monomer component, and a polymerization solvent during the said polymerization reaction.
  • the photoelastic coefficient of the (meth) acrylic copolymer (A) is as described above.
  • the weight average molecular weight (Mw) measured by the gel permeation chromatography method (GPC method) of the (meth) acrylic copolymer (A) is a polystyrene conversion value, and is usually 300,000 to 2,000,000, preferably Is 400,000 to 1.8 million, more preferably 500,000 to 1,500,000.
  • the molecular weight distribution (Mw / Mn) of the (meth) acrylic copolymer (A) measured by the GPC method is usually 20 or less, preferably 2 to 15, more preferably 2 to 9.
  • the glass transition temperature (Tg) of the (meth) acrylic copolymer (A) can be calculated by, for example, the Fox formula from the monomer units constituting the copolymer and the content ratio thereof.
  • the (meth) acrylic copolymer (A) is synthesized so that the glass transition temperature (Tg) determined by the Fox equation is usually ⁇ 70 to ⁇ 10 ° C., preferably ⁇ 60 to ⁇ 20 ° C. It is preferable to do.
  • Tg glass transition temperature (K) of the (meth) acrylic copolymer (A)
  • Tg 1 , Tg 2 ,..., Tg m glass transition temperatures (K) of homopolymers composed of the respective monomers.
  • W 1 , W 2 ,..., W m are the weight fractions of the structural units derived from the respective monomers in the copolymer (A).
  • the charging ratio of each monomer to the total monomers at the time of copolymer synthesis can be used.
  • the glass transition temperature of the homopolymer composed of each monomer in the Fox formula for example, a value described in Polymer Handbook Fourth Edition (Wiley-Interscience 2003) can be used.
  • the monomer in which Tg is not described in the said literature the value obtained by the method mentioned above is used, for example.
  • the content of the (meth) acrylic copolymer (A1) is 100% by mass of the solid content excluding the organic solvent in the composition, usually 60 to 99.95% by mass, The amount is preferably 70 to 99.5% by mass, particularly preferably 80 to 99.0% by mass.
  • the content of the (meth) acrylic copolymer (A1) is in the above range, the performance as an adhesive is balanced and the adhesive properties are excellent.
  • the content of the (meth) acrylic copolymer (A2) is 100% by mass of the solid content excluding the organic solvent in the composition, usually 60 to 98.0% by mass, The amount is preferably 70 to 96.2% by mass, particularly preferably 80 to 92.6% by mass.
  • the content of the (meth) acrylic copolymer (A2) is in the above range, the performance as an adhesive is balanced and the adhesive properties are excellent.
  • the 1st adhesive composition further contains the isocyanate type crosslinking agent (B1) which does not have an aromatic ring.
  • the second pressure-sensitive adhesive composition further contains an isocyanate-based crosslinking agent (B2) having an aromatic ring.
  • Isocyanate-based crosslinking agent (B1) As the isocyanate-based crosslinking agent (B1), an isocyanate compound having 2 or more isocyanate groups in one molecule and having no aromatic ring is usually used. By crosslinking the (meth) acrylic copolymer (A1) with the crosslinking agent (B1), a crosslinked body (network polymer) having excellent durability can be formed. Further, by using the crosslinking agent (B1) having no aromatic ring together with the copolymer (A1) having a photoelastic coefficient in the range of ⁇ 200 to +200, an adhesive having a photoelastic coefficient in the range of ⁇ 200 to +200. An agent layer can be formed.
  • the number of isocyanate groups in the crosslinking agent (B1) is usually 2 or more, preferably 2 to 8, and more preferably 3 to 6. When the number of isocyanate groups is within the above range, it is preferable from the viewpoint of the crosslinking reaction efficiency between the (meth) acrylic copolymer (A1) and the crosslinking agent (B1) and the flexibility of the pressure-sensitive adhesive layer.
  • diisocyanate compound having 2 isocyanate groups in one molecule examples include aliphatic diisocyanate and alicyclic diisocyanate.
  • aliphatic diisocyanate examples include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4 -Aliphatic diisocyanates having 4 to 30 carbon atoms such as trimethyl-1,6-hexamethylene diisocyanate.
  • Examples of the alicyclic diisocyanate include those having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
  • An alicyclic diisocyanate is mentioned.
  • Examples of the isocyanate compound having 3 or more isocyanate groups in one molecule include aliphatic polyisocyanates and alicyclic polyisocyanates.
  • Examples of the crosslinking agent (B1) include multimers (for example, dimers or trimers, biurets, isocyanurates) and derivatives (for example, many) of the above isocyanate compounds having 2 or more isocyanate groups. Addition reaction product of a dihydric alcohol and two or more molecules of the diisocyanate compound), and a polymer.
  • polyhydric alcohol in the derivative examples include trivalent or higher alcohols such as trimethylolpropane, glycerin and pentaerythritol as low molecular weight polyhydric alcohols; high molecular weight polyhydric alcohols such as polyether polyols, Examples include polyester polyol, acrylic polyol, polybutadiene polyol, and polyisoprene polyol.
  • Examples of such an isocyanate compound include a biuret or isocyanurate of hexamethylene diisocyanate, a reaction product of trimethylolpropane and hexamethylene diisocyanate (for example, a trimolecular adduct of hexamethylene diisocyanate), polyether polyisocyanate, Polyester polyisocyanate is mentioned.
  • hexamethylene diisocyanate-based cross-linking agents are preferable because they can improve aging properties and light leakage prevention properties.
  • examples of the hexamethylene diisocyanate-based crosslinking agent include hexamethylene diisocyanate and derivatives thereof, biuret or isocyanurate. Examples of commercially available products include “D-94” manufactured by Soken Chemical Co., Ltd.
  • a crosslinking agent (B1) may be used individually by 1 type, and may use 2 or more types.
  • the content of the crosslinking agent (B1) is usually 0.05 to 10 parts by mass, preferably 0 with respect to 100 parts by mass of the (meth) acrylic copolymer (A1). 5 to 8 parts by mass, more preferably 1 to 5 parts by mass.
  • the content of the cross-linking agent (B1) is in the above range, it is preferable in terms of easy balance between durability and light leakage prevention.
  • Isocyanate-based crosslinking agent (B2) As the isocyanate-based crosslinking agent (B2), an isocyanate compound having an aromatic ring having 2 or more isocyanate groups in one molecule is usually used. By crosslinking the (meth) acrylic copolymer (A2) with the crosslinking agent (B2), it is possible to form a crosslinked body (network polymer) excellent in durability. Further, by using the crosslinking agent (B2) having an aromatic ring together with the copolymer (A2) having a photoelastic coefficient in the range of less than ⁇ 200, an adhesive layer having a photoelastic coefficient in the range of ⁇ 200 to +200 is obtained. Can be formed.
  • the number of isocyanate groups in the crosslinking agent (B2) is usually 2 or more, preferably 2 to 8, and more preferably 3 to 6. When the number of isocyanate groups is within the above range, it is preferable from the viewpoint of the crosslinking reaction efficiency between the (meth) acrylic copolymer (A2) and the crosslinking agent (B2) and the flexibility of the pressure-sensitive adhesive layer.
  • diisocyanate compound having 2 isocyanate groups in one molecule examples include aromatic diisocyanates.
  • aromatic diisocyanate examples include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
  • isocyanate compound having 3 or more isocyanate groups in one molecule examples include aromatic polyisocyanates. Specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4 ', 4 "-triphenylmethane triisocyanate.
  • crosslinking agent (B2) examples include multimers (for example, dimers or trimers, biurets, isocyanurates), derivatives (for example, many) of the above isocyanate compounds having 2 or more isocyanate groups. Addition reaction product of a dihydric alcohol and two or more molecules of the diisocyanate compound), and a polymer.
  • polyhydric alcohol in the derivative examples include trivalent or higher alcohols such as trimethylolpropane, glycerin and pentaerythritol as low molecular weight polyhydric alcohols; high molecular weight polyhydric alcohols such as polyether polyols, Examples include polyester polyol, acrylic polyol, polybutadiene polyol, and polyisoprene polyol.
  • Examples of such an isocyanate compound include diphenylmethane diisocyanate trimer, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate biuret or isocyanurate, and reaction reaction of trimethylolpropane with tolylene diisocyanate or xylylene diisocyanate.
  • diphenylmethane diisocyanate trimer polymethylene polyphenyl polyisocyanate
  • tolylene diisocyanate biuret or isocyanurate and reaction reaction of trimethylolpropane with tolylene diisocyanate or xylylene diisocyanate.
  • a trimolecular adduct of tolylene diisocyanate or xylylene diisocyanate polyether polyisocyanate
  • polyester polyisocyanate polyester polyisocyanate.
  • cross-linking agents (B2) at least one selected from a tolylene diisocyanate cross-linking agent and a xylylene diisocyanate cross-linking agent is preferable in that aging property and light leakage prevention property can be improved.
  • a cross-linking agent is more preferable.
  • tolylene diisocyanate crosslinking agents include tolylene diisocyanate and derivatives thereof, biuret bodies or isocyanurate bodies.
  • xylylene diisocyanate-based crosslinking agent include xylylene diisocyanate and derivatives thereof, biuret or isocyanurate.
  • commercially available products include “L-45” manufactured by Soken Chemical Co., Ltd.
  • a crosslinking agent (B2) may be used individually by 1 type, and may use 2 or more types.
  • the content of the crosslinking agent (B2) is usually 2 parts by mass or more, preferably 4 to 30 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer (A2). Part, more preferably 8 to 15 parts by weight.
  • the content of the crosslinking agent (B2) is in the above range, even a composition containing the copolymer (A2) having a negative photoelastic coefficient can form a layer having a photoelastic coefficient of around 0. This is preferable in terms of easy balance between durability and light leakage prevention.
  • the first and second pressure-sensitive adhesive compositions respectively contain other crosslinking agents other than the crosslinking agent (B1) or the crosslinking agent (B2). Furthermore, you may contain.
  • the durability is further improved while maintaining the photoelastic coefficient in the range described later. You can also.
  • the other cross-linking agent is not particularly limited as long as it is a component capable of causing a cross-linking reaction with a cross-linkable functional group derived from a cross-linkable functional group-containing monomer.
  • a metal chelate compound (B3), an epoxy compound (B4) Is mentioned.
  • the content when other crosslinking agents are used is preferably 2 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic copolymer (A). More preferred is 0.01 to 1.5 parts by mass, and still more preferred is 0.03 to 1 part by mass.
  • Metal chelate compound (B3) examples include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium, alkoxide, acetylacetone, and ethyl acetoacetate. Examples include a coordinated compound.
  • an aluminum chelate compound is particularly preferable.
  • Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethyl acetoacetate / diisopropylate, aluminum trisethyl acetoacetate, and aluminum trisacetylacetonate.
  • Examples of commercially available products include “M-12AT” manufactured by Soken Chemical Co., Ltd.
  • a metal chelate compound (B3) may be used individually by 1 type, and may use 2 or more types.
  • the metal chelate compound (B3) crosslinks the (meth) acrylic copolymer (A) by coordination bond (pseudocrosslinking).
  • the metal chelate compound (B3) is further used as a cross-linking agent, the cross-linking is maintained at room temperature and the polymer exhibits cohesiveness, whereas the cross-linking is partially released at a high temperature and the pressure-sensitive adhesive layer is more excellent. Show flexibility.
  • Epoxy compound (B4) an epoxy compound having 2 or more epoxy groups in one molecule is usually used.
  • the pressure-sensitive adhesive composition of the present invention preferably further contains a silane coupling agent (C).
  • a silane coupling agent (C) contributes to the point which adheres an adhesive layer firmly to adherends, such as a glass plate, and prevents peeling of a polarizing plate in a high-humidity heat environment.
  • silane coupling agent (C) examples include polymerizable unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane Epoxy groups such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Containing silane coupling agent; amino such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Group-containing silane coupling Grayed
  • the content of the silane coupling agent (C) is usually 1 part by mass or less, preferably 0.8 parts per 100 parts by mass of the (meth) acrylic copolymer (A). 01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass.
  • the content is in the above range, peeling of the polarizing plate in a high humidity environment and bleeding of the silane coupling agent (C) in a high temperature environment tend to be prevented.
  • the antistatic agent (D) can be used, for example, to reduce the surface resistance value of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
  • examples of the antistatic agent (D) include a surfactant, an ionic compound, and a conductive polymer.
  • surfactant examples include cationic surfactants having cationic groups such as quaternary ammonium salts, amide quaternary ammonium salts, pyridium salts, primary to tertiary amino groups; sulfonate groups, sulfate esters Anionic surfactants having an anionic group such as a base or a phosphate ester base; amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfates, glycerin fatty acid esters
  • Nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines and alkyldiethanolamides It is done.
  • a reactive emulsifier having a polymerizable group is also exemplified as the surfactant, and a polymer surfactant obtained by increasing the molecular weight of the monomer component containing the above surfactant or reactive emulsifier can also be used.
  • the ionic compound is composed of a cation part and an anion part, and may be either solid or liquid at room temperature (23 ° C./50% RH).
  • the cation portion constituting the ionic compound may be either an inorganic cation or an organic cation, or both.
  • the inorganic cation alkali metal ions and alkaline earth metal ions are preferable, and Li + , Na + and K + having excellent antistatic properties are more preferable.
  • organic cations include pyridinium cation, piperidinium cation, pyrrolidinium cation, pyrroline cation, pyrrole cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, pyrazoli Examples thereof include a nium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and derivatives thereof.
  • the anion moiety constituting the ionic compound is not particularly limited as long as it can form an ionic compound by ionic bonding with the cation moiety.
  • Examples of the ionic compound include lithium bis (trifluoromethanesulfonyl) imide, lithium bis (difluorosulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methane, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (difluorosulfonyl) imide, 1 -Ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (fluoro Sulfonyl) imide, 1-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide, tributylmethyl Ammonium bis
  • the conductive polymer examples include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
  • the content of the antistatic agent (D) is usually 3 parts by mass or less, preferably 0.01 parts per 100 parts by mass of the (meth) acrylic copolymer (A). To 3 parts by mass, more preferably 0.05 to 2.5 parts by mass.
  • the pressure-sensitive adhesive composition of the present invention preferably contains an organic solvent (E) in order to adjust its applicability.
  • an organic solvent the solvent illustrated as a polymerization solvent in the column of the manufacturing conditions of a (meth) acrylic-type copolymer (A) is mentioned.
  • the pressure-sensitive adhesive composition can be prepared by mixing the polymer solution containing the (meth) acrylic copolymer (A) and the polymerization solvent obtained by the above copolymerization and the crosslinking agent (B). it can.
  • the content of the organic solvent (E) is usually 50 to 90% by mass, preferably 60 to 85% by mass.
  • solid content refers to all components excluding the organic solvent (E) among the components contained in the pressure-sensitive adhesive composition
  • solid content concentration refers to the pressure-sensitive adhesive composition 100. It refers to the ratio of the solid content to mass%.
  • the pressure-sensitive adhesive composition of the present invention includes an antioxidant, a light stabilizer, a metal corrosion inhibitor, a tackifier, a plasticizer, a crosslinking accelerator, You may contain the 1 type (s) or 2 or more types selected from the (meth) acrylic-type polymer and rework agents other than A).
  • the pressure-sensitive adhesive composition of the present invention is prepared by mixing the (meth) acrylic copolymer (A), the cross-linking agent (B), and other components as required by a conventionally known method. Can do.
  • the cross-linking agent (B) and, if necessary, other components may be added to the polymer solution containing the polymer obtained when the (meth) acrylic copolymer (A) is synthesized. It is done.
  • a pressure-sensitive adhesive layer is formed on a polarizing plate having a polarizer protective film on only one side of the polarizer and on a polarizing plate having no polarizer protective film on both sides of the polarizer.
  • the light leakage phenomenon can be suppressed.
  • even when the pressure-sensitive adhesive layer is in direct contact with the polarizer, tearing of the pressure-sensitive adhesive layer, peeling of the polarizing plate, and the like can be suppressed under a high temperature and high humidity environment.
  • the said composition is suitable for the bonding application of the board
  • the 1st adhesive layer for polarizing plates of this invention is formed from the above-mentioned 1st adhesive composition.
  • the 2nd adhesive layer for polarizing plates of this invention is formed from the above-mentioned 2nd adhesive composition.
  • the first and second pressure-sensitive adhesive layers are collectively referred to as “the pressure-sensitive adhesive layer of the present invention”.
  • a pressure-sensitive adhesive layer having the following photoelastic properties can be formed.
  • the photoelastic coefficient of the pressure-sensitive adhesive layer of the present invention is ⁇ 200 to +200, preferably ⁇ 150 to +150, more preferably ⁇ 100 to +100, and further preferably ⁇ 70 to +70.
  • the unit of the photoelastic coefficient is “ ⁇ 10 ⁇ 12 m 2 / N”.
  • the photoelastic coefficient is measured at a measurement wavelength of 633 nm, for example, by laminating the pressure-sensitive adhesive layers a plurality of times to produce a laminate having a thickness of about 1.0 mm. Details of the measurement conditions are as described in the examples.
  • the pressure-sensitive adhesive layer of the present invention has the above properties, it is excellent in light leakage prevention properties under a high temperature and high humidity environment. Moreover, since the adhesive layer of this invention is excellent in durability, it is hard to generate
  • the pressure-sensitive adhesive layer of the present invention has a gel fraction of preferably 40% by mass or more, more preferably 50 to 97% by mass, and still more preferably, from the viewpoint of distortion suppression of the polarizing plate, cohesive strength, adhesive strength, and removability. Is 60 to 95% by mass. When the gel fraction is in the above range, the pressure-sensitive adhesive layer exhibits excellent durability. Details of the measurement conditions are as described in the examples.
  • the pressure-sensitive adhesive layer of the present invention specifically cross-links the (meth) acrylic copolymer (A) with the cross-linking agent (B) by, for example, advancing the crosslinking reaction in the above-mentioned pressure-sensitive adhesive composition. Is obtained.
  • the conditions for forming the pressure-sensitive adhesive layer are, for example, as follows.
  • the pressure-sensitive adhesive composition of the present invention is applied onto a support and varies depending on the type of solvent, but is usually 50 to 150 ° C., preferably 60 to 100 ° C., usually 1 to 10 minutes, preferably 2 to 7 Dry for minutes to remove the solvent and form a coating.
  • the film thickness of the dried coating film is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m, and the film thickness of the finally obtained pressure-sensitive adhesive layer is preferably in the above range.
  • the film thickness can be measured by, for example, a dial thickness gauge.
  • the pressure-sensitive adhesive layer is preferably formed under the following conditions. After applying the pressure-sensitive adhesive composition of the present invention on a support to form a coating film under the above conditions, and applying a cover film on the coating film as necessary, it is usually 3 days or more, preferably 7 to It is cured for 10 days in an environment of usually 5 to 60 ° C., preferably 15 to 40 ° C., usually 30 to 70% RH, preferably 40 to 70% RH. When crosslinking is performed under the aging conditions as described above, a crosslinked body (network polymer) can be efficiently formed.
  • a predetermined thickness is obtained by a known method such as spin coating, knife coating, roll coating, bar coating, blade coating, die coating, or gravure coating.
  • coating can be used.
  • polyester films such as polyethylene terephthalate (PET); plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • PET polyethylene terephthalate
  • plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • the pressure-sensitive adhesive sheet for polarizing plates of the present invention has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
  • the pressure-sensitive adhesive sheet include a double-sided pressure-sensitive adhesive sheet having only the pressure-sensitive adhesive layer, a base material, and a double-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed on both surfaces of the base material, the base material, and one of the base materials.
  • Examples thereof include a single-sided pressure-sensitive adhesive sheet having the above-mentioned pressure-sensitive adhesive layer formed on the surface, and a pressure-sensitive adhesive sheet having a peel-treated cover film attached to the surface of the pressure-sensitive adhesive sheet that is not in contact with the base material.
  • polyester films such as polyethylene terephthalate (PET); plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • PET polyethylene terephthalate
  • plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • the conditions for forming the pressure-sensitive adhesive layer are the same as the conditions described in the column [Plastic pressure-sensitive adhesive layer].
  • the thickness of the pressure-sensitive adhesive layer is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m, from the viewpoint of maintaining adhesive performance.
  • the thickness of the substrate and the cover film is not particularly limited, but is usually 10 to 125 ⁇ m, preferably 25 to 75 ⁇ m.
  • the polarizing plate with an adhesive layer of this invention has a polarizer and the adhesive layer formed from the adhesive composition of this invention directly laminated
  • polarizing plate is used to include “polarizing film”.
  • the polarizing plate As the polarizing plate, a conventionally known polarizing film can be used.
  • positioned on a polarizer is mentioned.
  • the pressure-sensitive adhesive layer is disposed in direct contact with the polarizer, for example, the polarizer protective film is disposed only on one surface of the polarizer, and the polarizer protective film is not disposed on the other surface.
  • positioned on both surfaces of a polarizer are mentioned.
  • Examples of the polarizer include a stretched film obtained by stretching a film made of a polyvinyl alcohol-based resin containing a polarizing component.
  • Examples of the polyvinyl alcohol-based resin include saponified products of polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, and ethylene-vinyl acetate copolymer.
  • Examples of the polarization component include iodine or a dichroic dye.
  • the polarizer protective film examples include a film made of a thermoplastic resin.
  • the thermoplastic resin include cellulose resin such as triacetyl cellulose, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, cyclic polyolefin resin (norbornene) Resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and a mixture of two or more selected from these resins.
  • cellulose resin such as triacetyl cellulose, polyester resin, polyethersulfone resin, polysulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, cyclic polyolefin resin (norbornene) Resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and a mixture of two or more selected from these resins.
  • the thickness of the polarizing plate is usually 10 to 200 ⁇ m, preferably 30 to 100 ⁇ m.
  • a polarizing plate can be reduced in thickness.
  • the pressure-sensitive adhesive layer is formed in direct contact with the polarizer.
  • a polarizing plate with an adhesive layer of the present invention for example, a polarizer protective film, a polarizer, and the adhesive layer are laminated in this order, the adhesive layer, the polarizer protective film, the polarizer, and the above
  • the cover film mentioned above may be arrange
  • the thickness of the pressure-sensitive adhesive layer is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m.
  • the pressure-sensitive adhesive layer only needs to be formed in contact with the polarizer on at least one surface of the polarizer, and the pressure-sensitive adhesive layer is formed only on one side of the polarizer, and the pressure-sensitive adhesive is formed on both sides of the polarizer.
  • the aspect in which a layer is formed is mentioned.
  • the layer which has other functions such as a protective layer, a glare-proof layer, a phase difference layer, a viewing angle improvement layer, for example may be laminated
  • a liquid crystal element is produced by providing the polarizing plate with the pressure-sensitive adhesive layer of the present invention obtained as described above on the substrate surface of the liquid crystal cell.
  • the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates.
  • An example of the substrate that the liquid crystal cell has is a glass plate.
  • the thickness of the substrate is usually 0.05 to 3 mm, preferably 0.2 to 1 mm.
  • HLC-8320GPC manufactured by Tosoh Corporation
  • -GPC column configuration The following four columns (all manufactured by Tosoh Corporation) (1) TSKgel HxL-H (guard column) (2) TSKgel GMHxL (3) TSKgel GMHxL (4) TSKgel G2500HxL ⁇ Flow rate: 1.0 mL / min -Column temperature: 40 ° C Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran) ⁇ Mobile phase solvent: Tetrahydrofuran ⁇ Standard polystyrene conversion
  • the photoelastic coefficient was measured as follows.
  • the polymer solution containing the (meth) acrylic copolymer obtained in the synthesis example was applied to the release-treated surface of the release-treated polyethylene terephthalate film, dried at 90 ° C. for 3 minutes, and a dry film thickness of 20 ⁇ m.
  • a coating film (polymer layer) was formed. Polymer layers with a dry film thickness of 20 ⁇ m were bonded together in an environment of 23 ° C./50% RH multiple times and treated with an autoclave adjusted to 50 ° C./5 atm for 20 minutes to produce a polymer layer with a thickness of 1.0 mm. .
  • a polymer layer having a thickness of 1.0 mm is cut into a size of 15 mm ⁇ 50 mm, and this is attached to an automatic wavelength scanning ellipsometer (model “M-220”, manufactured by JASCO Corporation) using a jig, Retardation was measured at a measurement wavelength of 633 nm while changing the stress.
  • the slope of the straight line when the stress is taken on the horizontal axis and the retardation is taken on the vertical axis was taken as the photoelastic coefficient of the (meth) acrylic copolymer.
  • the obtained (meth) acrylic copolymer 1 has a weight average molecular weight (Mw) of 800,000, a molecular weight distribution (Mw / Mn) of 7.5, and a photoelastic coefficient of ⁇ 58 ⁇ 10 ⁇ 12 ( m 2 / N).
  • Example A1 (1) Preparation of pressure-sensitive adhesive composition Based on the polymer solution obtained in Synthesis Example 1 (solid content concentration of 30% by mass) and 100 parts (solid content) of (meth) acrylic copolymer 1 contained in the solution As the isocyanate compound, 2.0 parts (solid content) of “D-94” manufactured by Soken Chemical Co., Ltd. and 0.2 part (solid content) of “M-12AT” manufactured by Soken Chemical Co., Ltd. as the metal chelate compound, As a silane coupling agent, 0.2 part of “A-50” (solid content: 100% by mass) manufactured by Soken Chemical Co., Ltd. was mixed to obtain an adhesive composition.
  • Example B1 and B2 Comparative Examples A1 and A2, B1 and B3
  • the adhesive composition was changed in the same manner as in Example A1, except that the polymer solution was changed to the polymer solution obtained in each synthesis example and / or the blending composition was changed as shown in Table 2. Thing, the adhesive sheet, and the polarizing plate with an adhesive layer were obtained.
  • This test plate was allowed to stand for 500 hours under the condition of a temperature of 80 ° C./dry, and light leakage was observed according to the following criteria. AA: No light leakage was observed BB: Light leakage was slightly observed CC: Light leakage was clearly observed
  • the polarizing plate with a pressure-sensitive adhesive layer obtained in the examples and comparative examples was cut into a size of 150 mm ⁇ 250 mm, and the test piece was cut. Created.
  • the PET film is peeled from the test piece, and a laminate composed of an adhesive layer / polarizer / polarizer protective film is laminated on one side of a 0.5 mm thick glass plate using a laminator roll. I stuck it so that it touched.
  • the obtained laminate was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes to prepare a test plate.
  • test plates Two similar test plates were prepared. The test plate is allowed to stand for 500 hours under conditions of a temperature of 80 ° C./dry (heat resistance) or a temperature of 60 ° C./humidity of 90% RH (moisture heat resistance), and defects (foaming, floating, peeling off) according to the following criteria: ) Was evaluated.
  • AA No defect
  • BB Defect area is 5% or less
  • CC Defect area exceeds 5%, there is a problem in practical use
  • D-94 Hexamethylene diisocyanate crosslinking agent (manufactured by Soken Chemical Co., Ltd., solid content 90% by mass)
  • L-45 Tolylene diisocyanate crosslinking agent (manufactured by Soken Chemical Co., Ltd., solid content 45% by mass, ethyl acetate / toluene solution)
  • E-5C Epoxy crosslinking agent (manufactured by Soken Chemical Co., Ltd., solid content 5 mass%)
  • M-12AT Aluminum chelate cross-linking agent (manufactured by Soken Chemical Co., Ltd., solid content 10% by mass, toluene / acetylacetone solution)
  • A-50 Silane coupling agent (manufactured by Soken Chemical Co., Ltd., solid content 50 mass%, toluene solution)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention vise à créer une couche adhésive qui est applicable à une configuration dans laquelle au moins l'un des films de protection de polariseur formés de manière classique sur les deux surfaces d'un polariseur est omis, et qui présente d'excellentes propriétés de prévention de fuite de lumière et durabilité. Pour ce faire, l'invention propose une couche adhésive destinée à des plaques polarisantes, qui est caractérisée en ce qu'elle est formée à partir d'une composition adhésive qui contient : un copolymère (méth)acrylique qui présente un coefficient photoélastique allant de -200 × 10-12 à +200 × 10-12 (m2/N) et comprend un motif constitutif dérivé d'un groupe ester de (méth)acrylate d'alkyle ayant un coefficient photoélastique d'un homopolymère allant de -1 000 × 10-12 à -100 × 10-12 (m2/N) et un motif constitutif dérivé d'un ester de (méth)acrylate contenant un cycle aromatique ayant un coefficient photoélastique d'un homopolymère allant de +500 × 10-12 à +2 000 × 10-12 (m2/N) ; et un agent de réticulation isocyanate n'ayant aucun cycle aromatique. La présente couche adhésive destinée à des plaques de polarisation est également caractérisée en ce qu'elle présente un coefficient photoélastique allant de -200 × 10-12 à +200 × 10-12 (m2/N) et en ce qu'elle est disposée directement sur un polariseur.
PCT/JP2016/072147 2015-08-18 2016-07-28 Couche adhésive destinée à des plaques de polarisation, et composition adhésive Ceased WO2017029959A1 (fr)

Priority Applications (3)

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CN201680046837.7A CN107924009B (zh) 2015-08-18 2016-07-28 偏振片用粘合剂层和粘合剂组合物
JP2017535310A JP6886401B2 (ja) 2015-08-18 2016-07-28 偏光板用の粘着剤層および粘着剤組成物
KR1020187005471A KR102243893B1 (ko) 2015-08-18 2016-07-28 편광판용의 점착제층 및 점착제 조성물

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JP2015-160924 2015-08-18
JP2015160924 2015-08-18

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CN (1) CN107924009B (fr)
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JP7327740B2 (ja) * 2017-08-09 2023-08-16 日本カーバイド工業株式会社 偏光板用粘着剤組成物及び粘着剤層付偏光板
JP7047088B2 (ja) 2017-11-10 2022-04-04 杉金光電（蘇州）有限公司 光学積層体
CN111406098B (zh) * 2017-11-30 2022-06-03 杉金光电(苏州)有限公司 光学层合体
JP7428494B2 (ja) * 2019-09-18 2024-02-06 リンテック株式会社 繰り返し屈曲積層部材および繰り返し屈曲デバイス

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JP2006259664A (ja) * 2005-02-18 2006-09-28 Fuji Photo Film Co Ltd 偏光板、偏光板用アクリル系粘着剤、及び該偏光板を用いた液晶表示装置
JP2008181105A (ja) * 2006-12-28 2008-08-07 Fujifilm Corp 偏光板及びそれを用いた液晶表示装置
JP2009191149A (ja) * 2008-02-14 2009-08-27 Soken Chem & Eng Co Ltd 偏光板用粘着剤組成物およびこれを利用した偏光板
WO2010098182A1 (fr) * 2009-02-27 2010-09-02 綜研化学株式会社 Adhésif acrylique, feuille adhésive pour film de polarisation l'utilisant, et film de polarisation adhésif

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WO2002050209A1 (fr) 2000-12-21 2002-06-27 Lg Chem, Ltd. Compositions adhesives acryliques pour films polarisant, et film polarisant utilisant de telles compositions
JP5379409B2 (ja) * 2008-02-15 2013-12-25 日東電工株式会社 光学フィルム用粘着剤組成物、粘着型光学フィルムおよび画像表示装置
JP5923231B2 (ja) 2008-09-01 2016-05-24 日本カーバイド工業株式会社 粘着剤組成物、光学フィルム、及び粘着剤組成物の製造方法
JP5697023B2 (ja) 2010-12-14 2015-04-08 サイデン化学株式会社 粘着剤層付偏光板およびその製造方法
WO2014203792A1 (fr) * 2013-06-19 2014-12-24 綜研化学株式会社 Composition adhésive autocollante pour plaques de polarisation, feuille adhésive autocollante pour plaques de polarisation, plaque de polarisation comprenant une couche adhésive autocollante, corps stratifié et écran plat
KR101622005B1 (ko) * 2013-08-22 2016-05-17 제일모직주식회사 편광판용 점착 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치

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JP2006259664A (ja) * 2005-02-18 2006-09-28 Fuji Photo Film Co Ltd 偏光板、偏光板用アクリル系粘着剤、及び該偏光板を用いた液晶表示装置
JP2008181105A (ja) * 2006-12-28 2008-08-07 Fujifilm Corp 偏光板及びそれを用いた液晶表示装置
JP2009191149A (ja) * 2008-02-14 2009-08-27 Soken Chem & Eng Co Ltd 偏光板用粘着剤組成物およびこれを利用した偏光板
WO2010098182A1 (fr) * 2009-02-27 2010-09-02 綜研化学株式会社 Adhésif acrylique, feuille adhésive pour film de polarisation l'utilisant, et film de polarisation adhésif

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KR20180042267A (ko) 2018-04-25
TW201713741A (zh) 2017-04-16
JPWO2017029959A1 (ja) 2018-06-07
CN107924009A (zh) 2018-04-17
TWI697534B (zh) 2020-07-01
CN107924009B (zh) 2020-09-04
JP6886401B2 (ja) 2021-06-16
KR102243893B1 (ko) 2021-04-23

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